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Nanostructured Materials for Electrochemical
Energy Production and Storage

Nanostructure Science and Technology
Series Editor: David J. Lockwood, FRSC
National Research Council of Canada
Ottawa, Ontario, Canada

For other titles published in this series, go to

Edson Roberto Leite

Nanostructured Materials
for Electrochemical Energy
Production and Storage


and similar terms. Lockwood National Research Council of Canada Ottawa. Ontario Canada ISBN: 978-0-387-49322-0 e-ISBN: 978-0-387-49323-7 DOI: 10. 233 Spring Street. . is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. LLC.ufscar. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer Science+Business Media. LLC 2009 All rights Series Editor David J.1007/978-0-387-49323-7 Library of Congress Control Number: 2008 941657 °c Springer Science+Business Media.Edson Roberto Leite Universidade Federal de S˜ao Carlos Centro de Ciˆencias Exatas e de Tecnologia Caixa Postal 676 S˜ao Carlos-SP Brazil derl@power. NY 10013. service marks. Use in connection with any form of information storage and retrieval. except for brief excerpts in connection with reviews or scholarly analysis. even if they are not identified as such. or by similar or dissimilar methodology now known or hereafter developed is forbidden. electronic adaptation. Printed on acid-free paper springer. The use in this publication of trade names. USA). computer software. New York.

focusing on advances in tailoring controlled shape nanostructures. is on novel strategies that exploit nanoscale architectures to enhance the efficiency of alternative energy conversion and storage devices and on the basic principles of electrochemistry governing the effects of nanoscale structures on electrodes and electrolytes. A general description is also given of nanoparticle synthesiza- tion methods (mainly oxides). therefore. causing a dramatic improvement in energy storage. The chapter presents a review on the properties and main features of nanoscale materials. and generation. emphasizing the dependence of key properties on size for energy purposes. Ribeiro and Leite describe assembly and properties of nanopar- ticles. etc. In chapter two. Applications include high-efficiency solar cells. Nanoscale structures dramati- cally alter the surface reaction rates and electrical transport throughout the material. mainly in the area of polymer electrolyte membrane fuel cells. Heinzel and K¨onig summarize the impact of nanostructured materials on fuel cell technology. the goal of this book is to present basic fundamentals and the most relevant properties of nanostructured materials in order to improve alternative energy devices. Furthermore.Preface The major problem facing new energy conversion and storage technologies remains device efficiency. Bueno and Gabrielli present the basic principles of nanotechnology in general and integrate fundamental electrochemistry with nanostructured materials in partic- ular. This book begins with a chapter by Gr¨atzel summarizing the use of mesoscopic thin films and hybrid materials in the development of new kinds of regenerative photoelectrochemical devices. conversion. This chapter illustrates how nanostructured materials can modify component performance such as electrocatalyst materials and membrane. Projects based on nanostructured materials can yield improved performance in devices involving electrochemical reactions and heterogeneous catalysis. The main focus of this chapter. the design of nanoscale materials to be applied in alternative energy devices is a predictable way to develop a wide range of new technologies for a more sustainable future. batteries. Therefore. such as fuel and solar cells. v .

and Pivkina. particularly those based on electrochemical processes. electrical properties. Zn. and electrochemical parameters. Zavyalov. This chapter reviews the importance of aerogel nanoar- chitecture in achieving high performance electrochemical properties. Pd. A wide range of metal (metal ox- ide)/polymer nanocomposites has been synthesized using Al. The authors make a powerful case for nanomaterials and nanotechnology as a way to transform such alternative energy sources into significant contributors to the future global energy mix. As the rapid development of nanostructured materials continues. A chapter focusing on the use of nanocomposites in electrochemical devices is presented by Schoonman. . this book illus- trates the impact of this class of materials on performance improvements of alter- native energy devices. oxidation kinetics. Sn. Preface Dong and Dunn describe advances resulting from the use of sol-gel technology on energy storage devices. The properties of the nanocomposites were studied by comparing structure. Results ob- tained with vanadium oxide aerogels are highlighted as these materials exhibit a number of desirable characteristics for secondary lithium batteries. and Ti as a metal source and poly-para-xylylene (PPX) as a polymeric matrix.

. . 219 vii . . . . . and Alla Pivkina Index . . . . . . . . . . . 185 Winny Dong and Bruce Dunn Nanostructured Composites: Structure. . . . . . . . . . . . Leite Electrochemistry. . . . . . . . . . . . . . . . . . . . . and Nanostructures . . . Properties.Contents Recent Applications of Nanoscale Materials: Solar Cells . . . . . . . . . . . . . . . . . . . . . . Nanomaterials. 33 Caue Ribeiro and Edson R. . . . . . . . . . 1 Michael Gr¨atzel Assembly and Properties of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sergey Zavyalov. . . . 81 Paulo Roberto Bueno and Claude Gabrielli Nanotechnology for Fuel Cells . . . . . . . . . . . . . . 201 Joop Schoonman. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151 Angelika Heinzel and Uwe K¨onig Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . and Applications in Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

prbueno@mail. km 235 – 13565-905. Los Angeles. 2600 GA Delft. Russia ix . CH-1015. Brazil Alla Pivkina. Box 5045. S˜ao Paulo. CA 90095. Russian Academy of Science.unesp. J. Brazil. 4. 201. P. Rua XV de Novembro. Laboratory of Photonics and Interfaces. Brazil Joop Schoonman.graetzel@epfl. 103064 Moscow. Germany Edson R.Contributors Paulo Roberto Bueno. CA 91768 Bruce Dunn. SP. Departamento de F´ısico-Qu´ımica. Delft Institute for Sustainable Energy. Karpov Institute of Physical Chemistry. Physique des Liquides et Electrochimie. SP. C. Semenov Institute of Physical Chemistry. Switzerland. Rod. Universidade Estadual Paulista. Germany Uwe K¨onig Centre for Fuel cell Technology (ZBT gGmbH). France Michael Gr¨atzel. 75252 Paris. 47057 Duisburg. Department of Materials Science and Engineering. Postal 355. CP 741. EMBRAPA Instrumentac¸a˜ o Agropecu´aria. California State Polytechnic University. Araraquara. Ecole Polytechnique F´ed´erale de Lausanne. Carl-Benz-Str. Lausanne. Moscow. 4 place Sergey Zavyalov. UPR 15 du CNRS. 1452 – 13560-970. Washington Luiz. USA. bdunn@ucla. 119991. Instituto de Qu´ımica. S˜ao Angelika Heinzel Centre for Fuel cell Technology (ZBT gGmbH). 10. Carl-Benz-Str. Vorontsovo Pole. The Netherlands. 14801-907. Delft University of Technology. Leite. Chemical and Materials Claude Gabrielli. Russia Caue Kosygin st.O. University of California. 201. michael. LIEC – Universidade Federal de S˜ao Carlos. Universit´e Pierre et Marie Curie. 47057 Duisburg. Pomona. Departamento de Qu´ımica. S˜ao Winny Dong.

graetzel@epfl. Re- cently there has been a surge of interest for devices that are based on nanoscale inorganic or organic semiconductors commonly referred to as “bulk” junctions due to their interconnected three-dimensional structure. Gr¨atzel Laboratory of Photonics and Interfaces. Nanostructured Materials for Electrochemical Energy Production 1 and Storage. The present chap- ter describes the state of the art of the academic and industrial development of nanostructured solar cells. offering the prospect of very M. with emphasis in the development of the dye-sensitized nanocristalline solar cell. Leite (ed. Research in this field has gained significant momentum with hundreds of groups being active to develop new mesoscopic solar cell variants and improve their performance. CH-1015.). ionic liquids. Lausanne. or inorganic and organic hole conductors and conducting E. DOI 10. for example. c Springer Science+Business Media LLC 2009 .Recent Applications of Nanoscale Materials: Solar Cells Michael Gr¨atzel Abstract Photovoltaic cells have been dominated so far by solid state p-n junc- tion devices made from silicon or gallium arsenide wavers or thin film embod- iments based on amorphous silicon. inorganic oxides and chalcogenides or fullerenes with organic electrolytes. nanocrystalline. Recently there has been a surge of interest for devices that are based on nanoscale inorganic or organic semiconductors commonly referred to as “bulk” junctions due to their interconnected three-dimensional structure. CdTe and copper indium gallium diselenide (CIGS) profiting from the experience and material availability of the semiconductor industry.1007/978-0-387-49323-7 1. Switzerland e-mail: michael. 1 Introduction Photovoltaic cells have been dominated so far by solid state p–n junction devices made from silicon or gallium arsenide wavers or thin film embodiments based on amorphous silicon. CdTe and copper indium gallium diselenide (CIGS) profiting from the experience and material availability of the semiconduc- tor industry. These devices are formed from junctions of. Ecole Polytechnique F´ed´erale de Lausanne. Nanostructure Science and Technology.

nanoparticles. respectively. Gr¨atzel low cost fabrication without expensive and energy-intensive high-temperature and high-vacuum processes. lower cost and shorter energy payback times. They are compatible with flexible substrates and a variety of embodiments and appearances to facilitate market entry. During the illumination of the cell the photo-excited dye molecules adsorbed on the nanoparticle surface inject electrons into the conduction band of the oxide. 1. 2 -bipyridyl-4. The nanoscale morphology produces an interface with a huge area.4 dicarbo-xylate). The sensitizer is regenerated by hole injection into a redox electrolyte or a solid-state p-type conductor. both for domestic de- vices and in architectural or decorative applications. coded N3 or N719 for the fully protonated or half protonated form. Published first in 1993 [4].4 -dicarboxylic acid). 1 Structure of the N3 dye cis − RuL2 (SCN)2 (L = 2. nanorods or nanotubes of a wide band gap semiconductor oxide (typically ZnO. Fig. The first embodiment and prototype of this family of devices is the dye-sensitized solar cell (DSC). invented in the author’s laboratory at the Ecole Polytechnique F´ed´erale de Lausanne [1–3]. SnO2 or TiO2 ) that is covered by a monolayer of sensitizer. including semiconductor quantum dots are known to date and their performance is rapidly improving. Although many organic or inorganic sensitizers. cis- RuL2 (SCN)2 (L = 2. Despite their disordered structure these novel solar cells have shown strikingly high conversion efficiencies competing with those of conventional devices while at the same time offering advantages of ease of production. it appears possible now to depart completely from the concept of classical. ruthenium poly-pyridyl complexes have maintained so far a lead as the most efficient and stable sensitizers. endowing these systems with extraordinary opto- electronic properties.2-bipyridyl-4. flat p–n junction cells to replace them with interpenetrating network junctions.2 M. At the heart of the DSC is a mesoscopic film com- posed by. See Color Plates . Thus. The structure of the N3 dye is shown in Fig. for example. has become the paradigm of a charge transfer sensitizer capturing a large domain of the visible spectrum.

the molecular sensitizer or semiconductor quantum dot is placed at the interface between an electron and hole conducting material. Electron and holes are gener- ated in different phases and their recombination across the interface is blocked to a significant extent by the presence of the sensitizer.5 global sunlight at 1. in order to harvest solar light efficiently. the performance of mesoscopic TiO2 films employed as electron collectors is benefiting greatly from recent advances in nanomaterial research. It also is the only photovoltaic device that separates the two functions of solar light harvesting and charge carrier transport. The challenge one faces with these systems is to make adequate provisions for contacting a large area of the junction by a suitable hole conductor or electrolyte in order to regenerate the sensitizer following light- induced electron injection and conduct the positive carriers to the back contact of the photovoltaic cell. the electrons and holes are charges that move in different phases to the front and back contacts of the photocell. Their recombination occurs across the interface separating the electron and the hole conductor materials. whereas conventional cells perform both operations simul- taneously resulting in stringent demands on the purity of materials and much higher production costs.000 W/m2 intensity. Therefore. However. Solid-state DSC equivalents using organic hole conductors have reached over 5% efficiency with ruthenium-based sensitizers [10] and over 4% with organic dyes [11] whereas nanocomposite films composed of inorganic materials.1% under standard reporting con- ditions (AM1. Upon photo-excitation the negative charge carriers are injected by the excited dye into an electron (n) conductor and the positive charges in a hole (p) conductor or an electrolyte. Taking advantage of the highly transparent nature of the sen- sitized nanocrystalline oxide film. such a TiO2 and CuInS2 have achieved efficiencies between 5 and 6% [12. the use of a bulk or interpenetrating network junction of meso- scopic dimension is necessary since the optical cross section of a dye or QD is much smaller than the area it occupies.Recent Applications of Nanoscale Materials: Solar Cells 3 Incident photon-to-electron conversion efficiencies (IPCEs) attaining almost unity have been obtained with this sensitizer in the wavelength range near its ab- sorption maximum corresponding to quantum yields for electric current generation near 100% when light losses due to the conducting glass current collector are taken into account [4–8]. The great advantage of this cell configuration is that the solar energy conver- sion process involves only majority charge carriers. The open circuit photo-voltage developed by the cell corresponds to the difference of the quasi-Fermi level of the electrons and holes in their respective transport medium. 13]. tandem structures employing a DSC and CIGS top and bottom cell reached a conversion efficiency of >15% [14]. . 298 K temperature) [9] rendering it a credible alternative to conventional p–n junction photovoltaic devices. The DSC is the only solar cell that uses a molecule to absorb photons and convert them into electric charges without the need of excitonic transport. In the DSC. Similarly. New dyes show- ing increased optical cross sections and capable of absorbing longer wavelengths are currently under development. The validated solar to electric power conversion efficiency of the liquid electrolyte-based DSC stands currently at 11.

such as TiO2 . Sunlight is harvested by the sensi- tizer that is attached to the surface of a large band gap semiconductor. Long-term accelerated testing shows that DSCs can func- tion in a stable manner for over 20 years.0 S /S+ e. Photo-excitation of the dye results in the Conducting glass TiO2 Dye Electrolyte Cathode Injection S* −0.5 Maximum Voltage 0 hν E vs NHE Red Mediator Ox (V) 0. 2 Band Diagram and Operational Principle of Nanocrystalline Solar Cells Figure 2 shows a band diagram of the dye-sensitized nanocrystalline solar cell (DSC) and explains its operational principle. Stable operating performance under both prolonged thermal stress (at 85◦ C) and AM 1. with emphasis being placed on the work performed in the author’s laboratory. Gr¨atzel Obtaining long-term stability for DSCs at temperatures of 80–85◦ C had re- mained a major challenge for many years and has only been achieved in 2003 [15]. From there they pass through the external circuit performing electrical work and re-enter the cell through the back contact (cathode) by reducing a redox mediator (ox). typically a film constituted by titania nanoparticles. Stabiliza- tion of the interface by using self-assembly of hydrophobic sensitizers alone or in conjunction with amphiphilic co-adsorbents has been particularly rewarding. if sealing and the interfacial engineering issues are properly addressed. The reduced form of the mediator (red) regenerates the sensitizer closing the cyclic conversion of light to electricity.4 M. These re- cent devices retained 98% of their initial power conversion efficiency after 1. Light absorption by the dye (S) produces an excited state (S∗ ) that injects an electron into the conduction band of a wide band gap semiconducting oxide. Solvent-free electrolytes such as ionic liquids or solid polymers have been introduced to provide systems that are suitable for practical applications. The electrons diffuse across the oxide to the transparent current collector made of conducting glass. See Color Plates . e- Fig.5 light soaking conditions (at 60◦ C) has now been demonstrated [16–18]. The present review is on the state of the art of the academic and industrial development of nanostructured solar cells.000 h of high-temperature aging.5 Diffusion 1. 2 Energy band diagram of the DSC.

in a mesoscopic junction. On the other hand. Only the molecules that are in direct contact with the oxide surface would be photoactive – the remainder filtering merely the light. tetrapods [20] and nanotubes [21. The dye is regenerated by electron donation from an organic hole conductor or an electrolyte that is infil- trated into the porous films. The use of mesocopic inter- penetrating network junctions has also overcome the fundamental problem posed by the notoriously short diffusion length of excitons or charge carriers that are en- countered in organic and hybrid photovoltaic cells. The latter contains most frequently the iodide/triiodide couple as a redox shuttle although other mediators such as cobalt(II/III) complexes [19. 20] or the TEMPO/TEMPO + redox couple [21] have also been developed recently as an alternative to the I− /I− + 3 system. Using multi-layers of sensitizer does not offer a viable solution to this prob- lem. For example in the well-known fullerene/polyhexylthiophene (P3HT) [23] or CdTe/P3HT [24] cells the excitons produced by light excitation of the polymer diffuse only over a distance of a few nanometers during their lifetime while the light absorption length in these films is several hundred nanometers. In this case energy transfer quenching of the excited sensitizer by the electrons in the semiconductor would inevitably reduce the photovoltaic conversion efficiency. where the electrons are supplied by migration through the exter- nal load completing the cycle. 22]. The voltage produced under illumination corresponds to the difference between the quasi-Fermi level of the electron in the solid and the redox potential of the electrolyte or the work func- tion of the hole conductor. 3 The Importance of the Nanostructure The nanocrystalline morphology of the semiconductor film is essential for the efficient operation of all mesoscopic photovoltaic devices. which could recapture the conduction band electron at the surface.Recent Applications of Nanoscale Materials: Solar Cells 5 injection of electrons into the conduction band of the oxide. Apart from poor light harvest- ing a compact semiconductor film would need to be n-doped to conduct electrons. the device is regenerative producing electricity from light without any permanent chemical transformation. On a flat surface a monolayer of dye absorbs at most a few percent of light because it occupies an area that is several hundred times larger than its optical cross section. The use of interpenetrating network junctions is essential for the DSC. Reduction of S by iodide regenerates the original form of the dye under production of triiodide ions. This prevents any significant buildup of S+ . the diffusion path to reach the interface is shortened to a few nanometers allowing generation of charge carriers from the excitons before they recombine. Thus. A whole range of nanos- tructures has been tested so far ranging from simple assemblies of nanoparticles to nanorods [19]. For this reason the conversion yields obtained from the sensitization of flat electrodes . The iodide is regenerated in turn by the reduction of the triiodide ions at the counter electrode. In a flat junction geometry the excitons recombine be- fore they reach the junction where they dissociate into electrons and holes that pro- duce the photocurrent.

Gr¨atzel 100 nm Fig. Because of the small size of the particles such films show high transparency and negligible . 3 Transmission electron microscope picture of a mesoscopic TiO2 (anatase) film.5 J/m2 ).1 Light Harvesting by a Sensitizer Monolayer Adsorbed on a Mesoscopic Semiconductor Film Consider a 10-μm thick mesoscopic oxide film composed of 20-nm-sized particles whose real surface area is over 1. The average particle size is 20 nm have been notoriously low. The use of nanocrystalline films to support the dye and collect the photo-injected electrons has permitted to overcome these problems re- sulting in a dramatic improvement of the performance of sensitized hetero-junction devices. Note the bipyramidal shape of the particles having (101) oriented facets exposed. which have haunted all solar energy conversion devices based on the sensitization of wide band gap semiconductors. Employing such oxide nanocrystals covered by a monolayer of sensitizer as light harvesting units allows overcoming the notorious inefficiency problems.6 M.000 times greater than the projected one. corresponding to the anatase crystal planes with the lowest surface energy (ca. 0. The particles have an average size of 20 nm and the facets exposed have mainly (101) orientation. Figure 3 shows a scanning electron microscopy picture of a mesoscopic TiO2 (anatase) layer. 3.

which is immersed in the dye solution. Using d = 10 μm and α = 2. A film exhibiting ordered mesoporous structure. 5 has an even higher internal surface area than one that is composed of randomly associated nanoparticles [24]. See Color Plates .8 × 103 cm−1 one obtains LHE = 99. (2) For example. The resulting deeply red-colored film is the photoactive part of the DSC.8 × 103 cm−1 and the absorption length 1/α is 3. where it has an absorption maximum. (3) where d is the thickness of the nanocrystalline film. the optical cross section of the N3 dye cis–RuL2 (SCN)2 (L = 2. despite of the fact that they are covered only by a monolayer of sensitizer. α = σ c. Because more sensitizer is adsorbed for the same film Fig. respectively. The value of σ can be derived from the decadic extinction coefficient ε of the sensitizer using the relation: α = 1.3% of the incident 530-nm light. such as shown in Fig. Lambert Beer’s law can be applied to describe the light absorption by the adsorbed dye monolayer yielding for the reciprocal absorption length.Recent Applications of Nanoscale Materials: Solar Cells 7 light scattering. Hence α = 2.4 × 107 cm2 /mole at 530 nm.4 dicarboxylate) is 1. On a flat surface the N3 dye would have only absorbed 0. (1) Here. σ and c are the optical absorption cross section of the sensitizer and its concentration in the mesoporous film. 4 Uptake of N3 dye by a nanocrystalline TiO2 film. On a flat surface the N3 dye would have remained invisible to the eye. and its concentration in the nanocrystalline film at full monolayer coverage is typically 2 × 10−4 mol/cm3 . The dramatic difference of the light harvesting efficiency is illustrated by the deep coloration of the nanocrystalline TiO2 layers shown in Fig. 000ε (cm2 /mol).2- bipyridyl-4. The light harvesting efficiency LHE is derived from the reciprocal absorption length via: LHE(λ ) = 1 − 10−d .6 μm for 530-nm light.8%. 4.

21. 6 Scanning electron microscope view of a film constituted of titania nanotubes.8 M.26]. One-dimensional nanostructures such as the titania nanotubes shown in Fig. The problem with mesoporous films of the type shown in Fig. reducing the absorption length and enhancing the absorption of solar light over that of a dye- covered layer of randomly associated colloidal TiO2 particles of the same thickness. 6 and ZnO nanorods have been the focus of much recent interest [19. These studies are motivated by the expectation that the transport of charge carriers along the tubes is more facile than within a random network of nanoparticles where the . which is not enough to produce cells with conversion efficiencies over 5%.22. Gr¨atzel Fig. 5 is that ordered structures can only be realized so far up to a thickness of 1 μm. The length of the tubes is about 5 μm thickness its concentration in the mesoscopic TiO2 layer is increased. 5 Top scanning electron microscope view of an ordered mesoporous TiO2 (anatase) film produced by a block-copolymer templating method [25] Fig.

where the light scattering layer is shown to enhance the photocurrent response of the DSC in the near IR and visible region of the solar spectrum. 400 nm size. Ltd. Japan). employed as light scattering centres to enhance the red response of the DSC (courtesy of Dr. For example. one-dimensional nanos- tructures should produce a lower diffusion resistance than the nanoparticle films facilitating the collection of photo-generated charge carriers. 7. This increases the absorption of solar light in particular in the red and near IR region of the spectrum where currently used ruthenium complexes show only weak light absorption.Recent Applications of Nanoscale Materials: Solar Cells 9 electrons have to cross many particle boundaries. Co.2 Enhanced Red and Near IR Response by Light Containment The light harvesting by the surface adsorbed sensitizer can be further improved by exploiting light localization and optical enhancement effects. incorporating 200–400-nm-sized anatase particles enhances significantly the absorption of red or near infrared photons by the film. Catalysts & Chemicals Ind. 7 Scanning electron micrograph showing anatase crystals of ca. The benefits from using such a photon capture strategies are clearly visible below. 3. Hence.. See Color Plates . Fig. Tsuguo Koyanagi. A scanning electron mi- crograph of such particles is shown in Fig. The gain in short circuit photocurrent through these optical containment effects can be as high as 30%. These light management strategies employ scattering and photonic band gap effects [27–29] to localize light in the mesoporous structure augmenting the optical pathway significantly beyond the film thickness and enhancing the harvesting of photons in a spectral region where the op- tical cross section of the sensitizer is small.

These dyes incorporate functional groups e. injection rates in the picosecond range may have to be attained in order to obtain φinj values close to 1. The structure shown represents the lowest energy con- figuration derived from molecular dynamics calculations [30] yielding for the area occupied by one adsorbed N3 molecule a value of 1. Gr¨atzel 3. carboxylate. hydroxamate or phosphonate moieties [30] that attach the sensitizer to the oxide surface. The green and red spheres present titanium and oxygen.10 M. (5) Typical kdeact values lie in the range from 103 to 1010 s−1 . Note that the left carboxylate group straddles two Ti(IV) surface ions from adjacent titanium rows corresponding to a bidentate bridging configuration while the right one forms a monodentate ester bond with one Ti(IV) ion. In a second step.3 Light-Induced Charge Separation and Conversion of Photons to Electric Current The incident photon to current conversion efficiency (IPCE) sometimes referred to also as external quantum efficiency (EQE) corresponds to the number of electrons measured as photocurrent in the external circuit divided by the monochromatic pho- ton flux that strikes the cell. the electron is injected from the LUMO into the conduction band of the nanocrystalline . The lowest energy electronic transition for ruthenium polypyridyl complexes. such as the N3 dye is of MLCT (metal to ligand charge transfer) character. LHE(λ ) is the light harvesting efficiency for photons of wavelength λ . By undergoing strong coordinative bonding with the titanium surface ions. Taking the sum of the rate constants of these nonproductive channels together as kdeact gives: (φinj ) = kinj /(kdeact + kinj ).64 nm2 . Charge injection from the electronically excited sensitizer into the conduction band of the semiconductor is in competition with other radiative or radiationless deactivation channels. The currently used sensitizers satisfy this requirement. φinj is the quantum yield for electron injection from the excited sensitizer in the conduction band of the semiconductor oxide and ηcoll is the electron collection efficiency. Hence.g. respectively. Figure 8 shows the side and top view of the RuL2 (NCS)2 (N3) sensitizer anchored to the (101) surface plane of TiO2 through coordinative binding of two carboxyl groups to the titanium ions. these groups enhance electronic coupling of the sensitizer LUMO with the Ti(3d) orbitals forming the conduction band of the semiconductor. Upon optical excitation an electron is shifted from the Ru (SCN)2 moiety of the complex to the lowest unoccupied molecular orbital (LUMO) of the carboxylated bipyri- dine ligands moving in close vicinity to the titania surface. albeit with significant delocalization of the highest occupied molecular orbital (HOMO) over the SCN groups [27]. The following product expresses this key parameter: IPCE(λ ) = LHE(λ )φinj ηcoll . (4) Here. Hav- ing analyzed above the light harvesting efficiency of dye-loaded mesoscopic films we discuss now the other two parameters. The quantum yield of charge injection (φinj ) denotes the fraction of the pho- tons absorbed by the dye that are converted into conduction band electrons.

Note that the left carboxylate group straddles two Ti(IV) surface ions from adjacent surface titanium rows while the right one forms an ester bond. See Color Plates titania particles. The surface of the cluster corresponds to the (101) plane. respectively. The formation of the oxidized sensitizer and conduction band electrons due .64 nm2 . 10 presents a schematic of the energy levels involved in the sensitization. Figure 9 shows the results from time-dependant DFT calculations [32] indicating the vectorial charge displacement from the HOMO of the sensitizer to the T(3d) orbitals of the oxide during the optical excitation and electron injec- tion process while Fig.Recent Applications of Nanoscale Materials: Solar Cells 11 Side view Top view Fig. 9 Calculated shift in electron density during optical excitation and charge injection from the N3 sensitizer into the conduction band of a TiO2 (anatase) cluster [31] consisting of 38 titanium ions. The structure shown represents the lowest energy configuration derived from molecular dynamics calculations and the area occupied by one adsorbed N3 molecule being 1. 8 Side and top view of the RuL2 (NCS)2 (N3) sensitizer anchored to the (101) TiO2 anatase surface through coordinative binding of two carboxyl groups to surface titanium ions. See Color Plates 1e− Fig. 11 is the transient absorption signal following femtosecond laser excitation of the N-719 dye adsorbed on the surface of nanocrystalline titania [33]. Shown in Fig. The green and red spheres present titanium and oxygen.

much slower injection kinetics extending into . The process rate is therefore likely to be limited only by the electron dephasing in the solid. Interestingly. 10 Interfacial electron transfer involving a ruthenium complex bound to the surface of TiO2 via a carboxylated bipyridyl ligand. Hence. See Color Plates to heterogeneous charge transfer from the excited ruthenium complex into the conduction band of the oxide occurs on a femtosecond time scale. this temporal resolution does not allow determination of the rate of the injection pro- cess accurately but its time constant can be estimated as being definitely shorter than 20 fs corresponding to a rate constant kinj > 5 × 1013 s−1 .12 M. Such high rate can be rationalized in terms of electronic coupling of the π∗ sensitizer LUMO with the t2g wavefunction of the Ti(3d) conduction manifold and a large density of acceptor states in the semiconductor. Gr¨atzel Fig. Figure 11 in- dicates that the reaction is completed within the femtosecond laser excitation pulse. the observed charge injection dynamics is certainly beyond the scope of vibration-mediated electron transfer mod- els [34–39]. Since nuclear motion in the molecule and its environ- ment takes place within a time frame of at least 20 fs. Fitted data provide a cross-correlation time of 57 fs that is consistent with the instrument response measured by Kerr gating in a thin glass window. Orbital diagram for the forward electron injection (rate con- stant kf ) from the π∗ orbital of the bipyridyl ligand into the empty t2g orbitals forming the TiO2 conduction band and the backward electron transfer from the conduction band of the oxide into the Ru(III) d orbitals.

Fitted instrument response is 57 fs (straight line). For the characteri- zation of the recombination rate. Sim- ulated exponential rises with time constants of 20 fs (dashed line) and 50 fs (dotted line) and con- voluted with the same instrument response are shown the picosecond time domain were observed when the sensitizer was present in an aggregated form at the surface of the titania films [40]. One of the reasons for this striking behaviour is that the electronic coupling element for the back reaction is one to two orders of magnitude smaller for the back electron transfer. the back reaction of the electrons with the oxidized ruthenium complex occurs on a much longer timescale of micro. since instead of electrical current it merely generates heat. 42]. On thermodynamic grounds. As the next step of the conversion of light into electrical current.3 eV. While for the N3-type sensitizer the forward injection is a very rapid process occurring in the femtosecond time domain. As the recapture of the electrons by parent sensitizer involves a d-orbital localized on the ruthenium metal the electronic overlap with the TiO2 conduction band is small and is further reduced by the spatial contraction of the wavefunction upon oxidation of Ru(II) to Ru(III). respectively. For the same reason the . Naturally this reaction is undesir- able. It is of great interest to develop sensitizer systems for which the value of kinj is high and that of kb low.Recent Applications of Nanoscale Materials: Solar Cells 13 Fig. 11 Transient absorption signal for N719 adsorbed on nanocrystalline titania (open circle) (pump wavelength 535 nm.5 and milliseconds. This places the electron recapture clearly in the inverted Marcus region reducing its rate by several orders of magnitude [41. A second important contribution to the kinetic retardation of charge recombina- tion arises from the fact that this process is characterized by a large driving force and small reorganization energy – the respective values for N-719 being 1. the preferred pro- cess for the electron injected into the conduction band of the titanium dioxide films is the back reaction with the oxidized sensitizer. probe 860 nm). an important kinetic parameter is the rate constant kb . a complete charge separation must be achieved.

so no drift term appears in the transport equation. the back reaction dynamics are strongly influenced by the trapping of the conduction band in the mesoscopic film. This explains the observation [47. If. Charge recombination is furthermore inhibited by the existence of an electric dipole field at the surface of the titanium dioxide film. the depth of the traps that participate in the electron motion affects the value of the diffusion coefficient. which elimi- nates the internal field. The electron charge is screened by the cations in the electrolyte. Gr¨atzel interfacial redox process is almost independent of temperature and is surprisingly insensitive to the ambience that is in contact with the film [43]. Figure 12 illustrates this local screening effect.6 ×10−4 S/cm if a value of 10−4 cm2 /s is used for the electron diffusion coeffi- cient [46]. While the depletion layer field within the oxide is negligible due to the small size of the particles and their low doping level. 3. a single electron injected in a 20-nm-sized particle produces an elec- tron concentration of 2. Finally. In reality the situation is more complex as the transport of charge carriers in these films involves trapping unless the Fermi level of the electron is so close to the conduction band that all the traps are filled and the electrons are moving freely.4 × 1017 cm−3 . 48] that the dif- fusion coefficient increases with light intensity. Therefore. the time law for the back reaction is a stretched exponential [45]. facilitating greatly electron percolation [50]. by contrast the interfacial back electron transfer is so slow that it becomes rate determining then the back reaction follows first order kinetics. If the diffusion of trapped electrons to the particle surface is rate determining. In aprotic media. Bisquert [51] has introduced a transmission line description to model these processes. Recent Monte Carlo modelling gives an excellent description of the intricacies of the electron transport in such meso- scopic semiconductor films [49]. This important process leads to nearly quantitative collection of electrons injected by the sensitizer. The electron motion in the conduction band of the mesoscopic oxide film is cou- pled with interfacial electron-transfer reaction and with ion diffusion in the elec- trolyte. the electrons can . The mesoscopic film is thought to be composed of a string of oxide nanoparticles (Fig. 12). The local potential gradient from the negatively charged sensi- tizer to the positively charged oxide drives the injection in the desired direction and inhibits the electrons from re-exiting the solid. Apart from recapture by the oxidized dye. a dipole layer is established at the surface by proton transfer from the carboxylic acid groups of the ruthenium complex to the oxide surface. This corresponds to a specific conductivity of 1. Li+ or Mg2+ are potential determining ions for TiO2 [44] as they charge the oxide positively. however.4 Charge Carrier Collection The question of charge carrier percolation over the mesoscopic particle network is presently attracting a great deal of attention.14 M. Of great importance for the operation of the DSC is the fact that charges injected in the nanoparticles can be screened on the meso- scopic scale by the surrounding electrolyte. The large band gap semiconductor oxide films used in dye sensitized solar cells are insulating in the dark.

Interfacial electron transfer from the conduction band of the nanoparticle to the triodide is modelled by a charge transfer resistance rct connected in parallel with their chemical capacitance cch . 12 that the movement of electrons in the conduction band of the mesoscopic films must be accompanied by the diffusion of charge-compensating cations in the electrolyte layer close to the nanoparticle surface. The latter is defined as the electric charge (measured in Coulomb) that is required to move the Fermi level of the of the semiconductor nanoparticles by 1 eV. It is clear from Fig. − (6) The equivalent electrical circuit shown in the lower part of the figure treats each particle as a resistive element coupled to the electrolyte through the interface. The cations screen the Coulomb potential of the electrons avoiding the formation of uncompensated local space charge. This justifies using an ambipolar or effective diffusion coefficient. The latter is presented by the chemical capacitance (cch ) connected in parallel with the resistance (rct ) for interfacial electron transfer. Two transmission lines are used to model the motion of the con- duction band electron motion through a network of mesoscopic semiconductor particles and the charge compensating flow of redox electrolyte.g. respectively The red dots present cations from the electrolyte.Recent Applications of Nanoscale Materials: Solar Cells 15 Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye RS rtrans rtrans rtrans rtrans Dye Dye Dye rct rct rct Dye Dye RFTO/EL cch cch Dye cch RCE Dye Dye CFTO/EL Electrolyte Zd Dye Dye CCE Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Fig. which contains both contributions from the electrons and charge-compensating cations [48. triiodide ions: I− − 3 + 2e cb(TiO2 ) → 3I . which would impair the electron motion through the film. The red dots denote electrolyte cations. Zd is the Warburg dif- fusion resistance describing the motion of triiodide ions through the porous network to the counter electrode while RCE and CCE are the charge transfer resistance for the reduction of triodiodide and the double-layer capacitance of the counter electrode. The electrical equivalent circuit treats each particle as a resistive element. See Color Plates be lost to the electrolyte by the reaction with the oxidized from of the redox media- tor. 12 Equivalent electric circuit diagram of a solar cell based on a nanocrystaline semiconductor film in contact with an electrolyte. 52] to . e.

iodide: 2S + 3I− → 2S + I− 3 (7) is crucial for obtaining good collection yields and high cycle life of the sensitizer.g. The efficient interception of recombination by the electron donor. e. In the case of N3 or its amphiphilic analogue Z-907 time-resolved laser experiments have shown the interception to take place with a rate constant of about 105 –107 s−1 at the iodide concentrations that are typically applied in the solar cell [54]. red dots: sensitizer. . 4: recapture of the conduction band electron by the oxidized sensitizer (S+ ). Gr¨atzel e− + * 3 S /S − 1 2 Oxidation − e Potential 5 + 4 Red/Ox TiO2 S+/S Couple Fig. 3: electron injection in the conduction band followed by electron trapping and diffusion to the particle surface. 1: sensitizer (S) excitation by light. green and blue dots: oxidized and reduced form of the redox couple. Grey spheres: titania nanoparticles. 5: recombination of the conduction band electrons with the oxidized form of the redox couple regenerating the sensitizer and transporting the positive charge to the counterelectrode. 2: radiative and nonradiative deactivation of the sensitizer. Figure 13 summarizes the injection and recombination processes. See Color Plates describe charge transport in such mesoscopic interpenetrating network solar cells although at the high electrolyte concentrations employed the electron diffusion is the dominating factor. Mastering the interface to impair the unwanted back reactions remains a key target of current research [53]. This is more than a hundred times faster than the recombination rate and >108 times faster than the intrinsic lifetime of the oxidized sensitizer in the electrolyte in absence of iodide.16 M. 13 Photo-induced processes occurring during photovoltaic energy conversion at the surface of the nanocrystalline titania films.

depending on their size.Recent Applications of Nanoscale Materials: Solar Cells 17 To reach IPCE values close to 100%. Light absorption produces excitons or electron–hole pairs in the QD. they also occupy a larger area on the surface of the mesoporous electrode . 57]. These time constants or resistances can be measured by impedance spectroscopy. A simple considera- tion shows that the electron collection efficiency is related to the electron transport (tτ ) and recombination time (tr ) or the respective electron transfer and recombination resistances (Rt and Rct ) by the equation [55]:   1 1 1 τt Rt ηcc = + = 1− = 1− . A key parameter is the electron diffusion length: √ Ln = De τr . (10) The thickness of the nanocrystalline layer required to satisfy the last conditions is typically of the order of a few microns depending on the optical cross section of the sensitizer and its concentration in the film as discussed earlier. which provides a power- ful tool for analyzing the circuit elements of nanocrystalline solar cells [56. respectively. Efficient and rapid hole injection from PbS quantum dots into triarylamine hole conductors has already been demonstrated and IPCE val- ues exceeding 50% have been reached without attempting to optimize the collector structure and retard interfacial electron hole recombination [59]. provisions must be made to collect all photo-generated charge carriers. However. (11) τt τt τr τ t + τr Rct + Rt The transport time of conduction band electron across a 10-μm thick nanocrystalline titania film is typically a few milliseconds while for good cells the recombination time is in the range of seconds. This explains why practically all the injected elec- trons reach the current collector before they recombine. 3. (8) where De and tr are the diffusion coefficient and lifetime of the electron. Collection of charge carriers is quantitative if the electron diffusion length exceeds the film thickness (d): Ln > d (9) The film in turn needs to be significantly thicker than the light absorption length (1/α ) in order to ascertain nearly quantitative harvesting of the light in the spectral absorption range of the quantum dot or the molecular sensitizer: d > 1/α .5 Quantum Dot Sensitizers Semiconductor quantum dots (QDs) can replace dyes as light harvesting units in the DSC [58. QDs have much higher optical cross sections than molecular sensitizers. The electron is subsequently injected in the semiconducting oxide support while the hole is transferred to a hole conductor or an electrolyte present in the pores of the nanocrystalline oxide film. 59].

The latter material is fluorine-doped tin dioxide (FTO) having a sheet resistance of 10–15 Ω/square and has an optical transmission of 80–90% in the visible including reflection losses. the value of the absorption length is similar to that observed for the dye-loaded films. The cell is sealed using a Bynel (Dupont) hot melt. Both the front and back contact are made of sodium lime float glass covered by a transparent conducting oxide. As recombination occurs on a femtosecond time scale. A recent exciting discovery shows that multiple excitons can be produced from the absorption of a single photon by a quantum dot via impact ionization (IMI) if the photon energy is three times higher than its band gap [60. the use of mesoporous oxide collector electrodes to remove the electrons presents a promising strategy opening up research avenues that ultimately may lead to photovoltaic converters reaching efficiencies beyond the Shockley Queisar limit of 31%. 61]. 14. Gr¨atzel decreasing the QD concentration in the film. The challenge is now to find ways to collect the excitons before they recombine. Redox electrolyte is introduced by injection through a hole on the back contact. A cross sectional view of the cell structure used in these experiments is shown in Fig. 14 Cross-sectional view of the embodiment of DSC used in the laboratory for photovoltaic performance measurements. 4 Photovoltaic Performance of the DSC Having dealt with the fundamental features of operation of a DSC we present now recent performance data obtained with this new type of thin film photovoltaic cell. The back contact is coated with a small amount of Pt to catalyze the interfacial electron transfer from the SnO2 electrode to triiodide the typical loading being 50 mg/m2 . As a result. Adsorption of the sensitizer monolayer occurs from solution by self-assembly.18 M. The nanocrystalline TiO2 film is deposited by screen printing onto the FTO glass serving as front electrode followed by a brief sintering in air at 450◦ C to remove organic impurities and en- hance the interconnection between the nanoparticles. See Color Plates . Fig.

3 M LiI and 0. This striking improvement defies expectation as such large-area junctions Fig.03 M I2 in acetonitrile . 15 Conversion of light to electric current by dye-sensitized solar cells. The incident photon to current conversion efficiency is plotted as a function of the excitation wavelength. in sunlight the photocurrent aug- ments more than 1.e. The mesocopic morphology has a dramatic effect on the performance of a dye-sensitized solar cell. As a consequence. Figure 15 compares the photocurrent action spectrum obtained from a single crystal of anatase to that of a nanocrystalline film. cis-RuL2 (SCN)2 (L = 2. where the N-719 sensitizer has an absorption maximum.2- bipyridyl-4. The electrolyte consisted of a solution of 0. Left: single crystal anatase cut in the (001) plane. The IPCE value obtained with the single crystal electrode is only 0. Right: nanocrystalline anatase film.Recent Applications of Nanoscale Materials: Solar Cells 19 4.13% near 530 nm. while it reaches 88% with the nanocrystalline electrode. which have been standardized to yield films composed of 15–20 nm-sized anatase.1 Photocurrent Action Spectra Mesoscopic TiO2 films are currently prepared mainly by hydrothermal meth- ods. Pictures of the two elec- trodes used as current collectors are also presented. both being sensitized by the standard N-719 ruthenium dye i.4 dicarboxylate).000 times when passing from a single crystal to a nanocrystalline electrode. The incident photon-to-current conversion efficiency (IPCE) or external quantum efficiency is plotted as a function of wavelength.

2 Overall Conversion Efficiency Under Global AM 1. the conversion of incident photons is practically quantitative in the 500– 600 nm range were the sensitizer has an absorption maximum. This exceeds the thickness of the nanocrystalline TiO2 film explaining why all photo-induced charge carriers can be collected.5 global. 16 shows the current voltage curve obtained with this cell. 16 Photocurrent density vs. (12) Under full sunlight (air mass 1. The conversion effi- ciency in AM 1. intensity Is = 1.4% was attained [62] in 2001. A new record efficiency over 11.18% . the open-circuit photo-voltage (Voc ).5 Standard Reporting Condition The overall conversion efficiency of the dye-sensitized cell is determined by the photocurrent density measured at short circuit (JSC ). A certified overall power conversion efficiency of 10.86 V and the fill factor values 0. voltage curve for a DSC employing the N-719 dye adsorbed on a double layer of nanocrystalline TiO2 and scattering particles.65–0.2% was achieved recently [3].and charge carrier collection effi- ciency must be close to unity to achieve this result.20 M. short circuit photo-currents ranging from 16 to 22 mA/cm2 are reached with state-of-the art ruthenium sensitizers. while Voc is 0. Impedance studies have shown the diffusion length of the conduction band electrons in the DSC to be typically in the 20–100-μm range. electron injection. the fill factor of the cell (FF) and the intensity of the incident light (Is ). Taking into account the optical losses in the FTO glass that serve as a front contact.8.5 sunlight was 11. ηglobal = Jsc ×Voc × f f /Is . It is apparent from (5) that the light harvesting. Fig. 4. Gr¨atzel should fare poorly in photovoltaic energy conversion the presence of defects at the disordered surface enhancing recombination of photo-generated charge carriers.7–0. 000 W/cm2 ). and Fig. The iodide/triiodide-based redox electrolyte employed a mixture of acetonitrile and valeronitrile as a solvent.

Using 1. The resulting gain in open circuit voltage can be calcu- lated from the diode equation: Voc = (nRT /F) ln[(isc /io ) − 1]. Because of the mismatch of the redox levels of the N-719 and the iodide/triiodide couple the regeneration reaction of the sensitizer consumes too large a fraction of the absorbed photon energy as is apparent from the band diagram shown in Fig.4 dicarbo- xylate) is adsorbed at the TiO2 surface via two of the four carboxylate groups. 66] and should ultimately lead to DSCs exhibiting Voc values above 1 V. 5 Development of New Sensitizers and Redox Systems While the improvements in DSC performance obtained recently are remarkable. (13) where n is the ideality factor. intro- ducing panchromatic sensitizers or dye mixtures can boost the efficiency of cells further.e. io is the reverse sat- uration current and R and F are the ideal gas and Faraday’s constant. which are able to suppress the dark current at the titania electrolyte junction. whose value is between 1 and 2. respectively. these should be designed to yield at least 24 mA/cm2 short circuit current under full sunlight and fill factor as well as open . Increasing the injection and lowering the recombination rates are critical for maxi- mizing the open circuit voltage of a cell as shown by (11). Alternatively. if the present iodide-based redox system is maintained. To give 15% conversion efficiency. 2. In addition guanidinium butyric acid was found to suppress the number of surface states acting as a recombination centers [63].Recent Applications of Nanoscale Materials: Solar Cells 21 4. The ruthenium dye N-719 i. The fact that the dye itself blocks the dark current of the DSC has been confirmed recently [64]. the reduction of the dark current by a factor of 10 would result in a voltage increase of 90 mV. The goal here is to make the dye layer insulating in order to block the dark current across the interface.2-bipyridyl-4. The spatial configuration of the adsorbed dye at the (111) oriented surface of the TiO2 nanocrystals has been assessed by FTIR analysis and molecular dynamics calcula- tion.5 as a value for the ideality factor in DSC. such as guanidinium ions. it would be very difficult to reach much higher efficiencies with the standard N-719 sensitizer unless the redox system is changed. boosting the conversion efficiency of the cell by at least 15%. cis-RuL2 (SCN)2 (L = 2. It is desirable to increase the order of the dye monolayer at the interface and render it denser.3 Increasing the Open Circuit Photovoltage We have identified additives. The dye monolayer is disordered and the lateral repulsion of the negatively charged dye molecules is attenuated by spontaneous co-adsorption of cations. rendering it more impermeable and reducing in this fashion the dark current of the cell. Although these effects remain yet to be fully understood it appears that these ions assist the self-assembly of dye molecules at the TiO2 surface. Work on alternative redox systems whose Nernst potential is better adapted to that of the N-719 dye is currently being done [65.

named Z-907. they enhanced the performance of systems containing ionic electrolytes and hole conductors. Here again the self-assembly of the dye molecules to a dense layer on the TiO2 surface plays an important role.5 global illumination [10]. with the COOH groups serving as anchors and the lithium coordination to the sensitizer affording local electrostatic screening assisting charge separation. Gr¨atzel COOH O HOOC N N N Ru N N C N S C S O Scheme 1 K-19 sensitizer with an extended p-system in one of its ligands. To achieve such photocurrents the light harvesting in the 650–900-nm range needs to be significantly improved. Subsequently. An analogue of this dye with long alkyl side chains on the bipyridyl group. The K-19 dye also exhibits excellent conversion yield and stability [17. showed excellent light conversion performance and cell stability [16]. . where their hydrophobic nature indeed became a helpful factor. Scheme 1 shows the structure of a heteroleptic ruthenium complex coded K-19. These dyes of Z-series have proved themselves to be very use- ful to solid-state DSC. and t-butyl pyridine have shown 54% energy conversion efficiency under AM 1. 18]. 7 DSC Stability While long-term accelerated light soaking carried tests have confirmed the intrinsic stability of current DSC embodiments [67] stable operation under high-temperature stress 80–85◦ C has been achieved only recently by judicious molecular engineering of the sensitizer used in conjunction with a robust and non-volatile electrolyte. which due to the extension of the π-system in one of its ligands has an enhanced absorption coefficient. 6 Solid-State DSCs Solid-state DSCs employing the lithium-coordinating K-67 dye and the hole- conductor spiro-OMeTAD [67] in conjunction with additives such as Li(CF3 SO2 )2N. See Color Plates circuit voltage values similar to those that are presently obtained.22 M.

the upper limit for the sum of the two branching ratios can be calculated for a cell operation of 20 years and is shown to be 1 × 10−8 . These destructive channels are assumed to follow first or pseudo-first order kinetics and are assigned the rate constants k1 and k2 . The turnover frequency. P1 = kinj /(k1 + kinj ) and P2 = kreg /(k2 + kreg ) where kinj and kreg are the first order or pseudo-first order rate constants for the injection and regeneration processes. The turnover frequency of the sensitizer is 25 s−1 in full sunshine and during 20 years of outdoor service it must support 100 million turnovers. By introducing the two branching ratios. thus closing the two redox cycles involved in the energy conversion process. which would compete with electron injection from the excited dye into the conduction band of the mesoscopic oxide and with the regeneration of the sensitizer. In analogy to natural photosynthesis. Scheme 2 illustrates the catalytic cycle that the sensitizer performs during cell operation.Recent Applications of Nanoscale Materials: Solar Cells 23 7. of the dye has been derived as 0. See Color Plates . Also. averaged over seasons and day–night time. 17 The two coupled redox cycles involved in the generation of electricity from light in a dye-sensitized solar cell. The fraction of the sensitizer molecules that survive one cycle can be calculated as the product P1 × P2 . Critical for stability are any side reactions that may occur from the excited state S* or the oxidized state of the dye (S+ ). Light Conduction – Band I S S* e – e– e– e– e– 1 2 I2 S+ Semiconducting e– Membrane Electrical Work Fig. respectively. The latter diffuses to the counter electrode where the electrons injected into the circuit by the sensitizer reduce it back to io- dide.155 s−1 . The dye is regenerated by electron donation from iodide producing iodine or triiodide.1 Criteria for Long-Term Stability of the Dye Figure 17 shows the coupling of two redox cycles involved in the solar energy con- version process. light acts as an electron pump initiating charge flow from the sensitizer via the conduction band of the oxide semi- conductor to the external circuit.

Hence the branching ratio is about 10−9 that is well below the limit of 10−8 admitted to achieve the 100 million turnovers and a 20-year lifetime for the sensitizer. In ethanolic solution prolonged photolysis of N3 dye leads to sulphur loss and formation of the cyanato-ruthenium complex probably via photoxidation by oxygen. It is also debatable whether this pathway is destructive as the product formed still acts as a charge transfer sensitizer. The regeneration rate constant for this sensitizer in a typical iodide/triiodide redox electrolyte is at least 2 × 105 s−1 . Assuming kinj = 1 × 1013 s−1 . Ruthenium sensitizers of the N3 type readily satisfy this condition.42] has confirmed . For exam- ple. They can undergo photo-induced loss or exchange of the thiocyanate ligand. a European consortium financed under the Joule program [41.24 M. Precise kinetic information has also been gathered for the second destructive channel involving the oxidized state of the sensitizer.2 Kinetic Measurements As indicated earlier. which however occurs at a much lower rate than the 105 s−1 limit. the key parameter being the ratio k2 /kreg of the rate constants for the degradation of the oxidized form of the sensitizer and its regeneration. Data from a recent study of Z-907 shows that the for- mation of its oxidized form occurs over the first 8–10 min after the addition of an oxidant. a destructive side reaction with k1 < 105 s−1 could be tolerated.3 Recent Experimental Results on DSC Stability Many long-term tests have been performed with the N3-type ruthenium complexes confirming the extraordinary stability of these charge transfer sensitizers. Gr¨atzel Scheme 2 The catalytic cycle of the sensitizer during cell operation 7. The S+ state of the sensitizer can be readily produced by chemical or electrochemical oxidation and its lifetime determined independently by absorption spectroscopy. The subsequent decay occurs with a lifetime of 75 min corresponding to k2 = 2. 7. However.2 × 10−4 s−1 . this reaction is not observed when the dye is adsorbed on oxide surfaces. for most of the common sensitizers the rate constant for electron injection from the excited state to the conduction band of the TiO2 particles is in the femtosecond range.

56 million coulombs of charge had passed per square centimeter of electrode surface corresponding to a turnover number of 60 million.e. i. 18 Temporal evolution of short circuit photocurrent and open circuit photo-voltage under long-term light soaking of a Z907-sensitized DSC using a non-volatile electrolyte (courtesy of Dyesol) . Recent stabilization of the interface by using self-assembly of sensitizers in conjunction with amphiphilic coadsorbents has been particularly rewarding by allowing the DSC to meet for the first time the specifications laid out for outdoor applications of silicon photovoltaic cells. the new am- phiphlic sensitizer K-19 shows increased extinction coefficients due to extension of the π conjugation of the hydrophobic bipyridyl and the presence of electron- donating alkoxy groups.000 h of continuous illumination 0. After 10.Recent Applications of Nanoscale Materials: Solar Cells 25 cell photocurrent stability during 10.000-h aging at 80◦ C while there was a ∼70-mV decline for a device stained with the K-19 sensitizer alone. The stabilizing effect of the DPA is attributed to the formation of a robust and compact molecular monolayer at the mesoscopicTiO2 surface.000 h of light soaking at 2. For example. During this time the measured JSC increased from initially 12 to 15 mA/cm2 while Fig. a ≥ 8% efficiency DSC has been realized showing strikingly stable performance under both prolonged thermal stress and light soaking [16].5 sun corresponding to ca. These results corroborate the projections from the kinetic considerations made earlier. The VOC of such a device drops only by 25 mV dur- ing 1. Taking advantage of the enhanced optical absorption of this new sensitizer and using it in conjunction with decylphoshponic acid (DPA) as co-adsorbent and a novel electrolyte formulation. This stabilization of the VOC allowed the solar cell to sustain the high conversion efficiency during extended heat exposure [16]. Figure 18 shows results from a recent long-term illumination experiment carried out at Dyesol with two cells over a period of close to 14 months. Hermetically sealed cells were used for long-term thermal stress test of cells stored in the oven at 80◦ C. A more difficult task has been to reach stability under prolonged stress at higher tem- peratures. 80–85◦ C. 56 million turnovers of the dye without any significant degradation. reducing the amount of adsorbed water and other interfering impurities.

26 M. Gr¨atzel

the Voc decreased slightly from 0.72 to 0.65 V. The opposite change of Jsc and Voc
reflects probably a small positive shift of flat-band potential of the mesoporous tita-
nia film under the thermal stress, which can result in a net enhancement of photo-
induced charge separation efficiency in the DSC.

8 First Large-Scale Field Tests and Commercial Developments

During recent years industrial interest in the dye-sensitized solar cell has surged and
the development of commercial products is progressing rapidly. A number of indus-
trial corporations, such as G24 Innovations (, Aisin Seiki in
Japan, and well as Solaronix in Switzerland are actively pursuing the development
of both flexible- and glass-based modules. Particularly interesting are applications
in building integrated photovoltaic elements such as electric power-producing glass
tiles. The Australian company Dyesol ( has produced such
tiles on a large scale for field testing and several buildings have been equipped with
a wall of this type. Aisin Seiki in Japan in collaboration with Toyota Research labo-
ratory has started DSC prototype production. The layout of these modules is shown
in Fig. 19. Note the monolithic design is using carbon as interconnect and cathode
material to keep the cost down.

Fig. 19 Production of DSC prototypes by Aisin Seiki in Japan. Note the monolithic design of the
PV modules and the use of carbon as interconnect and counter electrode material. The red dye is
related to N-719 while the black dye has the structure RuL (NCS)3 where L = 2, 2 , 2 -terpyridyl-
4,4, 4 tricarboxylic acid. See Color Plates

Recent Applications of Nanoscale Materials: Solar Cells 27

Field tests of such modules have already started several years go and the results
of these tests revealed advantages of the DSC with regards to silicon panels under
realistic outdoor conditions. Thus, for equal rating under standard test conditions
(STC) the DSC modules produced 20–30% more energy than the polycrystalline
silicon (pc-Si) modules [68]. The superior performance of the DSC can be ascribed
to the following factors:
• The DSC efficiency is practically independent of temperature in the range of
25–65◦ C while that of mono and pc-Si declines by ca. 20% over the same range.
• Outdoor measurements indicate that the DSC exhibits lower sensitivity to light
capture as a function of the incident angle of the radiation, although this needs to
be further assessed.
• The DSC shows higher conversion efficiency than pc-Si in diffuse light or cloudy
While it is up to the commercial supplier to set the final price for such modules
it is clear that the DSC shares the cost advantage of all thin film devices. In addition
it uses only cheap and readily available materials [26]. Finally, in contrast to amor-
phous silicon and CIGS cells the DSC avoids high vacuum production steps that are
very cost intensive. Given these additional advantages at comparable conversion ef-
ficiency, module costs well below 1 are realistic targets even for plants having well
below GW capacity. The DSC has thus become a viable contender for large-scale
future solar energy conversion systems on the bases of cost, efficiency, stability and
availability as well as environmental compatibility.
These DSC panels have been installed in the walls of the Toyota dream house
shown in Fig. 20, offering a building-integrated source of solar power to the

The Toyota Dream House

made by

Fig. 20 The Toyota “Dream House” featuring DSC panels made by Aisin Seiki. For details see
web announcement 1204.html. See Color Plates

28 M. Gr¨atzel

Fig. 21 First commercial flexible lightweight cell produced by G24 Innovation on a large scale for
us as telephone chargers. See Color Plates

G24 innovation has been the first to realize large-scale, role-to-role production
of lightweight flexible cells, which are sold presently on the market for mobile tele-
phone charging. A photograph of such a cell is shown in Fig. 21.

9 Future Prospects

Reaching much beyond 12% conversion efficiency for DSC, by relying mainly on
panchromatic and IR absorbing dyes or surface modifications will require enhanced
light collection in the 700–900-nm region. An alternative and promising approach
will be the use of a tandem concept, where the top and bottom cells are judiciously
chosen to absorb complimentary components of the available light including the
IR region. Such a device was recently tried in our laboratory and obtained 15%
conversion efficiency

10 Summary

Using a principle derived from natural photosynthesis, mesoscopic injection solar
cells and in particular the DSC have become a credible alternative to solid-state
p–n junction devices. Conversion efficiencies over 11% and 15% have already been

Recent Applications of Nanoscale Materials: Solar Cells 29

obtained with single junction and tandem cells, respectively, on the laboratory scale,
but there is ample room for further amelioration. Future research will focus on im-
proving the Jsc by extending the light response of the sensitizers in the near IR spec-
tral region. Substantial gains in the Voc are expected from introducing ordered oxide
mesostructures and controlling the interfacial charge recombination by judicious
engineering on the molecular level. Hybrid cells based on inorganic and organic
hole conductors are an attractive option in particular for the flexible DSC embodi-
ment. Nanostructured devices using purely inorganic components will be developed
as well. The mesoscopic cells are well suited for a whole realm of applications
ranging from the low power market to large-scale applications. Their excellent per-
formance in diffuse light gives them a competitive edge over silicon in providing
electric power for stand-alone electronic equipment both indoor and outdoor. Ap-
plication of the DSC in building integrated PV has already started and will become
a fertile field of future commercial development.

Acknowledgements Financial support from the EU and Swiss sources (ENK6-CT2001-575 and
SES6-CT-2003-502783), as well as the United States Airforce (USAF contract No. FA8655-03-
13068) is acknowledged.


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Washington Luiz. Brazil e-mail: derl@power. as soon as the latter become environmentally and eco- nomically more attractive alternatives. emphasizing the dependence of key properties on size for en- ergy purposes. Leite (ed. Nanostructure Science and Technology. c Springer Science+Business Media LLC 2009 . etc. Rod. Leite Abstract A short review is presented on the properties and main features of nanoscale materials. Designs based on nanoscale-range materials can provide new or improved technologies for devices involving electrochemical reactions and heterogeneous catalysis such as fuel and solar cells. Nanostructured Materials for Electrochemical Energy Production 33 and Storage. convert. DOI 10. Leite () LIEC – Universidade Federal de S˜ao Carlos. and generate energy. fossil fuels may be abandoned far earlier than generally believed in favor of clean renewable energy sources. considerably improving its ability to store. Furthermore.). the design of nanoscale materials for application in alternative en- ergy devices is a predictable way to develop a wide range of new technologies for an environmentally friendlier E. focusing on advances in tailoring controlled shape nano- structures.R. The main problem of new energy conversion and storage technologies remains the efficiency of devices. SP. batteries. Nanoscale struc- tures dramatically alter surface reaction rates and electrical transport throughout the material. The physical and chemical properties of nanoscale materials (usually defined in the 1–100 nm range) are of immense interest and increasing importance for fu- ture technological applications.1007/978-0-387-49323-7 2.ufscar. 1 Introduction Most of today’s energy needs are still met by fossil fuels (finite reserves). the terms nanoparticles and nanocrystals are synonymous) generally display properties E. Nanoparticles or nanocrystals (in this work. However. S˜ao Carlos. Departamento de Qu´ımica.R. km 235 – 13565-905. A general description is also given about nanoparticle synthesization methods (mainly oxides).Assembly and Properties of Nanoparticles Caue Ribeiro and Edson R.

These interesting results confirm that any observation of nanoparticles must take into account the surface effects. especially in very small particles.. The literature provides several examples of properties. These changes are known as quantum size effects. changing the Au particle size [8].34 C. specific heat. The dependence of the surface area on size is. including energy conversion [9–14]. and their origin is directly related to the type of chemical bond in the crystal [7]. Gilbert and coworkers [24] applied wide-angle X-ray scattering technique (WAXS) on 3. 16]. nanostruc- tured materials offer a way for alternative energy devices such as solar and fuel cells to become truly feasible and for the performance of batteries and super-capacitors for energy storage to be dramatically improved. as well as processes that allow such nanoparticles to be manipulated and controlled. These developments can lead to new technologies. metal oxides. This introductory chapter discusses basically two topics. The future of these new technolo- gies is strictly dependent on the development of synthetic routes to process metal. 2 Nanoparticles Surfaces The surface of a material plays a key role in many of its characteristics. nanoparticle light-emitting diodes [20. Special attention is given to fundamental subjects such as quantum confinement. therefore. catalysis and sensors [15. this is due to the fact that an inner atom in the particle will interact with other atoms in its surroundings. The correlation between properties and particle size has been known since the nineteenth century. From the standpoint of energy. which can be affected by particle size [1–6]. and growth processes. the simplest way to observe the modulation of properties in nanoparticles. i. Simply stated. hence. and semiconductor nanoparticles. interest in nanoparticles has only grown considerably over the last decade. The correlation between the surface area and volume of a spherical particle can be determined by the formula .4 nm ZnS nanoparticles. The driving force for this increase in research activities is the ability to control a material’s properties by controlling the size and shape of crystals and the arrangement of such particles. and special pigments [22]. Leite that differ from those of bulk material. such as magnetic and optical properties. despite the subject’s long history. attributing pair distribution functions (PDF) to the nanoparticles. how size modifies a material’s properties. phase transformation and nucleation. melting point. Faraday demonstrated that the color of colloidal Au particles can be modified.e. and how to synthesize nanocrystals with a controlled morphology. the properties of nanoparticles or. ranging from chemical reaction rates to optical properties [2]. ultrahigh density data storage media [17–19]. This interaction enables nanoparticles to contribute substantially to the material’s surface disorder and. whereas the surface atoms do not have neighbors in a given direction [23]. Ribeiro and E. when M. to its properties.R.21]. Their results revealed structural disorder caused by nanoparticle strain and contraction of the bond lengths at the surface. A material’s prop- erties are usually very substantially modified in the 1–10 nm sizes. more precisely. However. and surface reactivity.

. the majority of the atoms forming a particle are at the surface. According to the liquid-drop model. i. In the rigid geometry of a solid.. the relation tends to infinity. as follows [25]: R3p N= . This surface energy is always lower in the liquid phase than in the solid. the total cohesive energy (Eb ) of a nanopar- ticle with N atoms is equal to the volumetric or bulk energy av N minus the surface energy. surface atoms tend to be unsaturated.e. a similar result is obtained for the ratio of surface atoms and inner atoms in a given particle. To normalize the relation for a given mass (to obtain the surface area in area/weight). There- fore. A decrease in the melting temperature has been observed with decreasing nanocrystal size in a wide range of materials. One of the first properties studied extensively as a function of particle size was the solid–liquid transition. This expression is the same as that of the binding energy per nucleon obtained from the liquid-drop model. these atoms tend to move to minimize energy. (2) ra3 where ra is the radius of an atom deduced from the atomic volume. Since nanoparticles are not true spheres.e. however. the latter term arising from the presence of atoms on the surface. Eb /N = av. Hence. i. Goldstein and coworkers [31] observed a temperature depression of over 50% for nanocrystals in the 15 nm range. and in the liquid phase. the cohesive energy per atom. the relation assumes a constant value (close to zero) only for large particles. ρ . we can derive a geometric ex- pression to give the number of atoms in a near-spherical shape. the surface atoms are constrained. and melting is a way to reduce the total surface energy. in very small particles.Rp . This phenomenon must be interpreted in light of the fact that given their high surface energy. (1) can be inter- preted as being related to the proportion of atoms on the particle’s surface. Comparing the final results with the reported bulk melting temperature – about 1. (3) N 1/3 where av represents the bulk’s cohesive energy and γ is the material’s surface energy. Since the number of atoms in a near-spherical nanoparticle with radius Rp is known (2). it is useful multiply the result by the material’s density. Practical conclusions can be observed in properties intrinsically related to the coordination of atoms in space.e. i. Since the nanoparticle volume is proportional to N and (by analogy) the number of atoms in surface scales is quadratically proportional to Rp . we can write . (1) Volume 4/3π Rp 3 Rp where Rp is the particle radius. In higher surface areas.690◦ C – the smaller nanoparticles melted at ≈ 600◦ C. the contribution of surface energy will be higher.Assembly and Properties of Nanoparticles 35 Area 4π R2p 3 = = . In CdS nanocrystals..Rp = av − γ = av − as N −1/3 . Thus. the variation of melting point with size [26–32]. and melting temperature will be reduced. is given by 4π ra2 av.

T0 .36 C.υ . Ribeiro and E. The linear relationship between Tm and R−1 was com- pared with experimental data for Pb and In nanoparticles. The results showed that this simple approach efficiently demonstrates the melting point’s dependence on size. Since empirical studies [26] have established a linear relation between the melting point (Tm ) and the cohesive energy av . as follows [25]: Tm 2βE.bulk = 371 K . it is well known that. in heterogeneous catalysis. Other aspects of the high surface area in nanoparticles appear in catalytic stud- ies. we can write a relation of Tm /T0 and the nanoparticle radius. [32]).T0 is a constant dependent upon surface energy. The metal has bulk melting temperature Tm. Leite 12υ0 γ av. atomic volume. This expression gives a qualitative view of the size dependence of the amount of energy required to remove an atom from a cluster. the rate of reaction is assumed to be proportional to the surface coverage [33]. (4) Rp where υ0 is the atomic volume. In fact. the greater Fig.R.υ . Therefore.Rp = av − . where the ap- proach seems to be valid. Similar results have been obtained from classical thermodynamic treatments. Figure 1 gives an example of melting temperature depression in sodium clusters [32].T0 = 1− (5) T0 Rp where βE. and for several metals in molecular–dynamic simulations [25]. 1 Melting of sodium nanoparticles (from Martin et al. and the bulk melting temperature.

while cubical nanoparticles comprise (100) facets whose edges and corners are less sharp than the tetrahedral ones. respec- tively. two effects on this scale are not negligi- ble: the adsorption of any counter ion is enhanced and can shift pHζ in more than two units [45] (this effect was explored by several authors to manipulate nanoparti- cles by attaching them to organic molecules [46.Assembly and Properties of Nanoparticles 37 the material’s surface area the greater is its catalytic activity. Irreg- ular shapes will strongly interfere in the vicinity of the surface atoms.2 kJ mol−1 ) nanoparticles. especially at the corners and edges. Pd.6 ± 1.1 nm). cubical. The following surface equilibrium condition must therefore be considered: MOH+  2  MOH + H + (6)  MO− + H+ MOH  (7) These two conditions of equilibrium are described by pK1 and pK2 values. However. mainly tetra- hedral. the surface area interferes in the absolute number of dispersed charges. This fact allows one to con- clude that. the spherical ones display the lowest catalytic activity but the greatest stability. The dissolution and poisoning of atoms in heterogeneous catalysis has been found to occur primarily in the corners and edges because of the higher activity attributed to these atoms in the structure. The lower activation energy of spherical particles was attributed to the lower particle size when compared with the cubical (4. 47]). Another interesting feature to be pointed out is the instability of these anisotropic shapes [41]. Narayanan and El-Sayed [38–40] compared the activation energy in the electron transfer reaction between hexacyano- ferrate (III) ions and thiosulfate ions catalyzed by Pt nanoparticles. are important properties that determine the stability of a colloid.8 nm) is consistent and clearly shows the dependence on shape. metal oxide surface chem- istry is controlled by the surface hydroxyl groups [42–44]. the sphere is the most stable geometry. and dipole interactions may affect the particle-to-particle interaction [48–50].0 ± 0. The classical equation for the en- ergy of dipole attraction in spheres (aligned dipoles). when it comes to nanoparticles of comparable sizes. However. Tetrahedral Pt nanoparticles are composed of (111) facets. mainly in metal oxides. mainly in metallic nanoparticles such as Pt. the most common liquid medium. In princi- ple. and any other shape will have a higher surface area to a given volume. In fact. it is not easy to separate the effects intrinsically dependent on size from those dependent on the shape of nanoparticles [39]. The authors observed lower activation energy in the above described reaction in tetrahedral nanoparticles (14. but does not affect the zeta potential [45]. E = −μD /2πε0 x(x2 − 4R2p ) . Also.9 against 7. with sharp edges and corners.3 kJ mol−1 ) and spherical (22. which ultimately means the corners/edges and the crystallographic planes at the surface. the distribution of crystallographic planes differs in each shape. In water. Several reports discuss this enhancement of catalytic activity.6 kJ mol−1 ) than in cubical (26. Another aspect of this topic is the colloidal stability of nanoparticles. together with the zero point of charge or zeta potential (pHζ ). and Co [34–38].4 ± 1. However. and spher- ical (or near-spherical) nanoparticles consist of numerous (111) and (100) facets with smooth corners and edges. the comparison with tetrahedral particles (4. Rh. The surface charge. and spherical.

some papers report ordered agglomeration or significant enhance- ment of viscosity or rheological properties in nanoparticulate colloids [51. (8) 2m dx2 where m is the particle mass.38 C. Ribeiro and E. Tang and coauthors [48] reported values of about 8–10 kJ mol−1 .R. the general solution for the equation (according to Levine [55]) is given by   nπ Ψ = 2/L sin x . On the one hand. (9) L and the energy of the particle is given by n2 π 2 h¯ 2 E= .52] when compared with microparticulate in the same solid load [44]. [53.54] reported that the same charge localization can interfere in the agglomeration of larger particles by repelling others. and Ψ is the associated wave function. Schr¨odinger’s equation is:   h¯ 2 d2 − +V Ψ = EΨ. 3 Quantum Size Effects Nanoparticles have few atoms that suffice only to form an identifiable (crystal) inte- rior and the interactions among these atoms in a small limited size bring the proper- ties close to the discrete conditions displayed by isolated molecules or atomic pairs. a depletion term due to the interaction between the micro and nanoparticles.6 nm in diameter. In a box with length L. Estimating these values for CdTe nanoparticles ranging from 2.285 μ m) and ZrO2 nanoparticles (≈3 nm). V is the potential energy barrier. This interaction implies that the nanoparticles avoided agglomeration of the larger ones. For an one-dimensional system.5 to 5. in fact. and are revealed mainly in optical and electrical properties. Leite (μD is dipole moment and x is the distance between the spheres) shows that this energy can assume significant values in small particles. Tohver et al. They ob- served this behavior in dynamic viscosity measurements in binary colloids of SiO2 microspheres (≈0. like “pearl necklaces”. On the other hand. The authors proposed that the total interparticle energy Vtotal would have an additional contribution beyond the van der Waals interaction and the repulsive electrostatic potential. Basic quantum mechanics provides an excellent example of energy level de- pendence on size: the particle-in-a-box model. reducing the expected viscosity. (10) 2mL2 .5 kJ mol−1 ). The authors pointed out that this effect can explain relative orientation in nanoparticulate colloids (such as those reported in the same paper and in others). These phenomena are commonly related to quantum size effects. E is the energy of the particle. These values are substantially higher than the regular molecular dipole–dipole attraction (≈1.

. The dependence of the length L was observed in both studies. The expression shows a strong dependence of the energy level on the size (as seen in Fig. and the interactions of nonneighbors are neglected (assumed to be zero). (11) N +1 where N is an integer and k = 1 · · · N. In these methods. by the number of atoms in the chain. the contribution of each atom is postulated as α . Another way to explain the influence of size on electronic properties can be through the semiempirical methods utilized to estimate interactions between molecules [55]. 2. as illustrated in Fig. Although the model is commonly referred to as only theoretical. 2): at large L values. eliminating the quantum regime. β  .Assembly and Properties of Nanoparticles 39 Fig. The general solution for the energies is given by kπ Ek = α + 2β cos . Inside the box V = 0 and outside V = ∞ (the particle is confined in the box) where n is an integer. The wave functions will have a number of solutions equal to the number of atoms in the molecule. while the contribution of the interaction with neighboring atoms is postulated as β . [56] in linear Cu chains and by Nilius and coworkers [57] in linear Pd chains. its implications were recently observed through scanning tunneling microscopy (STM) by F¨olsch et al. Let us assume a particle with N equal atoms and two energy levels – a fundamental level and an excited one. 2 The energy of the three first levels (n = 1–3) of a particle with mass = electron mass in a 1-dimensional box with length L. all the energy levels tend to- ward a single level (level superposition). α  and β . with α . Enhance- ment of the particle energy is easily observed in small sizes.

the band gap is the energy necessary to create an electron (e− ) and hole (h+ ).R. this feature is clearly visible in a qualitative plot of the (11) for k = 1 and k = N in the two cases (fundamental and excited). More precisely. In semiconductors. By definition. as shown in Fig. the level spacing scales with d −3 . 3 Diagram of levels in a single-atom metal according to semiempirical methods . For a semimetal (such as carbon). the Fermi energy would probably be found in a gap between adjacent levels. The discreteness of the electronic level structure was discussed in detail by Kubo and Kawabata [59. Thus.. the existence (even in the bulk) of the characteristic band gap requires a better understanding of the conduction mechanism. 60]. small particles have few conduction electrons ne and a smaller number of electronic states at T = 0. the ionization potential Ei of a semiconductor can be treated as Ei = Eg + Ea . following a free-electron model (EF = h¯ 2 (3π 2 ne /2m)2/3 ) and is therefore independent of the particle size [58]. The Fermi energy depends only on the density of electrons n. the particle’s behavior is similar to that of a semiconductor. Since the density of electronic states is proportional to the volume. in the presence of fewer atoms. and reviewed by Halperin [58]. In this situation.40 C.e. and the particle would reveal a nonmetallic state. 3. Fig. where Eg is the band gap energy and Ea is the ionization energy from the edge of the conduction band [61]. As can be seen. δ . Ribeiro and E. which differs entirely from that of metals. δ = 4EF /3ne . However. i. the space between the filled states. Now let us take a single particle at a given temperature where kB T δ (where kB is the Boltzmann constant). the metallic behavior appears only in a cluster with a significant number of atoms. to describe their quantum size effects [61–63]. it shows a forbidden band depen- dent on the number of atoms in the particle. is inversely proportional to the particle size – for spherical particles. Leite respectively.

me are the effective masses of the hole and electron. one must consider polarization terms due to the Coulomb interaction in the presence of the crystalline surface. (14) 2m Rw 2Rw where P is an average over the 1S function [61]. In small sizes (assumed to be spherical). (16) 2me 2mh where Se and Sh are the electron and hole positions inside the sphere (V0 is con- sidered infinity outside the sphere). Consequently. the eingenfunction will be dominated by the carrier confinement. Sh ). Hence. (13) 2m∗ R2w The internal motion in a small particle can be interpreted by a specific eigenfunction. On the basis of this assumption. an exciton [64]. (15) 2mh 2me ε |re − rh | where mh . as defined by (12). (12) r h¯ 2 π 2 n2 En = . the simple uncorrelated function may be an acceptable approximation (especially for direct-gap semiconductors): . we can write Φ ≈ Ψ1 + ∑ Ψn . respectively). and ε is the semicon- ductor dielectric constant. At small values of Rp . Sh ) = EΦ(Se . However. which may form a bond state. the Schr¨odinger equation is written as follows   h¯ 2 h¯ 2 − − +V0 (Se . for the total energy h¯ 2 π 2 n2 e2  E≈ ∗ 2 + P.Assembly and Properties of Nanoparticles 41 The S eigenfunctions (in spherical coordinates) and their energy levels in a charged particle (electron or hole) with effective mass m∗ confined in a spherical well of infinite depth and radius Rw are defined in classical quantum mechanics by the equations sin(nπ r/Rw ) Ψn (r) = C . and the solution can be obtained by the variational method using the S wave function for a particle in a sphere (12 and 13) as a tentative function. Assuming some error. given by a direct expansion of Ψn . the barrier to the ionization Ea lowers with size. the small size implies the approximation of the carriers (e− and h+ . This interesting result is equal to the ionization potential or electron affinity of a small particle with radius Rp (making Rw = Rp ). Φ. with radius re and rh . Thus. Both terms decrease with the size Rp of the particle. the band gap energy is the ionization limit of the hydrogenic electron–hole bound states. By analogy. and the charge – the electron or the hole – is less stable in small sizes. or. Sh ) Φ((Se . the pair can be described approximately by a hy- drogenic Hamiltonian [62–64]: 2 2 = − h¯ ∇2h − h¯ ∇2e − e2 H .

e. albeit still small particles. the third term of (18) is neglected and the second term is only significant when aB ≤ Rp [79]. More complex solutions may be necessary for anisotropic shapes. as experimentally demonstrated by Buhro and Covin [80] for InAs. the diameter-range where these size effects are expected can be deter- mined by an exciton Bohr radius. (17) In this condition. However. 66] compared experimental results of absorbance in the UV–Vis range for CdS and ZnS nanocrystals in colloidal suspensions with predictions from classical Mie scattering theory [81]. Finally. but also on that of the surrounding medium. assuming that small crystallites are characterized by the same wavelength-dependent dielectric constant as that of the bulk material.R. 64. the pair becomes confined and the effects are observable. ε  is the ratio of the complex dielectric coeffi- cient of the bulk crystal to the real dielectric coefficient of the external medium. using bulk crystal proper- ties. some unpredicted plateaus or peaks were observed. since other correlation functions (with more complex solutions) are possible. the mode is known as strong confinement. as follows [64]: h¯ 2 aB = ε . Al- though the authors found a general shape congruent with the spectra obtained with the Mie curves. The authors concluded that the classical treatment of the Mie theory was invalid. i. the mode is known as weak confinement [64]. The peak was subsequently reported to be a resonance peak resulting from the creation of the electron–hole pairs [63. In general. and the curves were displaced to higher energies. Rossetti and coworkers [65. The third term is the energy loss given by the solvation in the surrounding medium. For particles that are much smaller than the optical wavelength λ in the external medium. ε . and using the reduced mass of the electron–hole pair μ . and the second term represents the Coulomb attraction. E eff (keeping in mind that the energy of the lowest excited state E is the shift of Eg . Ribeiro and E. one has the effective band gap energy. In these particles. This theory provides an exact solution to Maxwell’s equations. 82]. (19) μ e2 When the crystal size approaches aB . (18) 2μ R2 εR R The first term represents the quantum energy of carrier confinement or localization. since ε is a col- lective property of the macroscopic material (the small crystal does not support the . indicating that the small particles had higher band gap energies than the bulk. the bandgap energy): h¯ 2 π 2 n2 1.42 C.. several experimental works have demonstrated the validity of the expression for near-spherical nanoparticles [65–79]. only the electric dipole term needs to be considered and the crystallite absorption cross section is given by σ = (8π 2 R3 )/λ · ℑ[(ε  − 1)/(ε  )]. whereas for larger. Ψ1 is an average sum over a Ψ1 function [62]. This model is a simplification. and will depend not only on the semiconductor’s dielectric constant.8e2 e2 E eff = Egap + E = Egap + − + Ψ1 . Leite Φ0 = Ψ1 (Se )Ψ1 (Sh ).

in the inset of the graph).. the exciton’s contribution is negligible. (21) 3 π Rp 3 The derivative dA/dRp is obtained by the slope of the absorbance curve (convert- ing the energy axis to Rp using (18)). i. On the basis of these observations.7 nm) implies that. as illustrated in Fig. The effect was explained by the resonance ex- citon peak. Absorbance measurements in water were carried out on nanoparticles synthesized by the hydrolysis of hydrated SnCl2 and were compared with size distribution measured by TEM (at least 200 particles). for it is sometimes difficult to make a . Using (18). however. The expression can be rearranged. the results were probably strongly affected by the sharp exciton peak (at 283 nm. more pronounced for sharp particle size distributions. They pointed out that the model predicts that the absorption coefficient is independent of size. The absorbance A at any wavelength λ in the quantum regime is related to the total vol- ume of particles with radius greater than or equal to the size corresponding to the onset of absorption. keep- ing in mind that when r → ∞. 4 [83]. assuming that the absorption coefficient is independent of particle size.e. we have ∞ 4 A(r) ∝ π R3p n(Rp )dRp . in many cases. The authors tested the assumptions on ZnO nanoparticles. n(Rp ) = 0: dA dRp n(Rp ) ∝ − 4 . comparing them with direct size measurements by TEM. in most cases. considerable deviations were observed in very small radii. According to Pesika. concluding that the observed spec- tra was the sum of widely differing spectra corresponding to various sizes. and that the crystallite size distribution itself should be used to predict the experimental absorption threshold data. the broadening of particle size distribution can interfere sufficiently in the absorbance spectrum near the onset to deviate gap measurements significantly by the onset of extrapolation. In fact. 78] proposed the inverse observation. but the smaller ones were not detected. (20) Rp 3 where n(Rp ) is the particle size distribution. the experimentally detectable ef- fects are related to a weak confinement regime. the authors concluded that only small fractions of the overall distribution are affected and. An acceptable agreement was found for particles over 1. This deviation is observed in SnO2 nanocrystals: the very small calculated Bohr radius (aB ≈ 2. in a diluted concentration limit (absorbance will occur contin- uously since the critical size is reached).Assembly and Properties of Nanoparticles 43 continuous distribution of electron or hole momenta due to the boundary conditions imposed by the surface). For spherical particles. the authors estimated the effective band gaps of some particle sizes ranging from 2 to 7. A good agreement with the statistical data was achieved. particle size distribution by absorbance spectra measurements. The case of SnO2 illustrates the experimental problems observed in width gap materials (as is the case of many oxides).5 nm.3 nm. Pesika and collaborators [77.

with better results for the average particle size in several conditions.R. The photoluminescence peak was considered a good estimate of the band gap. as discussed earlier herein. few report on nanocrystalline rutile [90. the obtained absorbance spectra. whereas absorbance of the photon will occur continuously. A typical case is the synthesis of TiO2 polymorphs. Although several papers report on the synthesis of nanocrystalline anatase [12. However. On the inset. The results depicted in Fig. brookite. 91] as an example. 4 Comparison between statistical measurement of SnO2 particle sizes by TEM and ab- sorbance spectra derived distribution (21). Ribeiro and E. 85–89]. . and ru- tile [84]. TiO2 has three crystalline polymorphs. anatase. and it has been established that rutile is the most stable TiO2 polymorph (observations of micrometric anatase are scarce) [92–96]. 4 Phase Stability and Transformation Something commonly seen in the synthesis of nanomaterials is that many metastable structures appear stable in the nanometric range. The confinement effect in this oxide was studied by photoluminescence measurements. showing the sharp exciton peak [83] good estimate of the band gap. since it relates to the emission of the lower excited level to the ground state. several papers state that the rutile formation passes through the three metastable phases. Leite Fig.44 C. 5 show a good congruence with the theory and also the weak confinement regime in this oxide.

One must keep in mind that the stability of a given nucleus or small cluster (in homogeneous nucleation) is given by the balance between the free energy of formation. as follows for a sphere [23. On the basis of this assumption. (23) ΔGV At this moment.97].crit ): 2γ Rp. [79]).ΔGV + 4π R2p γ . Thus. (22) 3 Making the first derivative of the expression equal to zero. The inset in the figure shows an scheme of the photoluminescence emission (adapted from [82]) It is well known that crystallization generally follows a sequence of metastable phases before the most stable phase is attained (known as Ostwald step rule) [94. and the work given by the new surface. 98] 4 ΔG = − π R3p . ΔGV . . phases with higher γ values will need larger nucleus to become stable in solution or melt. we have the minimum ratio for a stable nucleus (Rp. γ A (the product of the surface free energy and the surface area).crit = . the others are often only slightly metastable by a few kilojoules per mole.Assembly and Properties of Nanoparticles 45 Fig. Although this final crystalline polymorph is the most thermodynamically stable. 5 Comparison between application of (18) to tin dioxide and experimental data – Eeff g obtained by photoluminescence emission and particle radius by TEM measurements (from Lee et al. d(ΔG)/dR = 0. we can consider that ΔGV is independent of size (we will further analyze the equation later on herein). 97. the immediate problem is to determine the surface energy of polymorphs.

4 ZrO2 monoclinic 6.46 C.6 ± 0. the effect of the volume variation. 99].2 0 TiO2 brookite 1. Under such conditions.7 ± 0.e. is expected to be small.2 0 γ -Al2 O3 1. Hence.100] – has no clear activation energy and may differ significantly from classical nucleation. eliminating water. obtained by substituting the value Rp. and the surface entropy is also expected to be slight.05 34 ± 4 Zeolitic SiO2 0. At room pressure.5 ± 0. Ribeiro and E. a conclusion dictated by common sense may hold true in some cases: the metastable structure of the nanoparticle comes from a memory of the precursor or. the precursor nanostructure constrains the atoms in positions such that crystallization is impossible. the competition between dissolution and reprecipitation renders this interpretation more complex. the first stages of the formation of a crys- tal may be the coalescence of two fairly large clusters.05 9. 94].4 ZrO2 amorphous 0.5 ± 0.crit in (22) [23. 97]: 16πγ 3 ΔG∗ = (24) 3ΔG2V In a reactional medium (such as water. Even though the main ideas remain valid.1 ± 0. protons. and OH − groups from the surface [2. PΔV . smaller surface energies lead to lower barriers to stabilization [93. the surface free energy can be approximated to the surface enthalpy (the variable that is properly measured in calorimetry).6 ± 0. On the basis of this assumption. Leite Table 1 Surface enthalpies and transformation enthalpies relative to bulk stable polymorph for oxides (adapted from Navrotsky [94]) Oxide Surface enthalpy Transformation (J m−2 ) enthalpy (kJ mol−1 ) α -Al2 O3 2.4 ± 0. 94].0 ± 0..4 ± 2.1 9 Calorimetric measurements are a way to determine this property [84. This step – often referred to as polycon- densation [43. At the surface. . An initial analysis of the data reveals (in accordance with the literature) that the surface enthalpy (or energy) decreases as the phase becomes more metastable (higher transformation en- thalpy relative to the bulk stable polymorph).2 ± 0.2 0 ZrO2 tetragonal 2. Table 1 shows surface enthalpies and trans- formation enthalpy data for some oxides and their polymorphs. so it is coherent with Ostwald’s step rule. phase transformations will depend on particle–particle contact. in the case of amorphous nanoparticles. the low coordination of atoms unbalances the bonding forces and generally causes any phase transformation to be easier at the surface.4 TiO2 anatase 0.01 8–15 SiO2 amorphous 0.7 ± 0.R. This analysis (albeit not at all correct) indi- cates that metastable phases tend to nucleate more easily than stable ones.0 TiO2 rutile 2.09 ± 0.1 13.2 0. i.1 2. for several materials). We can interpret the same result by stating that metastable phases have a lower activation energy ΔG∗ .5 ± 0.

According to the authors. Barnard and Zapol [109] proposed a general model for the phase stability of any nanoparticle based on the Gibbs free energy of an arbitrary particle.33 1. 109]: 2σ Peff = . The unbalanced forces in small particles can be un- derstood as an excess of pressure upon the whole solid particle. other factors may predominate and may also be related to the afore- mentioned phenomena. following a scaling law of the type Ptransf ≈ 1 + C /Rp . a Si cubic nanocrystal with 200 atoms will have 9% of the Table 2 Surface energies for SnO2 calculated for several crystallographic planes in vacuum (adapted from Beltran et al. (101) 1.9 GPa). The transformations were found to be fully reversible. the correct treatment of the free energy must include contributions from the edges and corners rather than only from the bulk and surface. which is coherent with the excess pressure at the surface. and may be approx- imated using such expressions as Laplace-Young’s equation [92. Solid surfaces of different crystallographic orientations have different surface energies and different affinities for absorbed ions and molecules [112] (as exemplified for SnO2 .30–1. [113] Ref. with a good corre- lation.20 1. showing an energy bar- rier to direct transformation. 101–107]. Zhang and Banfield [92] assumed that the increase in activation energy would be proportional to the excess pressure.66–1.27 1. However.36 . (100) 1.04 1. where Ea is the effective activation energy. As an example. C are proportionality constants. albeit with some hysteresis. Ea = E∞ +CPeff = E∞ +C Rp .72 2. They observed an increase of ≈35% in transition pressure in 10 nm nanoparti- cles in relation to 21 nm nanoparticles (3.40 (010). 110. To adapt this feature. E∞ is the bulk energy activa- tion.65 (101).Assembly and Properties of Nanoparticles 47 while the kineticrate constant of the process may also be size-dependent (as shown experimentally) [92. and C.84 1.63 – – (001) 1. in Table 2 [113–116]). 116] (110) 1. since the total amount of surface energy depends on the exposed crystallographic planes [117].14 1. The difference in Ea to the total range was ≈60 kJ mol−1 . [114] Ref. Excess pressure is also observable in pressure-driven phase transformations. [113]) Surface Ref. The fact is that shape is an important variable in the stability of nanocrystals. a significant value in view of the estimated bulk activation energy (E∞ = 185 kJ mol−1 ). 108.55 (201) 1. [115. Tol- bert and Alivisatos [2.43 1. The authors confirmed this assumption for the transition of TiO2 -anatase to rutile in the 5–100 nm range. 111] showed that a significant increase in pressure in- duced wurtzite to transform into rock salt (from the less dense to the denser phase) in CdSe nanocrystals. (25) Rp where σ is the surface tension.6–4.

In the above formulation. Leite atoms in edges. w the edge and the corner to volume ratios..e. and g j .R. one has M Gsurface = γ (T )A = q ∑ fi γi (T ). p. Ribeiro and E. G0x = Gbulk x + Gsurface x + Gedge x + Gcorners x . indirectly. with 103 atoms. L is the total length of edges and W is the total number of corners. (28) j M ρ ∑ Gcorner x = τ (T )W = w hk τk (T ). For a given x nanoparticle. Gbulk x = ΔG0x (T ). Using the relations of density ρ . (27) x ρ i where fi is a weight factor of the facets i in the crystal (∑ fi = 1). hk weight factors. Substituting and rearranging the terms.48 C. The second term is expressed in terms of surface energy γi for each i plane on the surface and molar surface area A. which is dependent on the temperature. molar mass M and surface to volume ratio q. i. the shape.3% will remain. (26) becomes M. 4% will be in the edges and with 105 only 0. the expression takes into account the crystallographic alignment of the properties and. These estimates highlight the importance of the small terms. in some cases. The edge and corner energies can be described by similar expressions: M ρ ∑ Gedge x = ξ (T )L = p g j ξ j (T ). (29) k where ξ (T ). τ (T ) are the edge and corner free energies. the free energy can be expressed as a sum of individual contributions. (26) The first term is defined as the standard free energy of formation.

The volume dilation ed is given as ΔV = ed = Peff βV . (30) However. (31) V where βV is the material’s compressibility. Al- though it is known that σ = γ + A(∂ γ /∂ A). when the dependence of γ on A is small. Peff can be estimated by (25) above. the approximation σ = . the effective pressure must be taken into account. ρ ∑ G0x = ΔG0x (T ) + q fi γi (T ) + p ∑ g j ξ j (T ) + w ∑ hk τk (T ) . as proposed by Zhang and Banfield [92].

γ is acceptable. The anisotropy should be included in the determination of .

γ . as done in (27). (30) becomes   M 2βV σ . Using these approximations.

(32) ρ R . G0x = ΔG0x + 1− q ∑ fi γi + p ∑ g j ξ j + w ∑ hk τk .

. and TiO2 polymorphs. spheres). partially and fully hydrogenated TiO2 anatase and rutile were obtained by density functional calculations (as shown in Table 3 [96]). Gilbert et al.60 0. [118–120] reported the reversible transition of ZnS wurtzite to a structure close to spharelite by the gradual substitution of methanol medium (from synthesis) by wa- ter. The slight variations of some values caused by ion adsorption can be extremely significant in small particles and in anisotropic shapes. Taking in account these parameters. N is number of units in the stoichiometric cell (considering a minimal slab). and review some methods commonly employed to produce such particles. 121].56 0..95 1. corner. This strong dependence on surface. with empha- sis on methods for synthesizing nanoparticles for energy purposes. the approach was tested successfully in simulations for Si.65 (110) 0.19 Although the Laplace–Young equation (25) is only applicable to spherical particles.55 0. [96. in the following sec- tions we discuss some of the fundamentals involved in nanoparticle synthesis. i.e. The authors predicted faceted shapes (e. as experimentally observed. 1  γi = A · ENsurf − NE bulk − Ny μy .35 0. and edge energies can induce unex- pected phase transformations through interactions with the medium. .82 (100) 0.51 0. which is contradic- tory to common sense (i.51 0. cubes or tetrakaidec- ahedrons) as preferred shapes in very small sizes for most cases. nanodiamonds.84 (100) 0. for the clean. (33) 2 where ENsurf and E bulk are the total energy for the surface and bulk for a given area A. partially hydrogenated and fully hy- drogenated low index surfaces of TiO2 anatase and rutile (adapted from Barnard and Zapol [96]) Anatase Rutile Surface Clean Partial Full Surface Clean Partial Full (001) 0. showing that interactions between water and ZnS reduce the surface energy. Ge. The authors explained the water-driven transformation through MD simulations. the surface energies for some crystallographic planes of clean.84 (101) 0.02 1. Ny is the number of absorbed molecules or ions and μy is the chemical potential of the y molecule or ion.e.86 0. 5 Synthetic Methods After reviewing the fundamentals of nanoparticle properties.71 1.63 (011) 0.47 0.Assembly and Properties of Nanoparticles 49 Table 3 Surface free energies γ (in J m−2 ).39 0. This as- pect can be explored by including the contribution of absorbed ions or molecules at each surface i.g.

(36) V = ςZ .1 Nucleation and Growth Many of the synthesization methods to produce nanoparticles are based on coprecip- itation steps. 108].R. Taking the derivative of the two expressions as Z. In such a condition. we can rearrange the expression as follows: ∑ γi Si γ= . or nucleation and growth in reactional media [98. 108. Because of the difficulties in isolating each process for independent study. (34) i where μ0 is the chemical potential of the bulk nucleus. a good understanding of the nucleation step is fundamental for grasping the nature of nanosize particles. Here we will not consider the contributions from edges and corners. (40) 3Z . (35) i dV since dn = dV /Vm (where Vm is the molar volume). one has: 2Vm γ μ = μ0 + αF . one has: dSi /dZ dSi 2Si = = . we discuss the correlation between the critical nucleus and surface energy (23). and applying it to a chain rule. as follows: Si = κi Z 2 . For a particle of any shape. 98.50 C. the surface area Si and the volume V can be written as generic equations for a given Z characteristic dimension. 124]: dG = μ0 dn + ∑ γi dSi . 123]. (39) ∑ Si Inserting the (38) and (39) into (35) and rearranging them. For the sake of simplicity. 3 (37) where κi are ς are geometric constants. as follows [23. In the section below. the nucleus possesses free Gibbs energy. A more complete analysis of precipitation must take into ac- count the chemical potential of the nucleus formed in equilibrium with the reactional media. γi is the surface energy and Si is the area for each surface i. (38) dV /dZ dV 3V As proposed by (27). as well as coarsen- ing and agglomeration processes [122. However. the surface energy can be inserted as an average surface ten- sion. Precipitation reactions involve the simultaneous occurrence of these steps. The equation can be rearranged to dSi μ = μ0 +Vm ∑ γi . although this contribution (as discussed) may be important. n is the number of moles. the fundamental mechanisms of precipitation are still not entirely understood. Ribeiro and E. Leite 5.

Comparing the equilibrium condition for precipitation. i. μ = μ  . we can consider the decrease of activation energy to nucleation (as given in (24)). (42) a0 3ZRT This equation is remarkable. one has: a 2Vm γ ln = αF . All the reactional parameters can be controlled by the proper selection of reactant relations [43. which are described as a function of the slowest mechanism present [129. is usual and commonly accepted as valid. and μ0 is the standard chemical potential in solution. a ≈ c. a large excess of water in relation to the metal source reactant leads to nanoparticles due to the fact that all the monomers present in solution are captured in primary nucleus – also. where a0 is the saturation activity. ΔG∗het = ΔG∗ (2 + cos θ )(1 − cos θ )2 )/4. This equation describes the chemi- cal potential of the formed nucleus. We can assume that the standard chemical potential μ0 in the particle is μ0 = μ0 + RT ln a0 . Applying the geometric relations of the contact with a cluster and a surface. The chemical potential of the substance μ  (or reactional product) in solution or melt is μ  = μ0 + RT ln a. 126–128].. 124. and rearranging it. Z = Rp and αF = 3. To obtain nanoparticles in solution.. (43) RT ln aa0 which is easily compared with (23).e. chemical potential and dimension Z. The heterogeneous nucleation is preferable only if the geometric relation is less than 1..crit . in these cases.Assembly and Properties of Nanoparticles 51 where αF is a shape factor defined as ∑ κi /ς . i. interface reactions – in each case.e. the initial particle size is closer to Rp. As an example. 130]. not dependent on reactional processes but dependent on diffusional parameters . The growth rate is governed by empirical power laws. i. The approximation in the equation of activity to the concentration. (42) reduces to 2Vm γ Rp = . adsorption in the crystal– solution interface.e. For a spherical particle. We can correct the set of equations to consider the reduction of surface energy by contact with other surfaces (which represents a heterogeneous nucleation process) by substituting γ to γeff . the growth process can be concurrent in some ways: transport of reactive species in solution. undesirable par- ticle sizes. in precipitation by hydrolysis. an effective surface energy obtained by contact with another surface [125]. the growth corresponds to the ordering of ions or molecular species (monomers) over the nucleus surface [42. While the nucleation process takes place. (41) where R is the universal gas constant. where θ is the contact angle with the two surfaces. a is the activity in solution. since it describes a general form to express the rela- tion among surface energies.131]. Special cases that must be analyzed are the growth mechanisms in equilibrium. it is usually necessary to stop the growth mechanisms or at least to control them to prevent uncontrollable growth and. hence.

the solubility is the same as that of the average particle size (Rp ).R. since dissolution and reprecipitation phenomena can easily occur [132]. (43) can be rearranged assuming the activity a is equal to the solubility of the formed particle Sp . Leite and on the particles’ relative mobility.0 [70]:   2Vm γ 1 Sp = Sb.0 · (1 + 2Vm γ /RT ) · 1/Rp . widely known as the Ostwald-Freundlich equation. A convenient form of Fick’s first law for a particle in a diffusion field is given as (in spherical coordinates) [133]: dRp dc 4π R2p = D4π r2 . the growth rate of the particles is likely to be limited by diffusion through a surrounding medium and can be described by Fick’s first law.52 C. and the equation can be linearized to Sp ≈ Sb. (45) dt dr where D is the diffusivity and dc/dr is the gradient in concentration at distance r. describes the dependence of the solubility of a formed particle on its size. If particles dissolve and grow readily without being limited by the rate of interfacial reactions. (45) can be rewritten for evaluation at r = Rp . (44) RT Rp This relation. and the saturation activity a0 as the bulk solubility Sb.0 exp . Considering that. in a distance r Rp . Initially. Usually the argument in exponential terms is too small. after integration of the right-hand side:    dRp D. This dependence is particularly important in very small particles. Ribeiro and E. This supposition is clearly valid in colloids and in reactional media.

If we assume that growth (in a closed system) is governed by the fastest growing particles. 134]: 3 3 3c0 DVm γ Rp − Rp. we obtain [23. known as Ostwald ripening. (48) . Substituting these values in (46) and integrating them.0 . (46) dt Rp Rp RT Rp Rp The concentration values are substituted by using (44) linearized. 135–137].0 = t. c0 D 2Vm γ 1 1 =− c(Rp ) − c(Rp ) = − − . (47) 4RT This growth mechanism. when Rp = 2Rp . we dis- cover that. A thorough analysis of the fundamental equations (44 and 45) leads to a general expression of the type [138–140] n n Rp − Rp. assuming c = Sp and c0 = Sb. provides a good descrip- tion of the growth behavior of a wide range of nanoparticles [71.0 ∝ t. If we take the second derivative d2 Rp /dt 2 = 0. 125. we have the condition of maximum growth rate. Figure 6 shows a schematic distribution of growth rates for some ar- bitrary values of particle radii. the maximum growth rate will occur in a defined range of particles. we can write dRp = dRp . as plotted in Fig. 6 by the straight line. 76. Clearly.

151–154]. which are not expected in precipitation-based growth. Recently. nanocrystals can grow by the alignment and coalescence of neighboring particles. recent studies have demonstrated that this mechanism cannot be considered responsible for the growth process in some systems [141–145]. investigated by molecular dynamics . The driving force for this mechanism is clearly the decrease in the surface and grain boundaries’ free energies. and may lead to the formation of anisotropic nanostructures in suspensions. by eliminating a common boundary. By the localized nature of oriented attachment. for n = 3. [163–166]. it is deduced that growth is controlled by dissolution kinetics at that particle–vicinity interface. 139]: for n = 2. The straight line refers to the maximum growth rate. by the consumption of nanoparticles as building blocks [48. the growth is controlled by the volume diffusion of ions in the vicinity. when Rp = 2Rp where n is an exponent dependent on the boundary conditions assumed in the growth [137. This mech- anism has already been theoretically studied [155–158] and experimentally ob- served in micrometer-sized metallic systems for several years [159–162]. the mechanism leads to the formation of nanoparticles with irregular morphologies. such as nanorods. in solid compounds). it is inferred that crystal growth is controlled by ion diffusion throughout the particle to its vicinity (the solution of a matrix. 6 Growth rate in Ostwald ripening of particles with arbitrary radius. which may occur during nanocrystal growth [146–150]. it was modeled by Moldovan et al. The oriented attachment mechanism was proposed as an- other significant process.Assembly and Properties of Nanoparticles 53 Fig. even in the early stages of nanocrystal growth. Several studies indicate that oriented attachment is very significant. By this mechanism. since the main postulates of the theory are frequently neglected. Despite the good applicability of the Ostwald ripening model. and when n = 4.

Penn also developed a kinetic model for oriented attachment growth. Penn and Banfield proposed that dispersed nanoparticles can be treated as molecules or molecular clusters [142] in solution. Leite studies [102. crystallographic alignment) was reached. 128. and confirmed experimentally [169–172]. This treatment was already used by Huang et al. until a thermodynamically favorable interface configuration (i.e. Figure 7 shows the oriented attachment of a SnO2 nanoparticle on the surface of a SnO2 nanoribbon. In all of the above-mentioned theoretical studies. Ribeiro et al. [104. Considerable efforts have reportedly been ded- icated to building adequate models to describe the coalescence of nanoparticles in suspension and at surfaces [173]. Oriented attachment occurred by means of rel- ative rotations between the particles or by plastic deformation associated with dis- placement motion. The authors considered that coalescence may also occur Fig. [176] proposed another mechanism for oriented attachment growth in dispersed nanoparticles.. the authors assumed that the nanoparticles were in contact with each other. 7 Example of a SnO2 nanoparticle attached to a single-crystalline surface (a SnO2 nanorib- bon) by the oriented attachment mechanism . Ribeiro and E. 174] in the development of a kinetic model serving to explain ZnS nanoparticle growth induced by hydrothermal treatments. 167. an aspect of particular interest is controlled growth under colloidal conditions. in nanoparticle synthesis. Edge discordances in the nanoparticle–nanoribbon interface evidence the attachment. 168].R. considering the electrostatic interaction between particles in solution [175].54 C. However.

growth by coalescence may be interpreted statistically. b attachment induced by rotation and alignment of particles in contact . This mechanism is based on the assumption that nanoparticles dispersed in a liquid medium present a very high degree of freedom for rotation and translation mo- tions. 8 Scheme of oriented attachment mechanism: a attachment by collision of two particles with similar crystallographic orientations. so nanoparticles in suspension are expected to present a high frequency of collisions. in suspensions where agglomeration does not take place. Figure 8 shows a generic scheme of the two proposed ways in which the oriented attachment mechanism works. since collisions can be considered effective (i. A recent paper by Cho and coauthors [50] discusses the oriented attachment process as the main mechanism involved in the construction of anisotropic PbSe nanocrystals in several shapes. growth by means of oriented collisions should be more effective than by surface mechanisms (i. Several papers have discussed the role of oriented attachment in the anisotropic growth of nanocrystals. Hence.Assembly and Properties of Nanoparticles 55 when particles with similar crystallographic orientations (or with slight differences) collide. The authors used the proposition of Fig.e..177–182]. coalescence induced by relative rotations between particles in contact). If we assume that all of the aforementioned considerations are valid. Dis- persed nanoparticles should present a high velocity in response to the Brownian motion. an elastic event). which is extensively used to explain polycrystalline colloidal growth and aggregation mechanisms in suspension. leading to coalescence) or ineffective (i.. Therefore. which explains the growth behavior in SnO2 colloidal suspensions.e. This mechanism is similar to Smoluchowsky’s coagulation model [126.. the coalescence of two particles in suspen- sion may be interpreted as the following chemical equation 49: k A + A −−−→ B (49) where A is a primary nanoparticle and B is the product of coalescence of two nanoparticles.e.

Leite the alignment of preformed nanoparticles by dipole–dipole interactions as the mech- anism responsible for the anisotropy associated with the attachment (as discussed before). but the oriented attachment mechanism may be involved.56 C. These reactions are always carried out in the presence of a large variety of stabilizers. and supple- mentary references on this subject are also available. The substrate decreases the activation energy in the crystallization process. This strategy allows one to obtain 3D arrays of several semiconducting metal oxides using controlled aqueous chemical processing at low temperatures (usually in the range of 90–95◦ C) and inexpensive precursors [194]. Ribeiro and E. An interesting feature was the subsequent coarsen- ing (Ostwald ripening) of the final nanorods. A strategy developed by Vayssieres [186–195]. The PBM strategy is based on the heterogeneous nucleation of the desired phase on a substrate. or the controlled decomposition of metastable organometallic compounds in an or- ganic or water solution. smoothing the nanoribbon surface. Anisotropic nanoparticle shapes are often desirable in charge-carrier devices such as solar cells or electrodes [184.2 Synthesis of Transition Metal Nanocrystals The development of metal nanocrystals is fundamental for devices where catalytic heterogeneous reactions take place. This growth process is usually associated with the Ostwald-ripening mechanism. The authors suggested that the formation of ZnS nanorods occurred through the oriented attachment of spherical nanoparticles formed in a precursor solution to preformed nanorods in solution. 5. [183] for the synthesis of ZnS. and agglomeration. A similar experiment was proposed by Yu et al. growth. This argument ex- plains the epitaxial growth of single-crystalline metal oxide nanorods perpendicular to the substrate. A recent review authored by B¨onnemann and Richards [197] contains a good discussion about the refined model. which are used basically to control the growth of the ini- tial nanocluster and to prevent particle coagulation or agglomeration. . and the direction of crystal growth is controlled by the surface energy of the oxide crystalline phase.196]. the mechanism of nanoparticle formation is generally based on a process of nucle- ation. whereby the nucleation and growth processes can be separated. The bottom-up methods of wet chemical nanocrystal synthesis are based on the chemical reduction of the salts. The growth mechanism is controlled basically by a dissolution–precipitation process. The process was observed concomitantly to the synthesis of the nanocrys- tals. This model still is valid and has recently been refined. The kinetics of nucleation and growth is controlled by the temperature and the hydrolysis rate. 185]. such as fuel cells. As discussed. called purpose-built materials (PBM). This process was proposed by Turkevich and is based on the synthesis of metal nanoparticles by salt reduction [34. appears to be a promising route for growth-oriented 3D crystalline nanorods in several kinds of substrates. promoting heteroge- neous nucleation at the surface of the solid. The experimental conditions are adjusted to ob- tain the most stable thermodynamic structure.R.

They also showed that the reduction rate of [PdCl4 ]− ions is an important factor in the production of smaller Pd particles. The reduction of metal salts by the addition of a reducing agent in a nonre- ducing solvent is a well-established synthetic route for the preparation of aque- ous suspensions of metal nanocrystals. forming a protective layer that prevents particle coagulation or agglomeration. and S donors (phosphanes. since the organic layer forms a nanometric scale second phase [198. N. among them polymers and block-polymers. In this process. organometallic compounds. poly(N-vynil-2-pyrrolidone) (PVP) and the kind and/or concentration of al- cohol in the solvent. An example of this kind of synthesis is the processing of palladium nanoparticles through the reduction of palladium acetate by methanol [200]. To prevent the coagulation process from occurring. ion concentration. the particle surface can be protected by electrostatic stabilization and/or steric stabilization [44]. This type of stabilizing system can be viewed as a nanocomposite material. which may replace the adsorbed ion on the particle surface. Turkevitch and coworkers [196] established the first repro- ducible standard protocol for the synthesis of gold nanoparticles. The synthesis of transition metal nanocrystals can be divided basically into two major groups: salt reduction and decomposition method.Assembly and Properties of Nanoparticles 57 Since nanocrystals are unstable from the standpoint of agglomeration and bulk. 199]. A detailed description of the several types of steric stabilizers used during the synthesis of metal nanocrystals is given by Bradley [42]. for instance. Their processing . The salt reduction method is a process whereby a reduction agent reduces the metal salt. in solution. amines. demonstrating that the mean diameter of Pd nanocrystals can be controlled from 1. the unprotected particle coagulates.7 to 3. thioethers). used phosphorous vapor to promote the reduction of [AuCl4 ]− in aqueous solution to synthesize gold nanoparticles [8]. Examples of these methods are described below. to metal.0 nm in a one-step process by changing the amount of protective poly- mer. such as ionic strength of the dispersing media. thus becoming more stable. The electrostatic stabilization process can be modified by several parameters. and sol- vents. Different kinds of reducing agents have been used to pro- cess gold nanocrystals. and the presence of neu- tral adsorbate. allowing for the processing of particles ranging from 1 to 100 nm in diameter. promoted by a double layer composed of ions adsorbed on the particle surface. In the absence of any extrinsic impediment. In an organic solution. the solvent can also act as a reduction agent. The reduction rate was controlled using different kinds of alcohol. particularly hydrogen-containing al- cohols. surfactants. Electrostatic stabilization is based on the Coulombic repulsion between particles. Steric stabilization is based on the steric hindrance caused by organic molecules that are attached to the particle surface. P. The solvent they used was water. the alcohol is oxidized to the corresponding carbonyl group. These reactions can be done in water or in an or- ganic solution. coagulation and agglomeration are the paths that nanoparticles follow to decrease their high surface area. Alcohols are generally useful reduction agents. basically under the action of van der Waals forces. Several kinds of protective groups can be used as steric stabi- lization agents. Teranishi and Miyake [37] reported on the reduction of H2 PdCl4 by alcohols to synthesize Pd nanoparti- cles. Faraday.

reagent concentration. On the basis of a similar process. Park et al. Using this process. using Co(η 3–C8 H13 )(η 4–C8 H12 ) and Pt2 (dba)3 (dba = bis-dibenzylidene acetone) as organometallic compounds. although a broad particle size distri- bution is usually obtained [127. pH. [209] synthesized nanoscale bimetallic Cox Pt1 − x particles. and the sequence of reagent additions. Park and Cheon [213] discussed an interesting synthetization route to process solid solution and core-shell type cobalt-platinum nanoparticles via redox transmet- allation reaction. Platinum nanoparti- cles can also be synthesized by the reduction of metal salts. Recently.R. [215] reported on the synthesis of iron nanorods and spherical nanoparticles using the thermal decomposition of Fe(CO)5 . An interesting synthetization route was recently developed based on the reduc- tion of organometallic compounds by dihydrogen at low pressure and temperature [204–208]. reporting they had obtained nanoparticles of solid solution and core-shell structures smaller than 10 nm. Leite of gold nanoparticles by the reduction of [AuCl4 ]− with sodium citrate. in the presence of surfactant. [203] demonstrated that the morphology of platinum particles could be controlled by controlling the synthetic parameters. the so-called polyol process [210] has been used successfully to process magnetic nanoparticles with a very narrow particle size distribution [211. resulting in nanometric particles. They found that rod-like particles. 203]. decomposing into their respective metals even under mild condi- tions. Ribeiro and E. The particles were stabilized by the presence of poly(vinylpyrrolidone) (PVP). could be obtained by changing the concentration of didode- cyldimethylammonium bromide (DDAB) during the reaction process. These alloys were formed by redox trans- metallation reactions between the reagents without the addition of reducing agents. Pt. organometallic compounds can be considered good sources to process metal nanoparticles. well-dispersed nanoparticles of Ru.58 C. Narrow particle size distributions were achieved in both processes. Ould Ely et al. The reaction between Co2 (CO)8 and Pt(hfac)2 (hfac = hexafluoroacetylacetonate) resulted in the formation of solid solution. The organometallic compounds of transition metals usually display low ther- mal stability. Ni. using a reducing agent [36. This process is based on the reduction of metallic salt in solution. protective polymer. while the reaction between Co nanopar- ticles and Pt(hfac)2 in solution resulted in “Co-core – Pt-shell” type nanoparticles. Owing to these properties.212]. at a high temperature (100 < T < 300◦ C). [216] recently reported on the control of the size and shape of Co nanocrystals. and Co with a narrow size distribution were synthesized. by the addition of a polyol (such as ethylene glycol). Metal carbonyl pyrolysis has been used for the synthesis of several metal nanoparticles. They found that the alloy’s composition was determined by the initial ratio of the two organometallic precursors. with a higher aspect ratio. Puntes et al. 214]. The organometallic compounds used were low-valent alkene or a poly- ene complex of the desired metal. These authors used various reducing agents and chloroplatinic acid as platinum salt. Van Rheenen et al. time. became a standard for histological staining applications [201] and for undergradu- ate experiments in surface and nanomaterials chemistry [202]. such as tem- perature. In this process. for example. surfactants such as oleic acid are used to control particle growth and stabilize the nanoparticles. .

The general process of metal nanocrystal synthesis can be divided. When the cluster grows to a critical size (step III). which leads to the formation of anisotropic particles such as nanorods. In fact. Chen and Nikles [217] synthesized ternary alloy nanoparticles (Fex Coy Pt100−x−y ). An interesting approach to synthesize metal alloy nanocrystals is the use of si- multaneous salt reduction and thermal decomposition processes. The nanocrystals are produced by injecting an organometallic precursor (Co2 (CO)8 ) into a hot (T ≈ 180◦ C) surfactant mixture (oleic acid and trioctylphosphine oxide (TOPO)) under an inert atmosphere. for didactic purposes.3 Metal Oxide Nanocrystals Metal oxides represent an important class of materials with a variety of technologi- cal applications. The nanocrystal self-assembly process requires a monodispersion system (particle size deviating by less than 10% from the average size) [219] and can be achieved by solvent evaporation [18. such as solar cells and Li ion batteries. occurs under a kinetic condition. the cluster will grow in a geometri- cal arrangement to minimize the surface energy. is prevented by steric stabilization under the influence of the molecules attached to the particles’ surface (step V). transition metal oxides are vital for a series of technolo- gies. On the basis of a similar approach. colloidal metal dispersion can be used as a building block to produce functional materials [218].Assembly and Properties of Nanoparticles 59 A synthetization route. and as extensively discussed earlier. Steps I and II are reversible. Particle size can be controlled with the aid of stabilizers (step IV). 5. resulting in a metallic cluster growth process. and metallic clusters will interact (step II). Step V is essential to control nanoparticle deposition. narrow particle size distribution and a high de- gree of shape control. based on the principles applied to the synthesis and control of CdSe nanocrystals. Several reports in the literature describe the effects of size on the various properties of this class of materials. which results in metal atoms (Mo ). This process. The first step (step I) consists of the reduction of the metal- lic precursor (M+ X− ). Sun et al. Nanocrystalline metal oxide semiconductors such as TiO2 . These metallic atoms. [18] reported on the synthesis of iron–platinum (FePt) nanoparticles through the reduc- tion of platinum acetylacetonate by a diol. The origin of this morphology is thermodynamic. In general. display . was used [143]. using a simultaneous reduction of acetylacetonate and platinum acetylacetonate and thermal decomposition of Fe(CO)5 and obtaining an average particle diameter of 3. These authors discussed the synthesis of Co nanoparticles with high crystallinity. into five steps. SnO2 and ZnO. and decomposition of iron pentacarbonyl (Fe(CO)5 ) in the presence of a surfactant mixture (oleic acid and oleyl amine). Thus. The presence of only one stabilizer can result in a spherical particle. ions. The presence of two simultaneous stabilizers may give rise to a preferential growth process caused by the preferen- tial adsorption of one of the stabilizers.5 nm and narrow particle size distribution. basically. 217] or polymer-mediated nanocrystal assembly [220]. for example. Parti- cle agglomeration. the process becomes irreversible (thermodynamic condition).

and deposition.R. Al. and other inorganic salts. the control of metal oxide nanocrystals is still incipient. Based on the above analysis. Si(OC2 H5 )4 (tetraethyl orthosilicate or TEOS). Ribeiro and E. with enlargement of the band gap as the particle size decreases [73. these developments are directly related to the development of synthetic methods that allow for controlled particle size. Ti. Colloidal nanocrystals with quantum size effects are promising building blocks for novel electrical and optoelectronic devices [2. 223]. for instance. the development of metal oxides of nanometric dimensions can result in devices and materials with superior performance. Zr. hydrolysis of metal halides. which require thermal or hydrothermal treatment to promote crystallization. as described in (51) and (52): M − OH + M − OR → M − O − M + ROH (51) M − OH + M − OH → M − O − M + ROH (52) This type of reaction leads to the formation of an inorganic polymer or a three- dimensional network formed of metal oxianions. This class of compound is highly reactive with water. this reaction is called hydrolysis. including the amorphous phase. is an alkoxide compound. 221]. Metal alkoxide compounds are defined as compounds that have metal–oxygen–carbon bonds. 222]. Because of the high reactivity of alkoxide compounds with water. R is a ligand such as an alkyl group. Compared with the control attained in the synthesis of metal and II-IV semiconductor nanocrystals.60 C. Hydrolytic reactions are strongly dependent on wa- ter content and catalysts. Equation (50) shows a typical hydrolytic reaction of an alkoxide compound [100]: M − OR + H2 O → M − OH ↓ + ROH (50) where M represents Si. the bottom-up methods of wet chemical nanocrystal synthesis are apparently the most viable approach to achieve such control. The sol–gel process allows for very good chemical homogeneity and offers the possibility of obtaining metastable phases. Once again. Leite a quantum confinement effect. The literature contains excellent reports pro- viding in-depth analyses of this method [100. A partially hydrolyzed metal alkoxide molecule can react with other partially hydrolyzed molecules by a polycondensation reaction. Because the hydroxyl ion (OH− ) becomes bonded to the metal of the organic precursor. particularly insofar as the synthesis of complex metal oxide nanocrystals (oxides formed of more than one cation) is concerned. Examples of these methods are described below. Several factors affect the sol–gel process. particle morphology. The chemical synthesis of metal oxide nanocrystals based on hydrolysis falls into two major groups: hydrolysis of metal alkoxides. The above-described process is called metal alkoxide-based sol–gel. This process normally promotes the forma- tion of amorphous metal oxides. including the kind . (b) chemical synthesis based on the nonhydrolytic method. However. 135. hydrolytic reactions must be carried out in an atmosphere devoid of water va- por and the solvents used must have very low water content. and other metals. and ROH is an alcohol. The synthesis of metal oxide nanocrystals by wet chemical processes can be divided basically into two major groups: (a) chemical synthesis method based on the hydrolysis of metal alkoxides or metal halides.

After nucleation oc- curs. particles can be synthesized with controlled size. Following this model. Different stabilizers can be used to stabilize these particles and prevent coagulation (step 2). This method has been extended to other metal oxide systems with similar success. the TEOS/alcohol ratio. particularly for TiO2 synthesis [85. In this condition. 230]. The method was developed by St¨ober. The ease with which protonation or deprotonation occurs will depend on the metal atoms and can be controlled by the pH.Assembly and Properties of Nanoparticles 61 of metal alkoxide. the solvated metallic ion. which act as chelating ligands (carboxylic acids. preventing further nucleation and precipitation. the supersaturation of hydrous oxides increases continuously (by a change in temperature or pH) until a critical concen- tration is reached. water concentration. Thus. water/alkoxide ratio. and others) and decrease the precursor’s reactivity [224]. is only achieved by considering the as-mentioned monomer. A good alternative to overcome this problem is to use organic additives. A steric stabilizer can be used to control the condensation reaction during the precip- itation of hydrous oxides. the sol–gel process requires control of the particle size and morphology during the precipitation and coagulation steps and during the heat or hydrothermal treatment to promote crystallization.000 nm. and Bohn (SFB) [226–229] and is based on the hydrolysis of TEOS in a basic so- lution of water and alcohol. and agglomeration. the stabilizer is added during the hydrolysis . reducing the concentration until an equilibrium concentration is achieved. Particle size depends on the reactant concentration. Thus. 232].e. The sol–gel process can generally be divided into three steps: (1) precipitation of hydrous oxide particles. the charge-determining ions are H+ and OH− . The hydrous oxide particles precipitated by the hydrolysis of an alkoxide compound have the same tendency to agglomerate as that described for metal colloid systems. particle size and morphology are more difficult to control. morphology. Precipitation decreases the supersaturation to levels below the critical concentration. pH of the reaction solution. while steric stabilization can be more effective in organic media [231. As previously discussed. The precipitation of amorphous metal oxide (step 1) is well described by the LaMer and Dinegar theory [225]. nucleation occurs very rapidly and leads to pre- cipitation. the applicability of the nucleation theory discussed above. β -diketones. i. in this case. By varying these parameters. Fink. The growth of particles may then occur especially by the Ostwald ripening mechanism (48). Controlled hydrolysis is one of the most popular methods for processing silica spheres in the range of 10–1. in metal oxide particles the surface charge is controlled by the protonation or deprotonation of their hydrous oxide sur- faces (M-OH). the nuclei thus formed grow. temperature. i. and pH (>7). There is not only a similarity but also a fundamental difference between the ap- proach used to control coagulation in the sol–gel process and that used for metal nanocrystal systems. When the metal alkoxide’s hydrolytic reaction rate is too fast.. similarly to the metal colloid systems. Then. These stabilizers control coagulation by electro- static repulsion or by steric effects [44]. and (3) crystallization of the hydrous oxide particle. (2) control of hydrous oxide particle coagulation. nature of the solvent and stabilizers [100]. Electrostatic stabilization is most commonly employed in the water solution sys- tem.. In this case.e.

If an amorphous phase is the final target. surface crystallization must occur first. for crystalline materials. A possible way to avoid this problem is to suppress surface crystallization by using an inhibitory surface layer. They first applied a 12-h treatment in Ar atmosphere at 700◦ C. Leite step [86. rendering it very dif- ficult to control particle morphology and shape. The presence of hydroxyl groups and other defects on the particle surface can contribute to reduce the Gibbs free energy for crystallization. In the case of crystallization by heat treatment. Since the amorphous phase crystallizes via the nucleation-growth process. However. Controlling the generation of polynuclei in a single amorphous particle is the main challenge involved in obtain- ing crystalline metal oxide freestanding nanoparticles through the sol–gel process or by any other process that requires crystallization by heat treatment at high tem- peratures. Peir´o and coworkers [235] recently reported on the synthesis of TiO2 anatase phase with a nanorod morphology (9 × 5 nm size) using controlled hydrolysis of tetraisopropyl orthotitanate (TIP) and tetrabutylammonium hydroxide ((TBA)OH) as a steric stabilizing agent. However. to burn out the carbon residue. a heat or hydrothermal treat- ment is often necessary to promote the crystallization of the generally amorphous hydrous oxide which is formed during hydrolysis. in air.R. Ribeiro and E. 236]. 87. the crystallization process (step 3) can be considered as the critical step in the sol–gel process when a crystalline phase is desirable. 234]. each hydrous metal oxide particle can generate several nuclei. During the heat treatment. This approach was used recently to process freestanding lead zirconate titanate (PZT) nanoparticles. normally done in an electric furnace. 233. Since crystallization occurs in a scenario of high driving force (high temperature of heat treatment). render- ing the surface crystallization more favorable than the bulk crystallization. Finally. If crystallization occurs at a temperature that favors bulk crystallization. inhibiting surface nucleation. a single nu- cleus can be generated. Freestanding particles are desirable in a variety of fundamental studies and in some technologies. particularly for ferroelectric metal oxides such as PbTiO3 . giving rise to a particle with several nuclei.62 C. the synthesis is complete in step 2. as in the case of SiO2 nanoparticle processing. The polynuclei process generates polycrystalline particles rather than freestanding ones. during crystallization. the hydrous oxide colloidal sus- pension must be dry before the treatment. Such subsequent treatments can lead to particle growth and modify the particles’ morphology. Freestanding PZT nanoparticles with a mean particle size of 17 nm were reported. crystallization occurs by a nucleation growth process into the generated nucleus and can be described by the discussed nucleation and growth the- ory [100. The origin of the polynuclei process occurring during sol–gel amorphous precursor crystallization is assumed to be related to the preferential heterogeneous nucleation process (at the surface and interface nucleation) in detriment to homoge- neous nucleation. particle size and growth can be controlled based on the separation of the nucleation phenomena from the growth process. followed or not by bulk crystal- lization. which formed a surface layer rich in carbonaceous materials on the nanoparticles. A second treatment was carried out at 500–600◦ C. Liu and coworkers [237] used a sol–gel process based on controlled hydrolysis and a two- step heat treatment. resulting in a freestanding particle.

239].Assembly and Properties of Nanoparticles 63 (PT). The hydrolysis of metal halides and other inorganic salts is a method widely employed to process metal oxide nanoparticles. controlling the particle size by the ratio BaTi(OR)6 /oleic acid. the solubility of the amorphous oxide particle is significantly enhanced. Another alternative approach to avoid the heat treatment process is to promote crystallization under hydrothermal conditions. the hydrolytic process normally occurs in a water solution. O’Brien et al. the steps used to describe the metal alkoxide hydrolysis-based sol–gel process can also be used to describe the sol–gel process based on inorganic salts. ZnO temeulenkamp98. in which the hydrolysis took place (injection-hydrolysis method). in any case. F− . control of the atmosphere and water content in the solvents is much less demanding. doped and undoped SnO2 [244–248]. Nonetheless.253] recently demonstrated that well-crystallized SnO2 nanocrystals could be produced at room temperature with no hydrothermal treatment. followed by dialysis to remove the Cl− ions. However. In fact. The process developed by Bahnemann et al. This process is based on the hydrolysis of SnCl2 in an ethanol solution. i.Ti)O3 (PZT). the above-described approach appears to promote and control crystallization with no extra heat treatment. NO− n+ 3 . and the crystallization may oc- cur concurrently to growth processes.e. 241]. allowing for good control of particle size and morphology. redissolution and reprecipitation of the particles – but in crystalline nuclei. such as TiO2 [90. as well as the synthesis of ultra fine rutile TiO2 phase obtained by hydrothermal treatment in an acidic medium. Freestanding and single crystallinenanorods of BT and SrTiO3 (ST) were recently obtained [238. Hydrolysis promotes the precipitation of an insoluble amorphous hydrous metal oxide. The synthesis based on this approach requires the same control described earlier for the sol–gel method related to the hydrolysis of metal alkoxide. among others. Urban and coworkers [239] reported on the synthesis of BT and ST single crys- talline nanorods using a similar process.. Leite and coworkers [252. The crystallinity of the formed particle is. Zinc Oxide (ZnO) nanocrystals have also been synthesized at room temperature. and others. In hydrothermal conditions. [238] synthesized BT nanoparticles with diameters ranging from 6–12 nm based on this approach. using an alkoxide sol–gel route and achieving the crystallization of anatase TiO2 phase with a mean particle size of 10 nm at 180◦ C. Y2 O3 [251]. The result of this dialysis is a transparent colloidal suspension formed by near-spheric particles. and others) and the cation (M ). meulenkamp981 . ZrO2 [245. In solution. the metallic salt generates the anion (Cl− . Ying and Wang [242] used hydrothermal treat- ment to promote the crystallization of anatase and rutile phases. The cation is normally hydrolyzed by pH changing. wong98. The approach used in both these studies to obtain this type of material was the injection of a bimetallic alkoxide compound into a solvent at high temperature (100–280◦ C). 250]. [67] consists of hydrolyzing zinc acetate dihydrate dissolved in 2-propanol by the addition of NaOH . BaTiO3 (BT). requiring less control than the hydrolysis of metal alkoxide. Thus. Pb(Zr. determined by thermody- namic and kinetic parameters. 9 later. a process that is widely used in the synthesis of zeolites [240. 243]. The origin of nanorod morphology is not yet well understood. This process is less sensitive to water content. as illustrated in Fig.

Ribeiro and E. Leite Fig. using the hydrothermal process. The authors used a solution of SnCl4 and SbCl3 or SbCl5 in fuming HCl as precur- sors and promoted hydrolysis by increasing the pH (using aqueous ammonium). The hydrothermal treatment was carried out at 150◦ C using 10 bar of pressure. However. they dissolved the zinc acetate dihydrate (Zn(Ac)2 · xH2 O) in ethanol and used LiOH to promote the Zn+2 hydrolysis. they used a solution of SnCl4 and SbCl3 or SbCl5 in ethanol. . however.64 C. The final particles (after elimination of residual chloride by dialysis) are near-spherical nanocrystals in a 2-propanol solution.R. meulenkamp981. An adequate route to obtain good crystallinity at low temperatures with minimum particle growth is the hydrothermal treatment. the major problem of the metal salts hydrolysis ap- proach is the crystallization step. This synthesization route produced nanocrystals in the range of 5 nm. again. Particles in the range of 3–6 nm were reportedly obtained by both these processes. N¨utz and Haase [244] synthesized well-crystallized Sb-doped SnO2 nanocrystals. However. 9 Tin dioxide (SnO2 ) particles synthesized by hydrolysis of SnCl2 at room temperature. with particles in the range of 4–9 nm. A colloidal suspension of crystalline ZnO nanoparticles is obtained without hydrothermal treatment. the most common product of synthesis is amorphous. [247] also reported on the synthesis of well-crystallized Sb-doped SnO2 . using a hydrothermal treatment of colloidal gel. Goebbert et al. Similar results were obtained by Span- hel and Anderson [254] and by Meulenkamp emeulenkamp98. The gel was treated in an autoclave at temperatures in excess of 250◦ C. like in metal alkoxide hydrolysis and. promoting hydrolysis by raising the pH (using aqueous ammonium).

Mn3 O4 . by replacing the hydroxyl group with the methyl siloxyl group before firing. using the rapid decomposition of molecular precursor in the presence of strong coordinating agents. Camargo et al. PZT [259]. which apparently involves no hydrolytic reaction and is carbon and halide-free. and ZrO2 nanocrystals (ranging in size from 1. before the crystallization step. particularly citric acid (CA).Assembly and Properties of Nanoparticles 65 Once again. They showed that the growth could be in- hibited by replacing the surface hydroxyl group. Trentler and coworkers [88] proposed an interesting route to process TiO2 nanocrystals. Cup = C6 H5 N(NO)O− ) in a hot solvent with surfactant. These au- thors reported that fully crystalline SnO2 . and PbHfO3 (PH) [261]. with a functional group that does not condense and that can produce small secondary- phase particles. The development of metal oxide nanocrystals by nonhydrolytic synthesization routes results in materials whose surfaces are free of OH− groups and produces nanocrystals with different properties particularly suitable for catalytic and sensor applications. An important nonhydrolytic chemical process is the so-called Pechini process or in situ polymerizable complex (IPC) [262]. PbZrO3 (PZ) [258]. [258–261] recently developed a new route to synthesize lead- based perovskite nanoparticles. based on the following reactions: TiX4 + Ti(OR)4 → 2TiO2 + RX (53) TiX4 + 2ROR → TiO2 + 4RX (54) where X is a halide ion (Cl− . This process results in an inorganic amorphous precursor that requires subsequent thermal treatment to pro- mote crystallization of the desired phase. Rusakova et al. The synthetic route involved injecting the metal alkoxide (Ti(OR)4 ) into a titanium halide mixed with trioctylphosphine oxide (TOPO) and a solvent at high temperature (300◦ C). which restrict boundary mobility at high temperatures. [255] used an interesting approach to control the par- ticle growth of hydrous metal oxide gels. On the basis of the strategy used to process II-IV semiconductor nanocrys- tals. is called the oxidant peroxo method (OPM) because it is based on the oxidation–reduction reaction between Pb(II) ion and water-soluble metal-peroxide complexes with high pH. Nanoparticles with a mean particle size of 7. This method. such as PT [260]. TiO2 . The low crystallization temperatures (400–450◦ C for the PT phase) of the amorphous precursor suggest that the OPM method favors the formation of a homogeneous inorganic compound. control of growth after nucleation is necessary to obtain desirable nanoparticles. This process is based on the ability of polycarboxylic acids. Br− . to form very stable water-soluble . I− ) and R an alkyl group.5 to 5 nm) can be obtained after heat treating the precipitate gel at 500◦ C. F− . Alivisatos and collaborators [257] demonstrated that transition metal oxide nanocrystals (γ -Fe2 O3 . Cu2 O) could be prepared using a nonhydrolytic process based on the thermal decomposition of metal Cupferron complexes Mx Cupx (M = metal ion. and the molecular chemistry of these various methods is discussed by Vioux [256]. Several nonhydrolytic processes have been developed to process metal oxides.3 nm and anatase phase were obtained. Their re- sults suggest that a good level of control can be achieved when this approach is used to process metal oxide nanoparticles.

Leite and collaborators [283. At a temperature of > 800◦ C. The particle growth process. can be synthesized at temper- atures as low as 450◦ C. this method has also proved suitable to process ox- ide thin films with superior performance [273–277]. A high concentration of CA leads to smaller particles with a soft agglomeration. The CA complex thus formed can be immobilized in a solid organic resin through a polyesterification reaction with ethylene glycol (EG). This approach was originally developed to control the particle growth of metal nanocrystals [5. This process leads to the formation of a polymeric precursor with the cations of interest randomly distributed in a three-dimensional solid lat- tice. but it is generally assumed to be as- sociated with the tendency of a poly-cationic CA complex to develop during the chelation step in water solution [279]. and the thermodynamic equilibrium configuration was kinetically suppressed [278]. Using this process. showed that growth occurs in two different stages [281]. During the crystallization process. for example. Segregation of the dopant on the nanocrystal surface occurs during the heat treatment. Quinelato et al. avoiding precipitation or phase segregation during the synthesis of the metal oxide compound [263]. Leite chelate complexes. it is very difficult to keep the nucleation and the growth processes separate. dur- ing the crystallization step [280]. In the last five years. 273]. with an activation energy in the range of 40–80 kJ mol−1 . decreasing the particle boundary mobility or the surface energy. Crystallization was observed at a temperature at which long-range diffusion had to be constrained. even at high temper- atures. Even cations with a high tendency to become hydrolyzed. Ribeiro and E. resulting in a metastable cubic PbTiO3 phase. preventing the hydrol- ysis and precipitation of hydrous metal oxide. two methodologies have been used to control the particle size of metal oxides processed by the IPC method. 285] and was used successfully to control the growth of metal oxide nanocrystals. which was studied in the final stage of the crystallization of nanometric powder processed by the IPC method. This method is widely used to process titanates [264–268]. [272] demonstrated that the particle size and morphology of CeO2 -doped ZrO2 could be controlled by con- trolling the metal/CA ratio. the growth process is associated with the surface diffusion mechanism.66 C. niobates [269–271] and other kinds of polycationic or single cationic metal oxides [272. resulting in agglomerates made up of nanocrystals. The technique used to achieve this high stability was to process supersat- urated solid solution between the SnO2 and the dopant. 284] showed that the par- ticle size and morphology of SnO2 could be controlled by the addition of dopants such as Nb2 O5 and rare earths. PbTiO3 thin film [277] and nanometric powder [278]. At heat treatment temperatures of <800◦ C. such as Ti+4 and Nb+5 . Basically. can be chelated by CA in a water solution. The ability to form complex metal oxides at low crystallization temperatures and metastable phases is not yet well understood. . The major problem with this process is maintaining control over the particle size and morphology. with a local symmetry close to that of the crystalline phase.R. and/or the tendency to form an inorganic amorphous phase. particle growth is controlled by densification of the agglomerate formed by nanometric particles and by the neck-size-controlled growth mechanism [282]. The same authors [284] also showed that doped SnO2 nanocrystals are highly stable against particle growth.

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therefore. Bueno () Instituto de Qu´ımica. as this chapter intends to demonstrate. Departamento de F´ısico-Qu´ımica. S˜ao Paulo. Brazil e-mail: prbueno@mail. today.). 1 Introduction An in-depth understanding of the processes involved in the operation of electrochemical cells is crucial in the development of new methods for the design of more efficient electrochemical cells destined specifically for energy conversion and storage.R. C.Electrochemistry. In are provided to a large extent by the nanosize effect of these cells’ functional E. is on novel strategies that exploit nanoscale architectures to enhance the efficiency of alternative energy conversion and storage devices and on the basic principles of electrochemistry governing the P. c Springer Science+Business Media LLC 2009 . and Nanostructures Paulo Roberto Bueno and Claude Gabrielli Abstract This chapter deals with the development of new methods for the design of more efficient electrochemical cells destined specifically for energy conversion and storage based on synthesis and design of functional electrodes and electrolytes. The main focus of this chapter. Araraquara. Nanomaterials. Indeed.unesp. Nanostructured Materials for Electrochemical Energy Production 81 and Storage. Universidade Estadual Paulista.1007/978-0-387-49323-7 3. future developments in this field will necessarily depend on nanoscience and nanotechnology. the chapter provides a review of fundamental electron transfer concepts of relevance to electrochemistry in general and alternative energy devices in particular. Leite (ed. Nanostructure Science and Technology. 14801-907. DOI 10. Postal 355. An indispensable aspect of this body of knowledge is a thorough grasp of the synthesis and design of functional electrodes and electrolytes with unusual and valuable properties which. The main focus of this chapter is on novel strategies that exploit nanoscale architectures to enhance the efficiency of alternative energy conversion and storage devices as well as on the basic principles of electrochemistry governing the effects of nanoscale design on electrodes and electrolytes.

Bueno and C. electrochemistry is a field of science that deals with the relationship between electrical current or potential and chemical systems. To begin to understand how these areas are interrelated to improve the performance of such devices. the potential impact of these products on basic science and applications is so great that the subject is inexhaustible. Moreover. the absence of this and other related topics clearly indicates. although the mechanism of formation or removal of small individual portions of solids plays a decisive role in the field of electrochemical nanotechnology.82 P. 2 Electrochemistry and Nanoscale Materials 2. In other words. It includes the properties and be- havior of electrolytic conductors in liquid or solid form. In addition. electrochemistry addresses the chemical and physical transformations underlying chemical energy storage and conversion and their relationship to limitations in the performance of electrochemical systems [2–6]. On the one hand. the thermodynamics and kinetics of reactions occurring in the interphase and mass-transport effects throughout it [2–6]. From a more specific standpoint. Modern electrochemistry covers all phenomena in which a chemical change is the result of electric forces and vice versa. a brief explanation about both areas must be given. both of which are gaining increasing importance in the development of high performance and reliable alternative energy devices (conversion or storage) [1–3]. As the name itself suggests. the use of electrochemistry as a tool for the preparation of nanostructures for electrode and electronic applications lies outside the scope of this chapter. can be understood as the interaction between chemistry and electricity. where an electric force is generated by chemical processes.1 Electrochemistry and Size Effects Electrochemistry and nanoscience (and/or nanotechnology) are interdisciplinary fields.R. from the start. Therefore. On the other hand. The electrochemical manufacture of small objects ranks high in the design of new materials and systems with special properties. that no attempt will be made to cover the field comprehensively here. in turn. although it encompasses far more than mere knowledge of chemical systems and the physics of electric fields or potential. this chapter must perforce be limited to objects and systems that already show real promise for a variety of applications. The scope of ensembles of nanosized objects and prod- ucts that have been and can be created is truly remarkable. Moreover. modern electro- chemistry can be divided into interfacial electrochemistry (electrochemistry of het- erogeneous systems) and bulk electrochemistry (electrochemistry of homogeneous systems). However. bulk electrochem- . interfacial electrochemistry differs from bulk electro- chemistry by dealing with topics such as the nature of an electrode–electrolyte in- terphase. particularly in view of the enormous diversity of nanosized objects. Electrochem- istry. this chapter intro- duces basic principles of nanotechnology to guide the reader through this incipient interdisciplinary boundary. Gabrielli effects of nanoscale on electrodes and electrolytes.

Electrochemistry, Nanomaterials, and Nanostructures 83

istry deals with ion–solvent and ion–ion interactions, activity coefficient, ionic mo-
bility, ionic conductivity, and so on [2–6]. Bulk electrochemistry describes the per-
formance of electrolytes and is the key to future improvements in electrochemical
components used as ionic sources and membranes in solar energy devices for elec-
tric power production, energy storage, e.g., batteries and supercapacitors, as well as
advanced electroanalytical sensor devices [2–6]. Bulk electrochemistry is discussed
briefly here, in the context of ionic conductivity of solid-state electrolytes. However,
most of this chapter focuses on the fundaments of interfacial electrochemistry and
its relationship to nanostructures, which is of vital importance in electrochemical
alternative energy devices.
The term nanotechnology has been defined in a variety of ways; however, we will
define it here as the technology of design, manufacture and application of nanostruc-
tures and nanomaterials [7, 8]. The study of the fundamental relationships between
physical and chemical phenomena and materials’ dimensions on a nanometric scale
are also referred to as nanoscience. Nanotechnology involves the fabrication, char-
acterization, and manipulation of materials with at least one dimension in the range
of 1–100 nm. Thanks to their diminutive size, nanoscale objects will lead to ground-
breaking discoveries and are expected to be at the forefront of technological inno-
vation for the next decade. The interrelation between interfacial electrochemistry
and nanoscience gives rise to new possibilities for designing chemical surfaces by
controlling surface structures at the molecular level, leading to innovative metal or
semiconductor surfaces and charge transfer lengths.
Improved nanostructured devices based on nanostructured electroactive material
can be designed in different ways [9–15]. For instance, the interfacial electrochem-
ical properties of specific materials can govern the performance of charge accumu-
lating at the interface, leading to highly efficient double layer capacitors [16–24].
In bulk electrochemistry, a proper understanding of the high performance of ion-
conduction properties on a nanolength scale is crucial [25–29]. Other examples will
be discussed later herein.
Micrometric-scale materials generally display the same physical properties as
those in bulk form; however, nanometric-scale materials may exhibit physical prop-
erties that are distinctively unlike those of bulk. Materials in this size range possess
remarkable specific properties deriving from the transition from atoms or molecules
to bulk form that takes place in this size range. On the one hand, the interfaces in
polycrystalline microstructured materials are considered as defects that influence the
macroscopic properties. On the other hand, in polycrystalline nanostructured mate-
rials, the interface dominates and the bulk plays a totally different role. Numerous
experimental studies have shown that, if a material’s particle size is less than the crit-
ical size of about 10 nm, its bulk properties change noticeably. A particle of about
10 nm contains 104 –105 atoms, 1–5% of which are on the surface of the particle and
contribute substantially to the material’s physicochemical properties [30]. Ensem-
bles of such nanostructures will be shown here to be important in electrochemical
applications such as electrodes [8, 9, 12, 13, 31–38].
Another example of the influence of nanometric effects is on the Debye tem-
perature, which decreases in nanocrystalline systems, and is lower when the same

84 P.R. Bueno and C. Gabrielli

system is on a micrometric scale. Thus, the nanometric scale gives an additional
contribution to the low-temperature heat capacity, and this contribution increases as
the scale decreases [39].
This effect can be explained by changes in the nanocrystals’ vibrational status
(an increase in the number of low frequency modes in response to a decrease in
the number of high frequency modes) as the size decreases. Therefore, nanometric-
scale crystals have a low melting point (sometimes below 900◦ C) and reduced lattice
constants, since the number of surface atoms or ions represents a significant fraction
of the total number of atoms or ions. In this case, surface energy plays a significant
role in the thermal stability, while bulk represents the defect in the properties. From
this standpoint, nanotechnology can be considered new, but nanometer scale re-
search is not new at all. Nanometric-scale engineering of many materials such as
colloidal dispersion, metallic quantum dots and catalysts [37, 40–49] has existed for
decades. Nanotechnology is therefore not a novelty; indeed, you can see it all around
you if you just know where to look.
Actually, nanotechnology is a combination of existing technologies, and our new-
found ability to observe and manipulate on the atomic scale makes nanotechnology
highly compelling from the scientific, business and political points of view. This
aspect of nanotechnology was already foreseen in a conference presented by Nobel
Prize winner Richard Feynman in 1959.
One can visualize another example of the nanoscale effect by picturing a bulk
material, e.g., a metal or n-type semiconductor metal oxide, simplistically, as con-
sisting of charged particles, positive ions, and electrons in the first situation, and
positive and negative ions in the second. In both cases, the total positive charge bal-
ances the total negative charge, so that there is no net electric charge in the material’s
bulk. Now imagine reducing a piece of this material to the nanoscale by applying a
top-down approach such as any lithographic technique in a vacuum medium. What
electronic properties will such a small, strongly charged material have? Consider-
ing the vacuum as the environment in which these properties are embedded, there
is a small degree of spillover of the electrons from the material into the vacuum,
resulting in a disturbance of the former balance of electrical charge in the surface
region of the materials, which in this case represents a substantial percentage of
the total volume. Note that interfaces in micrometric or millimetric materials can
also be electrified, but there are some differences. A totally different functionality
arises on the nanoscale, because of the size range involved [30]. Indeed, changes
in the electronic properties of nanoscale materials due to the size effect must be
interpreted in the domain of quantum chemistry [50]. If the size of the nanocrystal
is compared with the de Broglie wavelength of elementary excitations, the quanti-
zation conditions of electron energy are changed and the energy bands split into an
energy system of energy level and, in this case, the pattern of the absorption spec-
trum becomes similar to that of the spectra of individual clusters. Semiconductor
nanocrystals possessing these properties are called quantum dots [50].
The physicochemical properties of nanometric-scale materials are part of the do-
main of nanoscience but, in specific situations, nanomaterials can converge with
electrochemistry. For instance, if our previously pictured nanomaterials (nanocrys-

Electrochemistry, Nanomaterials, and Nanostructures 85

talline particles) are immersed in an appropriate solution, a colloidal system is likely
to arise [51, 52]. The use of nanoparticles to form colloidal systems has a long his-
tory, as exemplified by a comprehensive study about the preparation and properties
of colloidal gold, which was first published in the mid-nineteenth century [53]. The
colloidal dispersion of gold prepared by Michael Faraday in 1857 [54] remained
stable for almost a century, showing no sign of spontaneous chemical degrada-
tion before it was destroyed in a Word War II air raid. Colloidal properties result
from the combination of the properties of an electrified surface and nanomaterials/
solution, the structure of the double layer thus formed being the most important
In the emerging field of nanotechnology applied to electrode design, the goal
is to create nanostructures or nanoarrays with special properties unlike those of
bulk or single particle nanosize elements. Thus, if nanoparticles are combined in
any way under a conductor substrate and inserted into an electrolyte, the resulting
properties will differ from those produced under the same conditions but without
nanoparticles or nanoscale materials [10, 12, 30, 37, 47]. Nanoparticles themselves,
or an electrode composed of nanoparticles, can exhibit unique chemical proper-
ties because of the limited size and high density of corner or edge surface sites
[7, 30, 55, 56], but as electrode-forming components, the most important properties
are those arising from the charge transfer rate, electronic and ionic transport, etc.
[8, 15, 30–32, 40, 42, 47, 57, 58].
It is a known fact that, from the standpoint of materials and surface science, many
of the properties of systems are controlled by interfaces and contact between differ-
ent materials [7]. However, knowledge of how to control and design new contact
(electrodic or electronic) properties on a nanometer scale is new and is very rapidly
gaining ground. Such contacts constitute the electrodes of galvanic cells which can
be used for the generation of chemical products by electric power (electrolysis), as
will be discussed later herein.
It is of primary importance to know how to differentiate between electrochem-
ical responses and events that result from changes in charge transfer length relat-
ing to the functionalized surface properties of nanoscale materials and those that
arise from transport properties through nanostructures. It is easy to demonstrate that
chemical reactions occurring in nanostructured electrodes (electrode reactions) and
mass and electrical transportation in such electrodes, and even in electrolytes based
on nanocomposites or other kinds of nanomaterials, will cause a tremendous rev-
olution in every aspect of applied electrochemistry [8, 12, 13, 15, 30, 32–34, 36, 38,
42, 43, 57, 59–70]. The main focus here is to show how these nanoscale effects re-
sulting from the use of designed nanostructured electrodes will inevitably contribute
to the development of alternative energy devices based principally on concepts of
We, therefore, need to know more about how to deal with and take advantage of
the continuous flow of electrons across electronic nanostructures and ionic species
in a nanoscale ionic conductor (electrolyte). Furthermore, it is also important to un-
derstand how charge transfer lengths are influenced on the nanoscale and how size
affects electrochemical properties [8, 30]. Accordingly, we will consistently address

86 P.R. Bueno and C. Gabrielli

the processes and factors affecting the transportation of charges across interfaces
between nanostructured chemical phases. In the latter case, electrochemical reac-
tions are involved and the transfer of electrons from the electronic phase to the ionic
conducting phase is classified as an oxidation–reduction (redox) reaction. In the
case of electrochemical conversion systems, it is also important to deal with charge
transfers occurring from molecules to semiconducting nanoparticles [71].

2.2 Challenges of Charge Transfer

It must also be emphasized that oxidation–reduction reactions always involve charge
transfers, without which we can no longer exist [8]. Electron transfers are vital to
our daily life. Indeed, we owe our very existence to photosynthetic and biochemical
electron transfer events, and we would be unable to function properly without the
myriad transistor-based electronic devices that control and amplify current flows.
Electron transfer and charge storage are correlated in a series of events in our body.
Another example of the importance of electron transfer reactions is photosynthe-
sis, which photoelectrochemical systems designed for energy conversion attempt to
imitate [3, 72]. In photosynthesis, a photon triggers an electrical current in the leaf,
activating the leaf’s electrons to produce H2 while the holes produce O2 .
Therefore, electron transfer events are basic to the understanding and develop-
ment of novel generations of electrochemical energy conversion and storage systems
based on the imitiation of the most efficient biological systems. Electrochemical en-
ergy conversion and storage devices form an important branch of alternative energy
emerging in the twenty-first century [1] that, like nanotechnology, has crucial scien-
tific, technological, and political implications.
At this point, however, it is important to stress that despite the importance
of properly grasping the charge transfer phenomenon, molecular and bulk level
charge transfer processes are still not fully understood and the characterization of
nanoscale (1–100 nm) processes is still incipient [8, 73]. Nanoscale charge trans-
fer is important both to the frontiers of fundamental science and to applications
in molecular electronics, including problems such as electrocatalysis [8] and solar
Progress in the area of nanoscale charge transfer requires interdisciplinary col-
laboration, combining a wide range of materials synthesis and electrochemical char-
acterization, a challenging range of experimental techniques to probe charge trans-
fer processes, and theory for their interpretation [8]. Current interest ranges from
the use of single or small groups of molecules (usually organic) as components in
electronic devices to the exploitation of semiconductor and metal nanoparticles be-
cause of their high surface areas and other size-dependent properties. The nature
of the attachment of such components to bulk metal and semiconductor surfaces
and the control of their properties are overarching concerns [8]. The experimen-
tal measurements used to characterize nanoscale charge-transfer properties include

and conductance/resistance measurements. depending on the nature of the system studied [30]. For a number of systems. the so-called electrified interfaces in electrodics. Some aspects relating to electrified surfaces in contact with electrolyte. the adsorbate layers and the edges of surface atoms on electrodes are spatially separated by gaps. These topics will be discussed in greater detail in other sections of this chapter. which are manifested in the reduction of anions on a negatively charged surface [74. whereby the energy from the source is . electrolytes and membranes) cover 5–10 orders of magnitude and the lower boundaries of the corresponding intervals approach typical sizes of specific space regions (layers) that arise only at the electrode–electrolyte junctions. spectroscopy.3 Nanomaterials and Nanostructured Films as Electroactive Electrodes Earlier herein we mentioned several challenges posed by nanoscience and electro- chemistry. the characteristic dimensions of conventional components of electrochemical systems (electrodes. In general. 75] along with the classical effects of the cation size. Nanomaterials. The conversion of energy necessarily in- volves some kind of energy transfer step. and the EDL structure. The prospect of using size effects to intensify electrode processes cannot be con- templated without including nanotechnology and electrode design. Predictions of the kinetics of electrons taking into account all size-dependent factors are possible only when adequate ion-molecular models of reaction layers are built. 2. Self-supporting colloid network structures allow for the coexistence of high conductivity with mechanical stability. In elec- trochemical systems.Electrochemistry. this problem can be solved successfully by employing quantum-chemical methods based on quantum mechanical theory of the charge-transfer elementary act [74. have been discussed briefly. According to modern notions of the interface structure. Also briefly mentioned earlier is the fact that the physical properties of the interface of nanoparticles in solution/solvent or electrolytes may lead not only to colloidal behavior but also to particle–particle interaction or particle–solvent inter- action. metal– or semiconductor– electrolyte junctions whose properties can control charge transfer length. 2. enabling colloidal gels to be used as elec- trolytes [76–78].3. un- doubtedly the most important question to be answered is “Why is nanoscience or nanotechnology so beneficial to electrochemical energy devices?” The answer lies in understanding the fundamental principles underpinning the electrochemical generation of electricity. Despite all these aspects of electrochemistry and nanoscale discussed so far. The latter will be introduced in Sect. charge transfer kinetics. 75]. and Nanostructures 87 rate constants. generally called Electrical Double Layer (EDL) [3–6]. the properties of this gap depend on the electrode potential (charge).

e. When the characteristic dimensions of nanoparticles are suffi- ciently small and quantum effects are observed. the amount of electricity produced scales with the amount of reaction surface area or interfacial area available for the energy transfer. this material can be prepared on a nanoscale (to enlarge the surface area) mainly in three distinct forms (a) zero- dimensional. 1). Single crystalline nanoparticles are often referred to in the litera- ture as nanocrystals.. several methods have been developed in recent years for the preparation of novel nanostructures [7]. All these nanosized structures [from (a) to (c)] are synthesized using either one of two manufacturing concepts. we must first offer a basic introduction to the term “electroactive materials” so popular in the electrochemical literature.g. (b) one-dimensional and (c) two-dimensional nanostructures. For now. i. 43. all electroactive materials are potential electrodes. At present. Further along in this chapter we will discuss the concept and definition of elec- trodes and electrochemical cells. Nanomaterials include molecular wires. 79–83]. dendrites.. top-down or bottom-up approaches.R. electrodes. There- fore. Therefore. which constitute the electric current. how can nanotechnology and electrochemical devices (e. the processing conditions must be controlled so that the resulting nanoparticles have the following characteristics (a) identical size of all particles (also referred to as monosized or quasi-monosized). transport and kinetic reactions occurring in these devices? To begin answering this question. In other words. nanoparticles – both semiconducting and metallic. respectively. also offer enormous potential for useful electrochemical functions [8]. nanotubes. Based on these two approaches. organic diodes. electroceramic electrode devices and sensors. and they play an increasingly central role in nanotechnology and electrochemistry. aerogels. and (c) identical or at least very similar chemical composition and crys- tal structure. 7. while the electrochemical cell is composed of a source and a sink electrode separated by an ionic conductor (electrolyte). Thus. This transfer occurs at a finite rate and must take place at an interface or reaction surface. these nanoparticles are commonly . Elec- troactive materials are materials that possess redox properties. Bueno and C. and magnetic and optical devices [1. Gabrielli passed along to electrons. the efficiency of the reaction and the amount of reaction depend. 8. such as filled zeolites. In this perspective. an electrode can be considered a source or a sink of electrons to be interplayed with the ionic conductor in contact with it. the wide range of applications for these materials include electrodes and membranes for electrochemical energy conversion and storage. Other products. and the connectors that link these objects together to create larger structures (Fig. (b) identical shape or mor- phology. For any practical applications such as electroactive components in electrodes. the zero-dimensional (0-D) nanostructure is composed of nanoparticles whose fabrication requires the control of more than merely their diminutive size. and layered polymers.88 P. it is not surprising that the desire for large surface areas has led researchers to focus on nanomaterials and electrochemistry in the search for nanosized structures for electrode applications. From the standpoint of nanotechnology. In the case of (a). energy conversion and storage devices) converge from a nanoscopic standpoint of electronic transfer. on the features of the sur- face and on the extent of the surface.

many of them based on bottom–up approaches. which are generally metallic. Ednan Joanni for providing some parts of this schematic representation described as quantum dots. 1 Nanostructured electrodes can be prepared by several methodologies. template-based synthesis and elec- trospinning are considered bottom-up approaches. 84]. By combining different electrodes.Electrochemistry. Nanomaterials. nanorods and nanobelts. Electrodes can . while lithography is a top-down technique [7. Spontaneous growth. From the electrochemical standpoint we are interested in the redox properties of such nanoparticles. which have been the object of intensive study for almost a century and for which many methods have been developed and improved. inorganic or compounds. one can attain a three-dimensional (3-D) integrated electrochemical cell [85–87]. it is important to stress here that most electrodes for electrochemical application in alternative energy devices are manufactured mainly by interfacing semiconducting nanostructures with conducting substrates. Insofar as the concept of electrode is concerned. Two-dimensional (2-D) nanostructures (c) involve thin films. This figure illustrated the ordered (left) and disordered (right) prepa- ration of brushlike structures obtained from nanowires and/or nanotubes. and Nanostructures 89 Fig. We are indebted to Dr. One-dimensional (1-D) nanostructures (b) are composed mainly of nanowires.

(2) the huge surface causes charge carrier perco- lation across the nanoparticulate lattice. A more specific example is the extremely large internal surface area. whereby they are assembled using 0-D. 2-D-based electrodes can be fabricated as homoge- neous thin films or by an assembly of 0-D and 1-D nanostructures. Some of these reasons are (1) sufficient adsorption of the monolayer of dye molecules to achieve efficient light absorption. 70. and 2-D). thin films can be considered 2-D nanostructures. 86]. and (3) the very rapid and highly efficient interfacial charge transfer between the oxide and each and every one of the dye molecules anchored to the particle surface. 37. thin film-based technologies have been responsible for the design of an enormous variety of thin film-based electrochemical devices.90 P. it is easily observed from the electrochemical literature that 2-D or 3-D struc- tured electrodes composed of architectures possessing high surface-to-volume ratio nanostructures.000 times greater than the geometric area expected for a compact and homogeneous 2-D struc- tured electrode. Bueno and C. We will provide specific examples in this chapter.. As can be seen. 1-D. In electrochemistry they are known as porous electrodes. Returning to the subject of nanostructures designed and used as electrodes. dye-sensitized solar cells (DSSC) is an example of 2-D and 3-D nanometer-sized structures assembled with quasi 0-D structures or building blocks (nanoparticles). 88–90]. which is made possible by the nanocrystalline particle nature of nanostructured semiconductor electrodes. particularly as regards the catalyst part of the cell where the oxygen reduction reaction can only occur in spatially confined regions [8. e. in the . As mentioned earlier. however.70. 8. Gabrielli also be developed based on a 3-D concept. We have already shown here that large surface areas translate into enhanced elec- trochemical performance and. which are constituted by the arrangement of multiple dimensional nanostructures (0-D. The charge transfer kinetics is often influenced and high surface areas provide greater numbers of electroactive charge transfer sites. The nanostructuring of electroactive materials introduces major changes in the electrochemical properties of the devices of which they are a part. from this perspective. and they sometimes possess an effective surface more than 1. porous thin film-related electrodes [92–96].88–90]. It is so important to note that. nanostructures are also very important for fuel cell devices [8. Therefore. 70. the porous effect is an important and significant as- pect of nanostructures applied as electrodes. but their thickness is not limited to nanolengths. They are usually referred to as nanostructured electrodes and most of them are highly porous. This huge surface area is crucial for the proper functioning of DSSCs for a number of reasons. and several other examples are given in the handbook. For instance. 1-D. are extremely useful in energy storage or con- version device applications because they improve storage capacity and conversion [1. 3-D electrodes can be similarly manufactured. therefore. In the recent past. the assembly and synthesis of these nanostructures with multiple dimensions is com- mon in electrochemistry.g. 2-D nanostruc- tures [91] composed of 0-D or 1-D materials are those that are associated with the interfacial properties of electrodes. or 2-D nanostructures. 15.R. the film’s thickness must be limited to the nanoscale.

Solid ionic materials of this kind are based on nanoceramics.4 Nanomaterials as Electrolytes Nanoscience and nanotechnology influence not only the design of nanoscale electrodes but also that of nanoscale electrolytes [9. lithium. and with the demonstration of feasible devices. the results achieved so far suggest that the emerging field of nanoionics has a healthy future [28.g. which is the prod- uct of defect concentration and mobility. Fuel cells based on these ma- terials – known as fast-ion conductors or solid electrolytes – offer a highly efficient and clean method of large-scale energy production [109]. All these materials are being investigated to improve their transport properties for the ionic species of interest. Nanomaterials.106]. The electrical conductivity at the melting point is eight orders of magnitude lower than in metal. e. The conductivities of a few materials even approach those of aqueous electrolyte solutions. implying that transport and heterogeneous transfer processes are strongly coupled in these systems [92–101]. is low in simple classic inorganic solid ionic materials such as NaCl.. enhancing the ionic conductivity of nanoscale materials is of great in- terest. 102–105]. The development of new solid materials for electrolyte applications is creating opportu- nities for new types of electrical power generation and storage systems. fuel cells. and hybrid organic–inorganic nanocomposites [102]. and sensors [108. We will discuss porous electrode theory further along in this chapter. Owing to the minute scale of the constituents of the porous lattice. or oxygen. 28. such as the scale-up of laboratory techniques for mass production. polymeric compounds. this aspect leads to the use of terms such as porous elec- trodes when referring to nanostructured electrodes [92–101]. and Nanostructures 91 electrochemical literature. Porous. or nanostruc- tured. An obvious technological target is the preparation of nanoscale lithium-ion conductors to make more efficient rechargeable batteries for portable electronics [107]. The concept behind nanoionic materials is based on the use of nanoscale effects to improve overall ionic conductivity [28]. The continu- ous research of new materials for electrolyte applications has led to advances in the design of nanostructured materials to improve ionic conductivity [25.109]. Solid state electrolyte material began to attract seri- ous attention with the discovery of new compounds and nanocompounds with high ionic conductivities. 28. 102]. . Therefore. charge ionic carriers in transit are always close to the surface. Overall conductivity. There are several new classes of materials based on the concept of nanoionics (nanostruc- tured materials for use primarily as electrolytes). electrodes form an electrochemical system when in contact with an elec- trolyte. Many problems still remain to be solved.Electrochemistry. Progress to date in solid-state ionics is largely the result of fast ionic conductors [29. 2. and is almost impossible to measure at room temperature. 107]. leading to the simultaneous transport of electronic and ionic species. particularly solid-state batteries. proton. for it offers a predictable way to design a wide range of new ionic materials with practical applications. Nonetheless.

Some experiments and theories indicate that dramatic increases in ionic conductivity should be expected when the spacing of interfaces is comparable to. exciting new avenues are being opened for storage using nanosized and nanostructured materials [102]. corre- sponding to diffusion parallel to interfaces. when dealing with nanosized materials and nanostructured electrodes for electrochemistry. to enhanced ionic conductivities in the space charge regions. the properties of electrolyte ceramic materials can be improved by the nanoscale surface properties. Electrical properties of solid electrolytes or mixed ionic–electronic conducting materials in the quantum confinement regime have not yet been described fully and represent a challenge to this field. and ionic conduction in this region is enhanced accordingly [28. It has also been stated [72] that the coefficients of oxygen diffusion in TiO2 . as in grain boundaries of polycrystalline materials or in nanoscale materials. For example. While the quantum confinement regime has been explored for some ionic ma- terials. 2. However.5 Nanoscale Electronic and Ionic Transport Finally. and interest in nanosized ionic materials continues to grow [1]. the surface has an excess of one type of defect. irrespective of yet unknown mobility effects. with hydrogen as the fuel. transport across interfaces involves transport perpendicular to the interface. if one considers the correct description of ionic dif- fusion coefficient suction of a crystal.R. therefore. and water as the waste product [109]. Bueno and C. it is important to sep- arate the different effects of interface on the electronic and ionic transport: the kinetics and mechanisms of transport along and across interfaces. the space-charge layer [28.92 P. the value obtained for the ionic coefficient on the surface is abnormally high in the nanoscale compared with the microscale [111]. As a result. it is evident that lowering the length scale may lead to enhanced de- fect densities and. or smaller than. The fossil fuel crisis and the need for better energy management will lead to increased activity in this area. The surface properties of an ionic crystal create a space-charge region. It is possible to show that. considering what was discussed previously. 110]. in which the concentration of defects at the surface is governed by the energies of individual defects and one type of defect in a pair can dominate. Gabrielli An example of classical solid state electrolyte is electrolytes based on zirconia polycrystalline material that conducts oxygen ions. 110]. In contrast. air as the oxidant. With regard to the safe stor- age of (sustainable) hydrogen. it is evident that thus far only optical properties have been related to the quantum confinement regime. The achieving of high ionic conductivity in nanostructure-based electrolytes requires a better understand- ing of the fundamentals of ion dissociation and transport in such kinds of nanosized materials [28]. as in the case of chemical doping. The literature commonly considers transport along interfaces as grain boundary transport. as across nanostructures limited to a thin layer of nanometric thickness.

in the formal physical definition). provided reliable electrical power to space missions for many years. as fossil fuel supplies are expected to become increasingly scarce.Electrochemistry. solar energy. and electricity generation. Oxygen conductivity can also be improved in the same way for ZrO2 -based solid electrolyte [102]. Sunlight can be used for heating. 000 W m2 [1. Closely related to solar cells are fuel cells. radiation on a horizontal sur- face is about 1. but nowadays the predominant source is fossil fuels. With an inexhaustible supply of free energy. the second law states that. the conversion efficiency of sunlight to electric power is not high. a quantity called entropy. having units of energy/temperature. in an isolated system. for it represents an entirely new source of energy generation affecting every aspect of our daily lives. and it can be concentrated to provide steam to run turbines. and sunlight varies according to the time of day.. Hence. 2. expensive. Nanomaterials. Sunlight is the source for the biosphere. ongoing sources of free energy (or just energy. almost anything can be done. When the sun is directly overhead and the sky is clear. It there- fore follows that increasing entropy. increasing depen- dence on energy conservation and alternative sources of energy are expected to be- come the most obvious solution. According to the first law of thermodynamics. a whole suite of sources is used. 71]. These have a considerably higher energy den- sity than that of sunlight. photovoltaics and solar cells have. loosely) are required for all biological and technological activities. lighting. Although fuel cells have been operating reliably and efficiently . which from Earth is ultimately radiated out into space. weather conditions and seasons. However. at present. but the critical constraint lies in the second law of thermodynamics. must always increase in any spontaneous process.6 Energy Conversion and Storage in Electrochemistry The conversion and storage of energy by electrochemical devices is a highly important technological issue of debate. and Nanostructures 93 nanocrystals are 5–6 orders of magnitude greater than in bulk crystals and that the coefficients of diffusion of dissolved hydrogen in palladium nanocrystals are greater than in the bulk specimen.e. less energy is available to perform useful work. which is the most fundamental resource. which convert fuel or chemical energy directly to electric energy. i. and its efficiency is tied in with the concept of free energy (the capacity to do work. The same concept can be applied to interfaces between the components of rechargeable solid-state lithium ion batteries. A certain amount is irretrievably lost. In the case of conventional technology. energy cannot be created or destroyed. in practice generally as low-grade waste heat. and environmentally impacting. implies that free energy cannot be fully recycled. In the way it is usually expressed. The principal disadvantages of solar energy are still that. in fact. To give an example. especially energy from the sun. thereby improving the performance and reducing the resistivities of dc batteries [102]. Although the total energy remains unchanged. The main chemical reactions involve the oxida- tion of CO and H2 . in turn.

. and their development and applications are growing rapidly [1. cathode. in turn. A galvanic cell is an electrochemical cell in which a spontaneous chemical reaction is used to generate an electric current.e. for they are at the heart of modern mobility and convenience [107]. These devices are also required to supply mobile energy for the portable electronic devices upon which our modern lifestyle is so strongly dependent. and electrolyte materials and processes are needed [1]. offering low costs. and higher efficiency. 3 Overview of the Principles of Operation of Energy Conversion and Storage Devices To understand the basic principles of operation of an energy conversion or storage device it is important to know what an electrochemical cell is. safety. what is the real importance of electrochemical alternative energy de- vices? There are several energy sources. with the prospect of providing something approaching a sustain- able standard of living for the entire world (so far enjoyed only by industrialized countries). alternative renewable sources of energy that do not depend on fossil fuels and that cause only marginal environmental im- pacts must be developed. while secondary cells are those that must be charged (i. it is a device in which a chemical reaction either generates or is caused by an electric current. There are three types of galvanic cell: the primary.. the secondary. Indeed. 109. An electrolytic cell. All of them involve electron transfer reactions. To meet the growing global demand for energy and to compensate for the depletion of fossil fuel supplies in the coming years. electrochemical nanostructure-based devices offer an important solution to this dilemma. especially because conventional energy supply technology is exhausting its resource base at an accelerating rate. exacerbated by the revolution of rising expectations in the less-developed world due to the global communications revolution. they have not yet been widely used on Earth. To make this technology commercially competitive. Basically. This rapid expansion in the study and development of electrochemical energy generation and conversion-based devices is due mainly to the fact that most of the world’s energy is supplied by fossil and nuclear sources. and the fuel cell [5. as presented earlier. Primary galvanic cells are those in which the reactants are built-in during the manufacturing process. Gabrielli in space missions for more than 40 years.R. Bueno and C. 71. largely because of their cost.. better anode. However. since they provide the capability for developing more efficient devices in all areas involving electrochemical alternative energy while causing a low environ- mental impact (sustainable development). on the electrochemical concept of storage of chemical energy. 112]. There is also a great demand for devices based on the concept of energy storage.e.94 P. 6]. is an electrochemical cell in which a reaction is driven in its nonspontaneous direction by an externally applied electric current. which face continual and increasingly severe issues of resource limitation and environmental pollution. i.

These electrodes are called cathodes and anodes. Fuel cells are the type of galvanic cells in which the reactants are supplied continuously as they produce current.25 0 0 0.e.50 0.00 μm Fig. 2 Design of 2-D and 3-D nanostructures from 0-D nanostructures. i. Nanomaterials. Both 2-D and 3-D nanos- tructures are very commonly applied as electroactive materials in the manufacture of nanostruc- tured porous electrodes used as electrolytic cells) before the reactants are present for the reverse. sponta- neous reaction [5. (1) . 6].00 20.0 nM 0. the removal of electrons that occurs in the anode can be described as follows: Ared → Aox + e− .50 0. an ionic conductor. and Nanostructures 95 1.75 1.2 nM 0.. An electrochemical cell comprises two electrodes in contact with an electrolyte. A cath- ode is the electrode that acts as a source of site for reduction reactions in the elec- trochemical cell.4 nM 0. while an anode is the electrode that acts as a source of site for oxidation reactions.Electrochemistry. Therefore.25 0.75 10.

whereas fuel must be supplied to a fuel cell from an external source. while Cred is the reduced site or species in the cathode. often with extremely high efficiency. 3. under appropriate conditions.3 and 3. carries its fuel around with it. in turn. The layered host lattice in the cathode and anode is also illustrated. constituting an electrical current that can be used to drive an external device. a fuel cell cannot become depleted and so long as fuels are supplied it will generate electricity.g. Cox corresponds to the oxidized form of a site or species in the cathode. 3 Schematic of a rechargeable lithium battery in discharge/charge mode. These systems can therefore be understood in terms of parts. Considering that both are electrochemical cells. a battery. The lithium ion is intercalated in the anode during charging and in the cathodes during discharging. Gabrielli in which Ared is the reduced form of a site or species and Aox is the oxidized site or species in the anode. Many oxi- dation and/or reduction reactions are also accompanied by the transfer of atoms or molecules. the former involving the transfer of electrons from one set of reactants to the anode and the latter involving the transfer of electrons from the cathode to a CHARGE Power supply e− Load O DISCHARGE Co Li ELECTROLYTE Carbon CATHODE ANODE Li1-xCoO2 Graphite Fig. electrons flow from the anode to the cathode. In other words. Batteries and fuel cells operate according to the same fundamental principle. the chemical free energy associated with a particular reaction can be converted into electrical energy.R.5. it is possible to demonstrate that during operation. e. Bueno and C. Unlike a battery. The fuel is an inherent part of the battery.. considering a cathode composed of a lithium cobalt host and an anode composed of a crystalline structure of hexagonal graphite. See Color Plates . (2) in which. see Figs. in other words. Recharging problems are therefore peculiar to batteries [107]. since the overall chemical reactions can be broken down into components of oxidation and reduction reactions. The following reaction occurs in the cathode: Cox + e− → Cred .96 P.

86. Indeed. and mesocarbons. supplying an electrochemical potential close to that of metallic lithium electrodes [121]. planar layers of carbon atoms forming fused six- membered rings and separated by intercalate layers. namely. 113–117]. ideally. 81. and Nanostructures 97 second set of reactants. in which the diffusion of Li ions must be reasonably . the interfacial boundary area can accommodate lithium to form Lix C with x > 1. (3) −−−−−→ where Li+ enters the electrolyte. The large number of boundaries resulting from the use of graphite nanostructures has proved useful for improving lithium intercalation capacity [102. 3. completely reversible in chemical terms [6]. and hence. or at least be miscible with. low electronegativity and high electron/atom mass ratio.Electrochemistry. 107. The most classic example is lithiated carbon (Lix C6 ). 121]. Despite its low density (0. all of which differ in degree of crystallization and stacking order. an increased reversible capacity [102.53 g cm−3 ).1 Lithium Ion Batteries Lithium-ion rechargeable battery solid state devices rank high among the alterna- tive energy devices in which nanostructured cathodes or anodes make a dramatic difference in improving rate capabilities [79. whose discharge functions as an electron donor can be expressed as: discharge −−−−−→ xLi charge xLi+ (electrolyte) + xe− . lithium is the preferred choice for the active element of the anode. The following reaction generally takes place at the cathode: discharge xLi+ (electrolyte) + xe− + MO2 −−−−−→ Lix MO2 . but all of which have the characteristic struc- tural feature of graphite. (5) which clearly indicates that to operate effectively. 107. 121]. and the electron exits the anode. 82. Other types of materials containing lithium (lithi- ated host materials) are also used as anodes [118–120]. carbon fibers. Nanomaterials. Lix MO2 (which represents a lithiated transition-metal oxide usually applied in commercial cells) must conduct electronically. an appropriate inert conducting ionic– electronic nanocomposite. moving to the external circuit to power the load. The anode reaction for this type of material is as follows: discharge −−−−−→ Lix C charge C + xLi+ (electrolyte) + xe− . The overall electrochemical device may be set up in such a way that electron-transfer reactions are rapid and. (4) −−−−−→ The carbon host materials that have been studied include natural and synthetic graphites.

R. Li+ ions engage in an electron-transfer reaction that decreases the chemical potential of lithium in relation to its value in the anode and calls for the compensating electron. Gabrielli facile and. are likely the most effective structure. allowing a high cell voltage to be developed. which may be as small as 50 nm [10–13. Nanoscale materials for lithium ion storage devices are emerging as a successful solution for improving the rate capability [86.98 P. one may have discharge xLi+ (electrolyte) + xe− + LiCoO2 −−−−−→ Li1+x CoO2 . The importance of lithiated transition-metal oxides (Lix MO2 ) is that they are capable of accommo- dating large quantities of lithium per formula unit and have low relative molecular masses. the cathode functions as an electron acceptor and the previous reaction (6) can be expressed alternatively as follows: xCo4+ + xe− −−−−→ xCo3+ . The intercalation refers to the reversible insertion of mobile guest species into a crystalline host lattice. This requires a large electrode–electrolyte interfacial area coupled with short diffusion distances within the electrodes themselves [10–13. It is widely believed that these limitations in the rate capabilities of Li ion batteries are caused by slow solid-state diffusion of Li+ within the electrode materials. which allow Li+ ions to diffuse easily throughout the bulk of the crystal. Two kinds of geometry are commonly applied to achieve a faster solid-state diffusion. while the structural integrity of the host lattice is formally conserved [122]. The first geometry is based on . giving rise to high power and energy densities. 4. highly reversible to enable the battery to be rechargeable. ideally. Materials for cathodes and anodes (insertion electrodes) for rechargeable lithium batteries are called intercalation compounds and constitute a special class of elec- troactive material [122]. A battery’s rate capability is its ability to deliver a large capacity when discharged at high C rates (a rate of C/1 corresponds to the current required to completely discharge an electrode in 1 h). in the cathode. the battery’s delivery capacity decreases to a fraction of its low rate value. (6) Therefore. In the cathode. as depicted in Fig. Upon discharge. the reactions must be reversible.118–120]. Lix MO2 is usually mixed with carbon black to raise the electronic conduc- tivity. Lithium cobalt and nickel oxides are commonly used as cathodes (Li1−y CoO2 and Li1−y NiO2 ). Bueno and C. 123–125]. Considering electrodes composed of nanoscale electroactive materials. since these oxides possess the transition metal in a highly oxidized state. 113. 113.86. During high-power pulses required for transmission of digitized and compressed voice data. Considering the lithium cobalt oxide. which contains an interconnected system of empty lattice sites of appropriate size. tremendous interest currently focuses on the research and development of nanostructured Li ion battery electrodes. 118–120]. For this reason. The latter requirement suggests that layered structures.113. whose nanostructure clearly restricts the distance that Li+ must diffuse. cathode (7) If the battery is to be rechargeable. 86. high en- ergy density and high power density (the same as rate capabilities) can be achieved simultaneously.

Nanomaterials. a Nanofiber structure or a template-like membrane. cells designed in 3-D nanostructures are also emerging as a new possibility for specific applications in the category of lithium ion batteries. All the electrochemical cell devices discussed in this section are based on 2-D electrode configurations in which electrodes can be assembled from 0-D or 1-D nanostructures (see Figs. In other words. from the current collector. Nickel and metal hybrid nanocrystalline materials have also been developed. and nanostructured ma- terials offer improvements in terms of power density and durability by controlling the charge diffusion and oxidation state on a nanoscale level. but the same configurations will prevail. or MEMS. as batteries to power microelectrome- chanical systems. and b spherical-like particle-based nanostruc- ture. whether or not the layers are based on nanoscale materials. 113] connected spherical-like nanoparticles while the second is based on nanofibers that protrude. Thus. as discussed herein. 2 and 4). The use of nanostructured materials for batteries is not restricted to lithium ion batteries. commercial lithium ion batteries are based on a layer-by-layer construction of the cell.e. and Nanostructures 99 a <100 nm <100 nm 0 L b Fig. Furthermore. i. are continuous along the length L [113]. The length L determines if the nanos- tructured electrode will be considered 2-D or 3-D and is very important in modeling electronic and ionic transport in the nanostructured electrode [86. in fact. respectively). despite their excellent energy . The use of novel nanoscale materials will offer im- provements in gravimetric and volumetric energy densities (W h g−1 and W h L−1 . thin-film batteries..Electrochemistry. Note that real nanostructures are not so regular. 4 Schematic of a highly porous nanostructured electrode protruding from a current collector. this type of nanostructured electrode geometry allows for improved rate capabilities. but both nanostructured phase and electrolyte. brushlike.

Elec- trolyte for this kind of fuel cell must exhibit good chemical stability with respect to the electrodes and inlet gases. which is coated with an ultrathin layer of ion-conducting dielectric (electrolyte).2 Fuel Cells As mentioned earlier.10 < x < 0. Three-dimensional configurations offer a means to keep transport distances short and yet provide enough material so that the batteries are able to power MEMS de- vices for extended periods of time [85. 3. i. Anode and cathode must be porous to physically offer low resistance to the transport of fuel. which is particularly O2− ion-conducting with a minimum of electronic conductivity. The cathode material most commonly used is porous or mesoporous perovskite manganite with the formula La1−x Srx MnO3 (0.e. 126]. have high electronic conductivity. the fuel cell is a particular type of galvanic cell. and its thermal expansion must be compatible with other components. There are high-temperature and low-temperature fuel cells [11. At sufficiently high temperatures it is possible to use solid ceramic-oxide ion conductors that have very high conductivities exceed- ing 900◦ C. cathode (9) 2 . fall far short of being able to power a smart dust mote for 1 day. anode (8) The cathode must also display good electrocatalyst activity for the reduction of O2 and offer good electronic conductivity. Bueno and C. Examples of prospective 3-D cell architectures for charge-insertion batteries are (a) array of interdigitated cylindrical cathodes and anodes. For this kind of cell. Gabrielli per unit volume. The typical electrolyte used is ZrO2 with 8–10 mol% of Y2 O3 . and the remaining free volume is filled with an interpenetrating. and the consequences of the 2-D nature of thin-film batteries are easily overlooked. and be stable in the reducing environment. (b) interdigitated plate array of cathodes and anodes. It is important to stress that 3-D cells are different from the 3-D electrodes con- cept. a well-mixed combination of ceramic and metal. continuous anode [85. (d) aperiodic sponge architectures in which the solid network of the sponge serves as the charge insertion cathode. The cathode reaction is as follows: 1 O2 + 2e− −−−−→ O2− . the material traditionally used as anode is 35% Ni − ZrO2 /Y2 O3 cermet. The anode requirements are that it must be an effective oxidation catalyst. The anode reaction is as follows: H2 + O2− −−−→ H2 O + 2e− . 126]. 109.100 P. it must have a high density to inhibit the crossover of fuel. Here. (c) rod array of cylindrical anodes coated with a thin layer of ion-conducting dielectric (electrolyte) with the remaining free volume filled with the cathode material.R. as briefly described later. 127]. 35. we will simply describe two common types of fuel cell to illustrate their main principles of operation.. since it must serve as the current collec- tor.15).

Current collectors are porous plates of carbon or graphite and the cell reactions are as follows: H2 −−−→ 2H+ + 2e− . In their simplest designs. Nanomaterials.Electrochemistry. and particular problems are experienced with the cathodes.5a).. anode (10) 1 O2 + 2H+ + 2e− −−−−→ H2 O. the membrane electrode of fuel cells [90]. Another important fuel cell that can be built in anal- ogy to the solid oxide-based fuel cell is based on solid proton conductors. This cell is a low-temperature fuel cell (about 150◦ C). all hy- drated oxides tend to lose water and if conduction takes place at all. and Nanostructures 101 a Load b Load H2 O2 H2 O2 H2 H2 O H2 O O2 ANODE CATHODE ANODE CATHODE diffusion path diffusion path H O O2. and electrolyte are called solid-oxide fuel cells (SOFC) (see Fig. it must do so through the metal or the oxide ion. in view of the obvious fact that. it leads to the so-called solid- polymer-electrolyte fuel cell (SPEFE) or polymer-electrolyte-membrane fuel cell (PEMFC) (see Fig. 5 Schematic cross section of the simplified planar anode–electrode–cathode structure of two typical fuel cells: a polymer-electrolyte membrane fuel cell and b solid oxide fuel cell. In the case of SPEFE or PEMFC. clusters of Pt or Pt/Ru or even other noble metals. at high temperatures. Several inorganic or organic solid proton conductors exist.g. It is important to mention that ZrO2 -based electrolyte. H + e− Fig. cathode (11) 2 Low operating temperatures dictate the use of noble-metal catalysts. are used in catalytic electrode layers. 3. because high-temperature solid proton conductors are still difficult or nigh impossible to obtain. can be used to decrease . See Color Plates Cells that operate using the aforementioned cathode. the electrolyte is criti- cal and is composed of a polymeric-membrane proton conductor based on polymers containing perfluorinated sulfonic-acid groups. such as nanoscale materials in SOFC systems. In fact. anodes and cathodes are formed either directly from metal particles or from catalyzed carbon particles bound to the membrane. anode. When an organic conductor is used. e. 3..g. Nanomaterials. they may not even exist at all. e.5b for a schematic representation of the operation of such cells).

Bueno and C. and Ta2 O5 . 128]. dyes. such as SnO2 . It is important to keep in mind that electrolyte is based on organic solvent contain- ing iodide-tri-iodide at the counterelectrode. although it is possible to make relatively efficient devices.R. Another variant is a photogalvanic cell. Gabrielli the operating temperature of the fuel cell by increasing the ionic conductivity [102].. Provided the LUMO lies just above the conduction-band edge in energy. other mesoscopic oxides can also be used. which illustrates the mode of operation of a DSSC. In the manufacture of photoelectrochemical solar cell it is important to establish contact between the n-type semiconductor and an electrolyte in the presence of a re- dox couple of appropriate reversibility. the energy contained in the light allows current to flow through the circuit from the semiconductor to the metal counterelectrode. 6. 3. allowing the cycle to begin again. in which case it is possible to obtain a photoelectrochemical cell called a dye-sensitized solar cell (DSSC).e. Illumination of this junction then generates holes and electrons that are separated by the field. Hence. giving rise to an electrical cur- rent. The semiconductor nanoparticle most commonly used is the anatase form of TiO2 . With this type of photoelectrochemical cell. electrons are injected into the conduction band of the semiconductor. I− − − 3 + 2e → 3I ) and the circuit − is completed by diffusion of the I back to the dye-sensitized electrode (see Fig. this oxidized form of the dye can be rereduced.102 P. WO3 . If a kinetically facile redox couple is present in solution. ZnO. Here.. our purpose is to show the operating princi- ples of DSSC cells and how nanostructures influence their efficiency and operation [71. forming close to a monolayer. This dye–semiconductor assembly is arranged over a transparent conducting oxide and the set is put into contact . again generating an electrical current [71]. 6b). which can be built provided its configuration is combined with materials called sensitizers. they are frequently plagued by stability- related problems because the semiconductor is so easily corroded by the electrolyte under the strongly oxidizing or reducing conditions at the interface. In other words. intermediate temperature SOFC development will be tremendously influ- enced by nanostructured electroceramics. 6 for details) [71]. i. and that the iodide is regenerated by reduction of tri-iodide at the counterelectrode (i. thereby breaking free of dependence on fossil fuels. According to Fig. however.3 Photoelectrochemical Solar Cells We have seen how lithium ion batteries and fuel cells generally operate and how they are dependent on the prior conversion of energy into electrical energy. the dye (D) absorbs a photon. leaving an oxidized form of the dye on the surface. with the concomitant excitation of an electron from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). Dye molecules are chemisorbed onto the semiconduc- tor (Fig. Nb2 O5 .e. Solar energy conversion devices are able to complete the cycle by finding ways of directly converting solar energy into chemical or electrical energy.

This serves to close the electrical circuit with a second transparent conducting electrode (counter electrode) in which a catalyst is deposited to facilitate the redox reaction [71. which is characterized by the total depletion of the semiconductor due to the small size of the nanoparticles and porous structure [65]. . step 2: diffusion of I− to dye-sensitized elec- trode. 87]. step 5: recombination. a Represents the different steps involved in energy conversion. 80. and Nanostructures 103 a D+/D* 4 hν 4 6 hν Vph 5 O/R O/R 1 3 SnO2/Pt 2 D+/D b nanostructured semiconducting + N oxide glass substrate N+ OH P O O OH + + N N P O O OH O + P N O + adsorbed dye molecules N Fig. Nanomaterials. Step 1 represents the regeneration of iodide by the reduction of tri-iodide at the counter electrode. composed of a network of nanoparticles that have been sin- tered together to establish electronic conduction. b Represents the dye molecule adsorbed on nanoparticles (based on appropriate semiconducting oxide) of the nanostructured electrode with a redox electrolyte (as mentioned earlier. 6 Schematic of DSSC operation for conversion of light into electrical energy.Electrochemistry. The horizontal line represents the Fermi level/redox potential/electrochemical potential of the electron. the electrolyte most commonly em- ployed is the iodide-tri-iodide redox system embedded in an organic solvent). Photoelectrochemical processes are substantially accelerated when they pass from massive to nanosize semiconductors. step 3: restoration of dye to the original state through electron donation by the electrolyte. Another important point to be emphasized regarding the nanosize effect in pho- toelectrochemical processes is the photoelectrolysis of water for hydrogen produc- tion [71] through solar energy. allowing for the generation of high photovoltages upon illumination [71]. 130]. As can be seen. The Fermi level in the dark is therefore near the bandgap center. and finally. Unmistakable nanosize effects can be observed in photoelectrochemical processes involving semiconducting particles separated from the metal surface by barrier layers. the heart of the device is the semiconducting mesoporous or nanocrystalline oxide. 79. step 4: photoexcitation of the dye and the resulting injection into the conduction band on the semi- conductiong oxide. The size effects are triggered by a shift of the absorption edge when the particle diameter ranges from 10 to 20 nm [129.

energy storage devices [16–24]. Nan- otechnology is therefore evidently important not only from this standpoint but also because it enables large surface areas to be obtained to optimize performance in terms of capacitance and ionic and electronic resistance. Bueno and C. However. which include electronic and ionic components for charging small pores rather than the ionic resistance between electrodes. Certain electrolytes display higher specific resistance than aqueous ones. 4 Concepts of Electrochemistry The general concepts and techniques used in more classical electrochemistry can be employed when electrodes or electrolytes are nanomaterials or nanostructured films. resulting in an increase in the equivalent series resistance. The goal . the amount of energy stored is given by the classical equation: CV 2 E= . 138–140]. in turn. they are all connected and easily accessible surface areas possessing low charging resistance. 24]. There- fore. i. Since the pores are open spaces in the entan- gled network. 22. which. it is important to consider appropriate boundary conditions.4 Electrochemical Double-Layer Capacitors Electrochemical double-layer capacitors (EDLC) or electrochemical supercapaci- tors (double-layer structures are explained in the next section) are like lithium ion batteries. Nanostructured metal oxide materials have also been inves- tigated for supercapacitor applications.R.. Nanostructured carbons have been developed to optimize high surface area in terms of capacitance and ionic and electronic resistance. An important point about EDLCs is the optimization of pore-size distribution for easy electrolyte access [132–134]. in terms of energy stor- age capacity. EDLCs fall in the gap between batteries and conventional dielectric devices. (12) 2 where V is the voltage and C the capacitance. (13) 4R where R is the equivalent series resistance.e. affects the maximum power according to V2 P= . to yield high-capacitance and low-resistance electrodes. The optimization of the operation depends on the electrolyte-supported voltages to reach the highest possi- ble level. although EDLCs have much higher power and a much longer cycle life (at least two orders of magnitude) [131].104 P. However. especially RuO2 and RuO2 · xH2 O nanotube composites [20. In carbon nanotubes. the main focus has been optimization of interparticle contact resistance and electrolyte wettability of the pores [17. Carbon materials contribute consider- ably to equivalent series resistances. Gabrielli 3. it is very important to develop materials with selected pore-size distribution [135–137].

passed during a period t. The total cell voltage required to bring about chemical changes by electrolysis is given by: V = E0C − E0A − |ηA | − |ηC | − IRcell . 146]. . When electrolysis occurs. (15) where E0C − E0A is the difference between the reversible potentials of the cathode and the anode in the cell. for instance. cyclic voltam- metry. The current I is a convenient measure of the rate of the global reaction and the charge q. The concepts could then be extended to other boundary conditions. to increase the rate at which an electrode reaction occurs. . in addition to electron transfer at the electrode. Nanomaterials. The rate of electrolysis will depend on the kinetics of the two electrode reactions. the potential of the studied electrode is measured with respect to a . when nanostructures are required. The charge required to convert m moles of material in an electrode reaction involving the transfer of n electrons per molecule is calculated using Faraday’s law: t q= I dt = mnF. some fundamentals of elec- trochemistry and an understanding of the methods’ theoretical backgrounds are helpful. 500 C mol−1 ). an electrochemical cell requires at least two electrodes – an anode and a cathode – to enable a current to flow through it. . and Rcell is the resistance of the electrolyte solution. . indicates the total amount of chemical reaction that has taken place. the initial aim of experiments is to separate charge transfer at the electrode from the mass transport of reactive species. It is usually essential to have an overpotential. which will be briefly reviewed in this section [97.1 Fundamental Concepts An electrochemical reaction is a heterogeneous chemical process involving the transfer of electrons between a metal or a semiconductor – the electrode. (14) 0 where F is the Faraday (96.Electrochemistry. for time techniques or frequency techniques are related to the elementary processes. η . chroamperometry. 4. After that. To understand how the current changes over time. We will begin by summarizing the fundamental concepts and then go on to the classical techniques: chronopotentiometry. As in classical electrochemistry using solid elec- trodes and aqueous solutions of electrolytes. and Nanostructures 105 of this section is to present the basic aspects of electrochemistry and techniques based on electrochemistry taking into account the classical boundary condition. according to the short picture given pre- viously. As explained earlier. impedance spectroscopy. In practice. 141–153]. The electrode reaction may be an an- odic (or cathodic) process when a species is oxidized (or reduced) by the loss (or gain) of electrons to (or from) the electrode. the reaction mechanism involved in the electrode must be detailed. and an ionic conductor – the electrolyte [141. ions must pass through the solution.

Eeq . which is used to polarize this three-electrode cell. Bueno and C. (17) nFA nF where j is the current density. (unit: cm s−1 ). therefore. (18) RT   α nF kc = k◦ exp (E − E ◦ ) . while ka and kc are the rate constants characteristic of the two processes of oxidation (anodic direction → ka ) and reduction (cathodic direction → kc ). With such laws. where ja = nFk2 cR (0.t) exp (E − E O ) − cOx (0.e. whereas the reduction rate constants tend to 0 and vice-versa when E decreases. (16) +k2 can be written as follows: I j = = k2 cR (0) − k1 cO (0).t) exp − (E − E O ) RT RT (20) At equilibrium potential. at the electrode surface.1 Kinetics of Electron Transfer Reaction at Interfaces The faradaic current relative to the following electron transfer reaction k1 O + ne− −−−− ←− −→ −− R. This behavior corresponds to the variation of the current density with respect to the potential E.106 P. one has I = 0. Its value is generally imposed by using a potentiostat whose details are given in all textbooks. (19) RT where α is the charge transfer coefficient.. such as:      α nF (1 − α ) nF j = nFk◦ cR (0. .1.t) and jc = −nFk1 cO (0. The concentrations involved in the expression of the rate are those existing at the location of the reaction. when E increases.t) are the anodic and cathodic com- ponents of the total faradaic current. j = ja + jc . the oxidation rate constant increases expo- nentially. Their value changes with the potential as follows:   ◦ (1 − α )nF ◦ k1 = k exp − (E − E ) .e. i.R. which is x = 0. Gabrielli reference electrode immersed in the cell.. i. 4.

(23) c∗R RT c∗O RT Figure 7 shows the current–voltage curve j = f (η ) and the partial current densities ja = f (η ) and jc = f (η ).8 −1.4 Total current I 0. Nanomaterials. the concentrations at the electrode of species R and O are equal to their value in the solution.t) exp (Eeq − E ) = cO (0. i. j. limiting diffusion current densities: jal and jcl . At low overvoltages: nF j ≈ jeq η. (22) nF c∗R At this potential.t) (1 − α )nF j = jeq exp η − exp − η . can be written in the Butler–Volmer form with respect to the overvoltage η = E − Eeq :      cR (0. as there is no current. j > 0 when | ja | > | jc | (for η > 0). and j < 0 for | ja | < | jc | (for η < 0).t) exp − O (Eeq − E ) O (21) RT RT In addition.6 −0. Hence.2 100 200 300 400 400 −300 −200 −100 h.. without mass transport limitation is plotted (dotted line) . and Nanostructures 107     α nF (1 − α )nF cR (0. the curve j = f (η ) where kinetics is the only rate-limiting step. The current density. At equilibrium where j = 0.4 −0.Electrochemistry.0 −Ii Fig. 7 Current–voltage curve j = f (η ) for mass transport limitation (continuous curve) and partial current densities ja = f (η ) and jc = f (η ) (dashed line). | ja | = | jc | = jeq . | j1 | = | j2 | = jeq .8 Ia 0.t) α nF cO (0. (24) RT I/ Ie Ii 1. so: RT c∗O Eeq = E O + ln .e. which is the exchange current at equilibrium potential (E = Eeq ). For comparison.2 Ic Ieq −0. mV Eeq −0.0 0.6 0.

Conversely. This concentration gradient produces transport by diffusion.108 P. i. • The consumption or the production of a species at the electrode surface leads to a decrease or an increase of the concentration of this species in the vicinity of the electrode. on the contrary. when jeq is low.1. a large value of k◦ and a low value of the charge transfer resistance are associated.   cR (0. 149]: • For ionic species.e. the charge transfer is equiv- alent to a resistance called charge transfer resistance at the equilibrium potential.e. a movement of the ensemble of the electrolyte produces transport by convection (i. Hence: • For η  0. (26) c∗R RT This relationship called Tafel relationship was proposed empirically in 1905. (27) c∗O RT The system is considered fast if jeq is large. an electric field in the solution produces transport by ionic electromigration. so the system is considered slow. Various transport modes can occur [147.2 Mass Transport Phenomena Involved in Electrochemical Processes Because electrochemical reactions are localized at the contact between the electrolyte and the electrode. the rate of the reduction process (cathodic) is practically 0 and the oxidation process (anodic) is dominant. (25) nF jeq In contrast. and the flux of the electric . equilibrium is established between the fluxes imposed by the various transport processes on the one hand. it is the reduction process (cathodic) that is practically preponderant:   cO (0. 4.R. Gabrielli In the linear range of the current–potential relationship.. • For η 0. In the permanent regime. one of the two exponential functions is preponderant. Bueno and C. • In liquid electrolytes. (Rt )eq RT 1 (Rt )eq = . k◦ is also low while the charge transfer resistance is large.t) α nF j ≈ ja = jeq exp η . far from the equilibrium potential (large overvoltages). an electrochemical reaction can evolve only if the electroactive species involved is present on the surface. stirring or flowing of the electrolyte or electrode movement).. This means that the dis- solved species arrives at the electrode surface by some transport process through the electrolyte in which it is initially homogeneously distributed.t) (1 − α ) nF j ≈ jc = jeq exp − η .

. (30) If the migration of each ion is independent of the migration of the others. → − Ionic electromigration in bulk electrolytes. Ji . This relation- ship implies that the global rate of the electrochemical process depends not only on the kinetics of the reaction occurring at the electrode but also on the mass transport kinetics.e. which is valid at infinite dilution. The flux density of the ion. This ionic movement of all the mobile ions maintains the electroneutrality of the solution. or both. anions and cations migrate in opposite directions: anions migrate toward the anode and cations toward the cathode. Because of the opposite signs of their charge. one has O + ne− → R. where κ = F ∑i zi ui ci is the conductivity of the electrolyte (S or Ω−1 ).. j = κ E . The electric field E = −Δφ (where φ is the potential in the bulk electrolyte) is the driving force for the electric charges. the rate-determining step of the global process can be controlled by either the reaction kinetics or the mass transport. (32) j = nFJOd ∗ = −nFJRd ∗ . This equilibrium is traduced by a relationship between the mass flux and the current density corresponding to the electrochemical reaction. which is the sum of the partial conductivities κi = Fzi ui ci for each species i. (33) by counting the fluxes leaving the electrode positively and the fluxes going toward the electrode negatively. → − → − J i = −ui ci ∇ φ (Ji in mol cm−2 s−1 ). Nanomaterials. (31) i i → − → − i. positive for a cation. is defined as the number of moles of the ion crossing a unit surface perpendicular to the transport direction per time unit. For an electrochemical reaction. then: → − → − → − j = ∑ j i = −F ∑ (zi ui ci ) ∇ φ . Jid ∗. and Nanostructures 109 charges transferred across the interface to produce the electrode reaction on the other hand. Therefore. (28) where ui is the electric mobility of the ion. and negative for an anion. (29) The electric quantity brought by the flux of the ion i (with charge zi ) is the current density (charge flux): → − → − → − j i = Fzi J i = −Fzi ui ci ∇ φ .Electrochemistry. The electrolytic current can be related to the mass flux densities at the electrode surface. Under its influence each ion gains a speed: → − → − v i = −ui ∇ φ . Transport by diffusion.

When a diffusion gradient is superimposed on this convection regime. of a motionless limiting layer with a thickness δN where diffusion occurs. which is based on the hypothesis of the formation. Fick’s second law is as follows: ∂ ci ∂ 2 ci = Di 2 . Fick’s second law for one-dimensional transport is as follows: ∂ ci ∂ 2 ci ∂ ci = Di 2 − v . at the electrode surface. which imposes a speed v on the electrolyte. called the Nernst diffusion layer. (39) ∂ x2 ∂x A very simplified model of the convective diffusion was introduced in electrochem- istry by Nernst (1904). Bueno and C.R. In this layer.110 P. the concentration gradients and the diffusion fluxes remain restricted in a layer. close to the electrode. (36) ∂t ∂x Transport by diffusion-convection. (41) ∂x δN . Gabrielli The flux density of species i transported by diffusion is equal to: → −d → − J i = −Di ∇ ci . Fick’s equations are easily solved: ∂ 2 ci =0 (40) ∂ x2 leads to ∂ ci c0 − c∗i = cte = i . (37) In this condition. which becomes as follows: ∂ 2 ci ∂ ci Di =v . (35) ∂x In the same way. The differential equation of the steady-state regime is obtained for ∂ ci /∂ t ≡ 0 in the general equation. (34) For a one-dimensional diffusion. is taken into account. If transport by convection (natural or mechani- cally imposed). Hence. if Di is independent of ci . the convective diffusion law is obtained. the density of the global flux is as follows: → − dc → −d → −c → − J i = J i + J i = −Di ∇ ci + ci → − v. (38) ∂t ∂x ∂x The solution for these equations requires complete knowledge of the velocity of the liquid. which depends on the mechanical device used to impose the convection. Fick’s first law is obtained: → −d ∂ ci J i = −Di . in the steady-state regime.

the concentration of the species in the homogeneous solution. The compensating charge on the electrolytic solution side is due either to an ex- cess of cations compared with anions. layer in the solution where the ionic distribution is not electrically neutral is much larger because of the size of the solvated ions.e. Hence. the concentration profile changes progressively from a linear variation close to the electrode to c = c∗ far from the electrode. depending on the sign of Δφ . Their centers are located in a plane (called Helmholtz plane). and c0i = c(x = 0) is the concentration at the other limit. The profile of the concentration is given in Fig. Nanomaterials. instead of the angular point at x = δN .Electrochemistry.1 A). or to an excess of anions compared with the cations (when the electrode is positively charged). The steady-state current density related to this diffusion flux is as follows:      nF d   nF d 0  stat    ∗  | j | =  Ji.. 8.3 The Electric Double Layer at Interfaces The accumulation of electric charges (nontransferable across the interface in the absence of electrochemical process) on each part of the interface results from the existence of mobile charge carriers in the two phases in contact with each other and an interfacial potential difference (Δφ El/sol = φ El − φ sol ) [153]. The charge brought by the electrode itself (qEl ) is constituted either by an excess of electrons (negative charge) or by a shortage of electrons (positive charge). . In reality. 4. i. The charge accumulated on one side of the interface is counterbalanced by the charge accu- mulated on the other side: qsol = −qEl . at the electrode.1. Double-layer structure. and Nanostructures 111 where c∗i is the concentration at the external limit of the diffusion layer (x ≥ δN ). It is generally assumed that the ions can approach the electrode only at a distance of a few angstroms. (43) νi νi where kid = Di /δN (cm s-1) is the diffusion transport rate across the Nernst layer. the steady-state flux is equal to: c0 − c∗i d Ji. The Helmholtz layer (or compact layer) would contain only solvent molecules oriented by the electric field.stat = −Di i (42) δN (∂ ci /∂ x > 0 and Ji < 0 for a species consumed at the electrode and ∂ ci /∂ x < 0 and Ji > 0 for a species produced). for Δφ < 0 (when the electrode is negatively charged).stat  =  ki (ci − ci ) . (44) where q represents the charge per surface unit (C cm−2 ). ˚ the thickness of the If the charged layer at the electrode surface is thin (< 0.

On the other hand. 8 Concentration profile of the electroactive species dissolved in the diffusion layer. Therefore. those that are specifically adsorbed (anions) are directly in contact with the elec- trode surface. . this is actually more complex.R. there are two Helmhotz planes. Bueno and C. They constitute the diffuse layer (or Gouy–Chapman layer). b species produced by the electrochemical reaction. The ions that are not adsorbed (gen- erally cations) are kept at a certain distance from the electrode by their solvation shell and by a layer of solvent molecules adsorbed on the electrode. Gabrielli a C(x) Cs (real profile) C* steady-state flux 0 δN x steady-state homogeneous diffusion layer solution (NERNST hypothesis) b C(x) steady-state C* flux Cs 0 δN x Fig. and in real values However.112 P. a Species consumed by the electrochemical reaction. the ions accumulated close to the electrode are under the influence of the thermal movement. Conversely. The concentration profiles are represented in the Nernst hypothesis (continuous curve).

τ = Cd Rcell . Its thickness is in the order of a few tens of Angstroms. Rcell . is thus equal to: 1 1 1 = + . Contrary to other techniques. In electrochemistry. chemical. etc. Nanomaterials. thanks to the advances in electronics. 151. Cd . because electrical quantities are easy to use and provide in- formation directly relating to the behavior of the interface. If a continuous change of the potential is imposed at the electrode. it proves in- adequate as the degree of complexity of the processes and their coupling increases. (45) Cd Cdiff Ccomp Capacitive current. which need no alteration of the electrode surface. or X-rays: EXAFS). The capacity of the double layer. (47) dE dt dt If E varies like E = Ei + bt. and Nanostructures 113 The ensemble Helmholtz layer/Gouy–Chapman layer constitutes the electro- chemical double layer. and the cell resistance. This layer is generally represented by the series combination of two capacitances relative to the diffuse and compact layers. a continuous capacitive current appears. One begins by studying the steady-state regime. The charging of the electrode/solution interface leads to a ca- pacitive current when a variation of the interfacial charge occurs: dqEl jcapa = .Electrochemistry. 153]. The decrease is very short (lower than 1 ms) since the time constant. Auger electron spectroscopy. 4. and/or electrochemi- cal reactions) requires the use of techniques to control the state of the electrode and to analyze the behavior of the interface. Although this study sometimes suffices for simple processes. In addition. which re- quire a vacuum chamber [low-energy electron diffraction (LEED). experimentalists can use more and more sophisticated . a permanent capacitive current is observed: dqEl dE dE jcapa = = Cd . they are particularly useful to identify interfacial processes. Nonsteady-state techniques must then be used [148.] or electromagnetic radiation (optical: ellipsometry. The capacitive current shows an exponential decrease relating to the values of the double layer capacity. Cdiff and Ccomp . (46) dt This phenomenon occurs when the electrode potential is changed as qEl changes with E. is in the order of a few tens of microseconds. Cd . which is pro- portional to the rate b.2 Techniques Used for Investigating Electrode Reactions To determine the elementary processes involved in a reaction mechanism occurring at an electrode/electrolyte interface (mass transport. electrical techniques can be used in situ on any surface state of the electrode.

However. oxido–reduction reaction without mass trans- port limitation) but is largely insufficient for multistep mechanisms with or without mass transport limitation. pressure. by means of a perturbation sine wave . They can be transposed to other quantities: pressure.. However. impedance measurements. the deriva- tion and the exploitation of the response of the interface to a large amplitude signal are often inextricable in complex processes. A perturbation of these quantities by the experi- mentalist changes the state of the system. By controlling the electrochemical reactions. the frequency response is usu- ally simpler. In potential step experiments. These electrical techniques will be only briefly presented. even in this condition. when complex heterogeneous reactions interact with mass transport. surface. with homogeneous chemical reactions. particularly where multistep electrochemical reactions occur. they give information on the rates of the reactions occurring at the electrochemical interface and provide a certain characterization of the intermediates. etc. In some very favorable situations. The plot of the steady state current–voltage curve allows reliable data to be quan- titatively obtained only for the slowest step in the overall reaction scheme. the potential of the work- ing electrode is changed instantaneously and the current–time response is recorded. several techniques can have comparable ef- fectiveness. Analyses of the transient regime can lead to information on these parameters and on the phenomenological equations that relate to them. For more complex systems. These techniques are restricted to pure electron trans- fer under mass transport limitation coupled. allowing for easy exploitation of experimental results. which can be used to clarify the phenomena involved at the interface between an electrode and an electrolyte. since de- tails can be found in reference books. rotation velocity of the electrode. However..R. the use of electrochemical quanti- ties allows for kinetic studies whereby the various elementary phenomena can be dissociated. The principle of the nonsteady-state techniques (also called relaxation tech- niques) is based on the fact that the steady state depends on some quantities (potential. In this way. Therefore. the monoelectronic steps of the reaction mechanisms can be distinguished and the often unstable intermediates involved in the reactions can be counted. the time transient response is generally very complicated. This may suffice for very simple systems (i. These techniques are known as chronoamperometry and chronopotentiometry when the potential response to a current step is recorded. Therefore. Gabrielli instrumentation. Although these techniques do not lead to an identification of the chem- ical bonds or the intermediates in the chemical sense. temperature).e. and their various couplings. The rate at which it tends to a new steady state depends on its characteristic parameters: reaction rate constants. one is well advised to use small signal techniques and particularly impedance spectroscopy. Sometimes it is appropriate to use chronocoulometry by plotting the total charge (determined by integration of the current) with respect to time. Bueno and C. In contrast. or not. diffusion co- efficient. analyses of the current or potential time transients lead to poor results if a reaction mechanism has to be resolved. temperature. low-amplitude signals are often used in electrochemistry. due to the nonlinearity inherent to electronic transfer. A frequency analysis is then more effi- cient.114 P.

capacitive loops related to diffusion char- acterized by a 45◦ part with respect to the real axis. and impedance spectroscopy. 44. On the other hand. An example will be given in the following paragraph. Nanomaterials. In the lower frequency range. 572.Electrochemistry. 38. . Plotted in the complex plane (Re[Z( f )]). 51. The latter approach will be developed later. These techniques are based on an analysis of the current response (or potential) to a low- amplitude perturbation. 47. On the other hand. In electrochemistry.141–153]. impedance techniques are increasingly used in electrochemistry as well as in academic studies or industrial applications to characterize electrode processes to dissect overall electrochemical processes. The impedance is measured with a frequency response analyzer. n◦ 8/9 (2006). after linearization. Among the nonsteady state techniques. one can observe capacitive or inductive semicircles. a special issue devoted to impedance techniques was published by J. one can look for a model involving kinetic equations describing the reactions and mass transport and. using transmission lines to describe the behavior of porous electrodes. where nonlinear behavior occurs because of the reaction rate constants. of the potential (or current). a capacitive loop is related to the parallel arrangement of the charge transfer resistance and the double-layer capacity. n◦ 7/8 (1996). which depend ex- ponentially on the potential. which can be compared with the experimental data. one can look for an equivalent circuit hav- ing the same impedance. the use of low-amplitude signal allows the system to be linearized. The experimental results can be in- terpreted in two ways. have been widely developed [97. the electrochemical nonlinear system is approximated by a linear system around the polarization point. n◦ 14 (1993). the high-frequency limit generally gives the electrolyte resistance and the low-frequency limit – the polarization resistance (inverse of the slope of the current–voltage curve). which represent the re- laxations of the reaction intermediates. often sinusoidal. Electroanal. This measurement is then repeated all along the current–voltage curve in the studied potential range. n◦ 24 (1999). On the one hand. chronoamperometry. Examples of applications of impedance analyses to various problems can be found in the special issues of Electrochimica Acta. n◦ 13/14 (2002). Chem. The measure- ment is carried out at constant polarization potential. n◦ 2 (2004). and negative resistance for passivation. and Nanostructures 115 signal with low amplitude in a wide frequency range.-Im[Z( f )). namely linear voltammetry. The electrochemical system is polarized using a potentiostat or a galvanostat. n◦ 10 (1990).001 Hz). Impedance is a quantity defined for a linear system. To illustrate the various techniques. as soon as the electrode has reached a steady state. The impedance gives information on the processes occurring at the interface (electrochemical and chemical reactions and diffusion) and on the structure of the interface. In the high-frequency range. 41. the same redox process limited by mass transport will be analyzed by three different methods. by varying the analyzing frequency in a large-frequency do- main (often from 50 kHz to 0. Therefore. calculate a theoretical impedance. which follow the Inter- national Symposia on Electrochemical Impedance Spectroscopy (EIS) that are held every 3 years: Electrochimica Acta 35.

Bueno and C.R. Gabrielli If an oxido–reduction reaction occurs between species O and R. 0) = c∗R .t) ∂ cR (x. +k2 where the reaction rate constants are     nF nF k1 = k10 exp −(1 − α ) E and k2 = k20 exp α E . c∗O and c∗R : for t ≥ 0 and x → ∞ one has cO (x. (52) Then. at a certain distance from the electrode sur- face.t) = DO (49) ∂t ∂ x2 ∂ cR (x.t) − k1 cO (0. such as: k1 O + ne− −−−− ←− −→ −− R.t) DO + DR = 0. and the concentrations of O and R species are then equal to c∗O and c∗R : for t = 0 one has cO (x.t) → c∗O and cR (x.116 P. that the concentrations of the species are equal to those found in the bulk electrolyte. (53) ∂t x=0 ∂t x=0 . with concentra- tions cO and cR . and their concentrations obey the following: ∂ cO (x. (b) The boundary conditions impose. (51) ∂x ∂z nFA where the faradaic current is given by the law of heterogeneous kinetics: IF (t) = nFA[k2 cR (0.t)].t) → c∗R . at t = 0. The fluxes of the O and R species are the same and are equal to the faradaic current (Fick’s first law): for t ≥ 0 and x = 0 one has ∂ cO ∂ cR IF (t) DO (0. 0) = c∗O and cR (x.t) = −DR (0. express the homogeneity of the electrochemical solution before switching on the current.t) 2 = DR .t) = . at the electrode surface. (48) RT RT the concentrations of species O and R should diffuse with coefficients DO and DR in the direction x perpendicular to the electrode surface. (a) The initial conditions.t) ∂ cR (x. (x = 0):     ∂ cO (x.t) ∂ 2 cO (x. (50) ∂t ∂ x2 The initial and boundary conditions describe the experimental conditions. (c) The boundary conditions at the electrode surface are imposed by the charge and mass balance.

2. and Nanostructures 117 4. (56) where ν is the rate of the potential sweep. the potential can be written as follows: RT cO (0. 4..t) = = DO . it can be shown that [146]: 1 CO (0.1 Linear Sweep Voltammetry For linear sweep potential voltammetry and chronoamperometry.2. the potential changes are expressed as follows: E(t) = Ei − vt.t)   cO (0. 9.2 Chronoamperometry In the case of chronoamperometry. (59) 0 (σ t − z)1/2 1 + DDR0 exp [σ (Ei − vt − E 0 )] where σ = (nF/RT ).t) E = EO + ln (54) nF cR (0.t) = CO∗ − [nFA(π DO )1/2 ]−1 i(τ )(t − τ )dτ .t) nF or = f (t) = exp (E − E ) . for a reversible redox process limited by diffusion. a reversible elec- trochemical reaction. If. (57) nFA ∂x x=0 Hence.t) −JO (0.Electrochemistry. Nanomaterials. The results of this integration are given in Fig. If E(t) is imposed on an electrochemical interface where a reversible redox reaction occurs from a potential . O (55) cR (0. is considered. the interpretation of the voltammograms relative to more complicated reaction mechanisms such as processes involving adsorbed intermediates becomes much more difficult.e.t) RT For linear sweep voltammetry. (58) O The change of the current with respect to the potential can be obtained from the numerical integration of: σt i(z)dz nFAc∗0 (π D0 σ )1/2 =  1/2 . linear cyclic voltammetry allows quantitative results to be obtained in a relatively short time. i. Thus. a redox process for which the reaction rate constants k1 and k2 are assumed to be very large. The flux at the electrode is proportional to the current intensity:   I(t) ∂ CO (x. E(t) is a potential step.

(62) πt i.R. (63) nF DO The concentration repartition with respect to the distance x is given by: . I(t). can be obtained by using the Laplace transform: nFAD0 c∗0 1 1/2 I(t) = √ (60) πt 1 + νξ where    nF(E − E O ) DO ν = exp and ξ= . obtained for E → −∞. I = Il /(1 + νξ ) and E = E1/2 + (RT /nF) ln(Il − I)/I. (61) RT DR The limiting diffusion current.3 Ep/2 Current 0. where the half-wave potential is equal to  RT DR E1/2 = E O + ln .. Bueno and C.e. Gabrielli Ep ip E1/2 0.2 0. is equal to: nFAD1/2 c∗ Il = √O O. 9 Voltamperogram with linear sweep of potential where there is no current to a more negative potential. Il .4 0.118 P. the current response.1 0 +100 0 −100 E-E1/2 Fig.

e. (64) 1 + νξ 2 DOt   ∗ ξ x cR (x. 1 + νξ 1 + νξ The solution of nonlinear evolution equations in the time domain is known ana- lytically only in very simple cases such as reversible redox processes limited by diffusion.t) = cO 1 − erfc √ . (66) π 1/2 0 Therefore.t) − k1 cO (0. By eliminating the terms in exp( jω t) on the two sides of the following relationship.2. The faradaic current associated to this process is then: IF (t) = nFA(k2 cR (0. Nanomaterials. is ob- tained by differentiating the equations describing the value of the faradaic current and mass transport. the corresponding current response.. These drawbacks are largely eliminated if the amplitude perturbation is limited to a sufficiently low value to allow the equations to be linearized. the solutions found to express the response to a perturbing signal depend specifically on the form of the perturbation.t) = c∗O .3 Electrochemical Impedance Here. nFA RT RT ∂ 2 Δci (x) jω Δci (x) = Di . one has the following when there is a transport limitation by diffusion: ΔIF (1 − α )nF α nF = k1 c¯O (0)ΔE − k1 ΔcO (0) + k2 c¯R (0)ΔE + k2 ΔcR (0). the treatment of nonsteady-state techniques generally requires calculations that are at least partially numerical. (68) ∂ x2 . In this case. as in the previous examples). (67) When a small amplitude perturbation ΔE exp ( jω t) is applied to the interface around the polarization potential. In addition.t) = c∗O 1 − and cR (x. analyses in the frequency domain are very powerful. and Nanostructures 119    ∗ 1 x cO (x.Electrochemistry.t)). (65) 1 + νξ 2 DRt where the function erfc(z) is defined by: z   2 erfc(z) = 1 − exp −y2 dy. the concentrations at the electrode surface are as follows:   1 ξ cO (0.t) = cO erfc √ . ΔIF exp( jω t). the process is not con- sidered fast (k1 and k2 are not infinite. For electrochemical nonlinear systems. the redox process is supposed to be irreversible. 4. i.

motionless solution). Mi = 0. c¯i (x) is the concentration of the species. the quantities exp( jω t) are only taken into account implic- itly. even if simply for the sake of derivation convenience. (72) Di Di The integration constants Mi and Ni result from the boundary conditions and depend on the hypothesis of the diffusion layer thickness. such as: ci (x.. Charge transfer resistance Rt . the preexponential terms ΔIF and ΔCi (x) also depend on the pulsation ω . otherwise Δci → ∞ when x → ∞. (73) Di By putting this value in the boundary conditions at the electrode surface. Diffusion layer of infinite thickness (e.t) = c¯i (x) + Δci (x)exp( jω t). one has:   jω jω ΔIF (t) = −NO nFADO exp( jω t) = NR nFADR exp( jω t). for a steady state polarization. (69) These equations lead to two important concepts: the charge transfer resistance and the Warburg impedance.t → ∞). Warburg impedance. (71) Rt RT where c¯i = ci (0.g. Bueno and C. (74) DO DR After elimination of the integration constant Ni between the last two equations: . In this case. and one has:    jω Δci (x) = Ni exp −x . Gabrielli where Δci represents a small variation of ci and i represents the indices O and R. The resulting perturbation of the concentration Δci (0.R. The charge transfer resistance is defined by:   1 ∂ IF = . at a distance x from the electrode. (70) Rt ∂ E ci The linearized expression of the faradaic current leads to: 1 n2 F 2 =A [(1 − α )k1 c¯O + α k2 c¯R ] .120 P. It must be kept in mind that.t) is de- duced from the general solution of the equation: ∂ 2 Δci (x) jω Δci (x) = Di ∂ x2 obtained after the terms in exp( jω t) have been cancelled:       jω jω Δci (x) = Mi exp x + Ni exp −x .

10). Diffusion layer of finite thickness (diffusion + convection). therefore. obtaining the kinetic quantities from the simple extrapolation of the 45◦ straight line can be difficult. 10 indicates. and Nanostructures 121 ΔcO (x = 0) 1 =− √ . The limiting value of the impedance when the frequency tends to infinity is equal to Rt . Cd . intercepts the real axis at: R0 = Re + Rt − R2t λ 2Cd . depending on the relative values of the parameters describing the charge transfer and species diffu- sion. Nanomaterials. By taking into account the double-layer capacity. (75) ΔIF nFA jω DO ΔcR (x = 0) 1 = √ . one obtains the Randles equivalent circuit [150] (Fig. except if λ 1. √ In the expression of the faradaic impedance. . δN ci (x.t) + [c∗i − ci (0. It can be shown that the high-frequency part of the impedance diagram plotted in the complex plane (Nyquist plane) is a semicir- cle representing Rt in parallel with Cd and the low-frequency part is a Warburg impedance. the extrapolation of the 45◦ straight line. (79) Various shapes can be obtained for the impedance diagrams. Re . (78) ΔIF jω  √   √  where λ = kd / DOx + ki / DRed . Hence.t)] for x < δN . the change of the faradaic current with respect to the potential is obtained:   1 k1 k2 ΔI ΔIF = ΔE − √ +√ √ F (77) Rt DO DR jω and. We now use the Nernst hypothesis. where the faradaic impedance ZF is represented by the transfer resistance Rt in series with the Warburg impedance W . As Fig.Electrochemistry. x ci (x. which assumes that the concentration of the reacting species that diffuse changes linearly in a layer of thickness δN and is constant thereafter. which represents the Warburg impedance. the charge transfer and diffusion phenomena are well separated. the term Rt λ / jω is usually called the Warburg impedance.t) = c∗i for x ≥ δN . the impedance is equal to:   ΔE λ ZF (ω ) = = Rt 1 + √ . (76) ΔIF nFA jω DR Thus. since. and the electrolyte resis- tance.t) = ci (0. in that case.

Bueno and C. 10 Electrochemical impedance for a diffusion layer of infinite thickness. the general solution of the diffusion equation leads to the following equation for the boundary condition at x = δN :       jω jω Δci (x = δN ) = Mi exp δN + Ni exp −δN = 0 for x ≥ δN Di Di    jω so Mi = −Ni exp −2δN δN       jω jω and Δci (x) = −2Ni exp −δN sinh (x − δN ) for x < δN Di Di . b Scheme of the impedance in the complex plane where δN is the thickness of the Nersnt diffusion layer. a Randles equivalent circuit. Gabrielli a Cd Re W Rc t b Re Re + Rct Rct 2 λ 2 Cd Fig.R. Thus.122 P.

then: ⎛  ⎞ tanh δN DjωO ZF (ω ) = Rt ⎝1 + (k1 + k2 ) √ ⎠.05 . 11 Faradaic impedance ZF (ω ) plotted for a finite thickness of the diffusion layer (Nernst hypothesis) (frequency in Hz). (c) If DO = DR .07 . (81) jω DO jω DR This impedance is represented in Fig. then Di Di Di  jω ΔcR (0) 1 1 ki tanh δN DR = W (ω ) = √ (80) ΔIF nFA δN nFA jω DR and the faradaic impedance is equal to: ⎛   ⎞ tanh δN DjωO tanh δN DjωR ZF (ω ) = Rt ⎝1 + k1 √ + k2 √ ⎠.03 . Nanomaterials.002 Rt kf δN Rt Re (Z) D0 Fig. as follows:  jω tanh δN D tanh(y) → 1 when y → ∞.24 . and i i (b) When δN → ∞. the Warburg impedance is obviously found again.14 .18 . It is noticeable that: (a) When ω → ∞. (82) jω DO Therefore.07 .03 −Im(Z) . if the double-layer capacity is considered. there is a coalescence of the 45◦ straight line and the high- . and Nanostructures 123 . the Warburg impedance is found in the high-frequency range. 11. therefore: √ jω D i ≈ √ j1ω D .09 .Electrochemistry. For comparison. the impedance is also plotted (dotted lines) for an infinite thickness of the diffusion layer        jω jω jω and ΔIF = 2nFANi Di exp −δN cosh δN .40 1 . as for the diffusion layer of infinite thickness.02 .02 .05 .11 .01 4 20 .

b1 and b2 . which is adsorbed at the electrode surface.124 P. Using the same approach. even for a reversible redox process. Bads becomes (1 − θ )k1 cA . by assuming a Langmuir adsorption isotherm. The formation rate of Bads is equal to k1 cA for a first order reaction in A.4 to 0. then Bads becomes β θ k2 . If θ is the fraction of the electrode surface covered by this adsorbate and β is the superficial concentration for a complete coverage by Bads . the oscillation above the Warburg straight line (at frequencies from 0. it was shown that.R. we will now examine the case of a multistep reaction. The kinetic parameter whose evolution governs the impedance is the concen- tration of the intermediate Bads in the adsorbed phase. 11. By taking into account the available area fraction. A numerical calculation taking into account the convection term in the transport equation showed that the impedance diagram is below the Warburg straight line. The consumption rate of Bads is equal to k2 β . The reaction rate constants are equal to: k1 = k10 exp (−b1 E) and k2 = k20 exp (−b2 E) . the impedance approach allows the more difficult case of an irreversible (finite reaction rate constants) redox process to be derived. C. . Thus. k Second step: Bads + e− −−−→ 2 Csol . which is very difficult to investigate using techniques of potential step cyclic voltammetry. the surface concentration of Bads is cB = β θ .4 Two-Step Charge Transfer with an Adsorbed Intermediate A species A in the solution should react at the electrode to give a species.2. 4. Bueno and C.14 Hz)) is related to the Nernst hypothesis. (83) In Fig. through a reaction intermediate B. • The evolution equation describes the balance of β θ and expresses the mass con- servation: β (dθ /dt) = formation rate – consumption rate. In contrast. By taking into account the area fraction occupied by Bads . the derivation of the current response in the time domain is far from simple. and the straight line crosses the real axis at: R0 = Re + Rt − R2t λ 2Cd . the reaction mechanism follows: k First step: Asol + e− −−−→ 1 Bads . are positive. Gabrielli frequency circle. where the Tafel coefficients. Within the electrochemical framework of this classical example of a redox pro- cess whose rate is limited by the transport by diffusion.

of the evolution equation at a polarization point Es . is obtained by putting d/dt ≡ 0. Thus. Nanomaterials. and I will be denoted by Δ. The coverage rate θ is not usually directly mea- surable. (84) dt where the values of the rate constants k1 and k2 are taken at the potential Es . (85) ΔE jωβ + k1 cA + k2 β For frequencies much greater than the rate constants. Solution of the linearized nonsteady-state equation. imposed by its evolution equation. k1 cA + β k2 The differentiation of I around the polarization point (θs . the kinetics of the variations of θ . Steady-state solution of the evolution equation. dt The potential E. The steady-state solution. i. The faradaic current I is the sum of the elementary currents of each step: I = −F((1 − θ )k1 cA + β θ k2 )... . E. θs = k1 cA /(k1 cA + k2 β ).e. which is perturbed. which leads to: (1 − θ )k1 cA − β θ k2 = 0. the linearized evolution equation is written as: dΔθ β = ((1 − θs )b1 k1 cA − β θs b2 k2 )ΔE − (k1 cA + k2 β )Δθ . and Nanostructures 125 The evolution equation for β θ is then: dθ β = (1 − θ )k1 cA − β θ k2 . Es ) gives: ΔI = F{((1 − θs )b1 k1 cA + β b2 k2 θs )ΔE + (−k1 cA + k2 β )Δθ }. At these high frequencies.Electrochemistry. the coverage is said to be frozen. The small amplitude changes of the quantities θ . the steady-state current is obtained: IF = 2F β θs k2 . By considering θ = θs in this equation. The so- lution of this equation for a sinewave potential perturbation of ΔE = |ΔE| exp( jω t) centered on Es is as follows: Δθ (1 − θs )b1 k1 cA − β θs b2 k2 = . by taking into account the steady-state value of θ β k1 k2 cA Is = −2F . does not explicitly appear in this equation but is implicitly involved through k1 and k2 . i. and will be calculated from the electrochemical current I. The impedance is the observable quantity. which means that Δθ /ΔE → 0.e. does not allow the perturbation of the po- tential to be followed. θs .

by substituting Δθ /ΔE and θs for their values. which is the limit of ZF when ω → 0. where θs = 0. which is the charge transfer resistance. the Rt Is product is a constant equal to: 2 Rt Is = . It is possible to ascertain that the polarization resistance. FZF k1 cA + k2 β (k1 cA + k2 β )( jωβ + k1 cA + k2 β ) When ω → ∞ ZF = (k1 cA + k2 β )/[F β k1 k2 cA (b1 + b2 )]. E) of the steady state behavior and the impedance of the two-step reaction mechanism when b1 > b2 . one obtains: 1 β k1 k2 cA (b1 + b2 ) β k1 k2 cA (b1 − b2 ) = + (−k1 cA + k2 β ) . For potentials lower than Ec . I1 and I2 : partial currents of the first and second steps. Upper part: variation of θ with respect to E . I: total current.5. The variations with the frequency of the faradaic impedance are determined by the sign of the numerator of the fraction coming from Δθ /ΔE.e. the impedance has an inductive loop. Ec is defined when the two steps have equal rates. Rp .5 0 log I E>Ec −Im[Z] ω=∞ ω=0 Rt Rp Re[Z] −Im[Z] ω=∞ ω=0 E<Ec Rt =Rp Re[Z] −Im[Z] Rp Rt ω=∞ Re[Z] ω=0 Ec E Fig. When ω → 0 ZF (0) = Rp . always remains positive and equal to the slope of the current–voltage curve.126 P. Bueno and C. b1 + b2 θs 1 0. whereas there is a capacitive loop for potentials greater than Ec . At this particular potential. which is the polarization resistance (i. 12 Scheme in the Tafel plane (log I. the slope of the current–voltage curve). For a two-step monoelectronic reaction mechanism.R. Gabrielli Then.5. the impedance is reduced to the charge transfer resistance Rt . Ec is the potential where I1 = I2 and θ = 0. Figure 12 shows the current–voltage curve and the impedance for b1 > b2 . This sign depends on the relative rate of the two steps of the total reaction..

98–101. respectively. Although the subject of porous theory has been extensively examined in the litera- ture [92. the effects associated with the capacitance of the ionic double layer at the electrode/electrolyte-solution interface.e. the best exam- ple of which are ac theory and impedance spectra representation. particularly due to the distributed nature of the pores . 95. or polarons). Therefore.101. and again the dimension of the liquid channel is very small... and Nanostructures 127 5 Porous (Nanostructured) Electrode Geometry As the use of nanotechnology in design electrodes and cells for energy conversion and storage devices continues to grow. For instance. Note that.189–199]. but the theory is usually applied in the ac regime [92. The transport and reaction processes occurring in nanostructured electrode can be understood by considering the electrochemical theory of porous electrodes. The transport of charge carriers in both phases is believed to be influenced by complex mechanisms.100. the desirable specifications for energy density and power density. Nanomaterials. This is true for EDLC or supercapacitors as well as for sec- ondary batteries and fuel cells. this corresponds to the assumption that the faradaic impedance is indepen- dent of potential or that the porous model may only be applied in the absence of dc current.e. The solid phase in contact with the conduct- ing substrate provides a continuous path for the transport of electrons (or holes. etc. i. 96. partic- ularly now that nanostructured electrodes are so widely applied and the capability to design different porous materials and electrodes for electrochemical applications continues to grow. but the dimension of the structural elements is extremely small. the system is characterized by the existence of two closely mixed phases in the electroactive nanostructured layer. where mainly small signal frequency-resolved techniques are used. who as- sumed that the interfacial impedance is independent of the distance within the pores to obtain an analytical solution. introduced in the previous section. In such a context. on the nanometric scale. the effect of the transport and reaction phenomena and the capacitance effects on the pores of nanostructured electrodes are equally impor- tant. The porous theory was first described by de Levi [92]. The porosity and nanostructures are very im- portant in energy conversion and storage devices. There- fore. one might deal with the ability of the electrolyte to penetrate the pores. displaying a large degree of disorder. It is a known fact that energy density decreases as the power density increases. 154–184]. contact with the very high surface area of the semiconductor is critical. thus. Because the dc potential decreases as a function of depth.Electrochemistry. with narrow channels for transport. The electrolyte penetrates the voids in the solid phase up to the substrate. with regard to energy storage devices. to apply the model. important aspects involving porous electrode theory will be presented and discussed in this sec- tion. The porous electrode theory was developed by several authors for dc conditions [185–188].. it continues to be of permanent interest. are related to capacitance effects. i. it is important to take into account the porous effect and how to characterize the electrode’s response to such porous and nanostructured architectures. The porous electrode theory is based on the fact that electrodes operate in contact with an electrolyte by simultaneous transport of electronic and ionic species in the solid and liquid phase.

the distance that Li+ must traverse to diffuse through the solid state (the current. The usable energy stored in EDLCs or Li-ion batter- ies diminishes as it is extracted at higher discharge rates. 13. The first geometry is based on connected spherical-like nanoparticles and the second on nanofibers that protrude. or nanoparticles (see Fig. the features expected in a homogeneous electrode are compared. as discussed earlier herein. for exam- ple. The role of the pores is to increase the screening of the electrons in the electrode. Bueno and C. the equipotential surfaces are planes. For a general view of this subject. 5. in nanostructured electrodes.and power-limiting step in Li-ion bat- tery electrodes) is significantly smaller [86. and such models . nor is the origin of photopotential in DSSC completely understood. A homogeneous electrode with a macroscopically flat surface is shown schematically in Fig. 4. later. Although this picture of the operation of such films is generally accepted.128 P. as depicted in Fig. a consensus has not yet been reached regarding the description of the transport and recombination mechanisms of electrons inside the porous matrix. become mixed inside the electrode region. it is important to understand not only the porous effect but also the distribution characteristics in- volved and to grasp their rationale to maximize the energy density at desired power densities in such devices. increasing the rate of charge transfer between the oxide and each of the dye molecules adsorbed on the particle surface.1 Transmission Line Description of Porous Electrodes To help elucidate some of the aspects involved in the boundary conditions of nanostructured electrodes. 14. In general. according to Fig.e. it has already been proven than nanostructured lithium-ion battery electrodes based on nanofibers or nanotubes of the electrode material protruding from an underlying current-collector surface like the bristles of a brush. 123–125. 4a) are able to dramatically improve the rate capa- bilities because. Two kinds of geometry are commonly employed to improve rate capabilities and achieve a faster solid-state diffusion. porous nanocrystalline materials for electrodes possess extraordinary physical and chemical properties thanks to their ultrafine structure (i. Therefore. The impedance porous model is adequately represented by the transmis- sion line approach. With regard to energy conversion devices. 202]. with those of a porous electrode in which two phases. grain size < 50 nm). 113. via adsorbed ionic solution species. from the current collector [113].. 200]. In addition. Impedance spectroscopy is one of the techniques exploited to increase knowledge in processes that occurs in DSSC devices [22]. a proper grasp of the theory of ac porous impedance is important to extract relevant information on the kinetics of specially designed nanostructured electrodes. The nanostructured electrode also provides sufficient monolayer adsorption of dye molecules to increase the efficiency of light adsorption [201. liquid and solid. brushlike.R. 91. the transmission line method is strictly one-dimensional. resulting in very important surface effects that render them appropriate for use as electrodes in DSSC devices. Gabrielli in nanostructured electrodes.

their impedances have well-defined frequency behaviors and the majority of methods usually presuppose that all the . and inductance are defined indepen- dently of frequency. basic electri- cal properties such as capacitance. for idealized cases. Note that in this picture Rs is the electrolyte resistance. The different models based on the trans- mission line approach differ from each other by the choice of these elements and partly by the possible addition of further discrete elements of the transmission line. 14 Scheme of a porous electrode with the equivalent general circuit model according to the theory explained earlier. Nanomaterials. 13 Schematic of a cross section of a macroscopically flat surface electrode. which is generally given by a pure resistance element such as the one indicated in Fig. and Ze is the impedance corresponding to the properties of the electrolyte. Zi is interfacial impedance of the electrode–electrolyte interface. Also. and Nanostructures 129 flat electrode Zc Zi Ze electrolyte conducting substrate Fig. Three different impedances are represented: Zc is the impedance of the contact between the current collector (conduction substrate) and the electrode. resistance. in this kind of approach of porous electrode representation. representing the ohmic drop in the electrolyte electroactive nanostructured electrode ϕ1 ϕ1 ϕ1 ϕ1 ζ ζ ζ ζ ζ Rs conducting ϕ2 ϕ2 ϕ2 substrate electrolyte x 0 L 0 L Fig. Therefore. indicating the impedance elements.Electrochemistry. 10 (Re ) and (14) (Rs ) or as Rcell in (15). which in the previous section was Rcell can hardly represent special types of pores.

130 P. ϕ1 or ϕ2 . 14. the flux of carriers is always normal to the plane of the surface. and the third. 14. but different situations arise according to the systems to be considered. but nonetheless. whereas the element ζ describes an exchange of electrical charge at the interface. First. the capacity and charge transfer resistance across the Helmholtz layer. to put it another way. (Ob- viously. In agreement with this description of electrical current distribution. Gabrielli elements throughout the layer are the same. as mentioned earlier with regard to Zi ). including the capacitance and resistance of the space-charge region. both i˜1 and i˜2 are parallel to the inner surface shown in the figure. the effect of surface states. the equivalent circuit branches at each point in each medium into an element that continues in the same medium. It is well known from studies of the interfacial impedance Zi of planar semi- conductor electrodes that several effects occur at the semiconductor/liquid inter- face. Now the porous structure gives rise to the spread of electrical current in various directions. Zi can be described by the series and/or parallel combinations of resistive and capacitive components. Moreover. and it is essentially independent on the position on the surface. another at the solid/liquid interface. at a given location. and the current density is the same at any point in the surface. respectively) and they follow the x direction in the scheme of Fig. Therefore.e. . and another impedance element ζ that crosses the interface. depending on media conductivity and more generally on trans- port properties. i. the constraint being obeyed that i˜T = i˜1 + i˜2 (the total current flowing through the external circuit) is independent of position. 14). i˜1 may decrease (increase) with a corresponding increase (decrease) of i˜2 . the form of Zi may become quite complex. 4). the equivalent circuit modeling of the cell impedance involves the connection of a series of elements de- scribing the division of the applied small-signal ac voltage in three parts: one at the bulk of the layer. Or. The impedance elements ϕ1 and ϕ2 describe a local ohmic drop at each point of the transport channels.. the vari- ous processes involved in Zi are localized in the sense that the potential difference driving these processes obeys two conditions: it resides essentially at the semicon- ductor/electrolyte interface.R. Con- sequently. Figure 14 schematically illustrates the cases in which the two phases are closely mixed in space because the layer is porous on a small scale. which includes the potential drop at the bulk electrolyte and metal contacts (see Fig. As can be seen. Bueno and C. The branching in the equivalent cir- cuit model is intended to occur continuously. the resulting ac currents are termed here i˜1 and i˜2 (the subscripts 1 and 2 denote the liquid and solid phase. A standard equivalent circuit model also is represented in Fig. the interfacial impedance ζ itself might consist of a complex equivalent circuit. This model assumes that the predom- inant contribution to the current is electrical field-driven rather than diffusive. current can flow in the normal direction to the inner surface due to electrochemical reactions and/or ca- pacitive charging. Both media are considered as effectively homogeneous and continuously con- nected phases. Therefore. and the diffusion of reacting species (details were given previously in Sect. describing the essential features of electrical transport along each phase and the exchange of charge through the inner surface. owing to faradaic currents and polarization at the pore surface. electrical charge can flow along each medium.

i. (87) ϕ2 ∂ x ∂ i1 1 = − (φ1 − φ2 ).e. the generalized solution of the model leads to the following impedance function [92. For this case. For such boundary conditions. Regarding the electrical potential distribution. 160. In addition to the differential equations. the simple assumption is made that an ac potential can be defined in each phase φ˜1 and φ˜2 which is. the ionic current is usually assumed to vanish at the end of the liquid channel. (89) ∂x ζ The quantities or elements ϕ1 and ϕ2 are impedances per unit length (Ω cm−1 ) cor- responding to the whole electrode area A. whereas the electronic current vanishes at the outer edge of the electrode. (90) ϕ1 + ϕ2 sinh(L/λ ) ϕ1 + ϕ2 in which  1/2 ζ δ= . (91) ϕ1 + ϕ2 and L represents the thickness of layered electroactive material over the current collector. One arrives at this result by considering the original perfect cylinder geometry described in de Levi’s original . is φ˜2 − φ˜1 . 190]:   ϕ1 ϕ2 2λ ϕ 2 + ϕ22 Z= L+ +δ 1 coth(L/δ ). the overvoltage in interfacial reactions. The overall impedance is isomorphous to that of a transmission line.Electrochemistry. so that i1 (L) = 0 and i2 (0) = 0. It follows that the ac potential difference between the two phases at a point x. and ζ is an impedance length (Ω cm−1 ). the boundary conditions must also be taken into account. (88) ∂x ζ ∂ i2 1 = (φ1 − φ2 ).2 Macrohomogeneous Concept (Two-Phase Model) It is important to emphasize that there are different types of assumptions regard- ing geometry and microstructure that lead to (5). at each frequency. and Nanostructures 131 The classical model for porous or mixed-phase electrodes is therefore formulated in terms of equations that describe the local variation of electric current and potential in each phase in the layer of thickness L by the following equations: 1 ∂ φ1 i1 = − . Or. Nanomaterials. no radial distribution of potential into the pores or solid particles is considered. L stands for the porous thickness length. 97. 5. (86) ϕ1 ∂ x 1 ∂ φ2 i2 = − . 95. in other words. a unique func- tion of position x..

the theory of the impedance of porous electrodes has been extended to cover those cases in which a complex frequency response arises in the transport processes [100] or at the inner surface [194. In specific cases in which a solid electrolyte is used. one can consider a solid phase having the form of connected channels of spherical-like particles or nanofibers that protrude from the current col- lector substrate and a liquid phase consisting of a penetrating electrolyte that reaches the current collector substrate.or even three-phase boundary.5). These unmeasurable local distributions define a penetration depth of the active zone and suggest an optimum range of current density and electroactive layer thick- ness with minimal performance losses and highest electroactive effectiveness. As the macrohomogeneous electrode theory has proven its worth in electrode diagnostics and design. In several papers. or from an effective macrohomogeneous de- scription of two closely mixed phases. Keiser et al. which is normally used provided that pore is long compared with its diameter. Bueno and C. Thus. as described by Paasch et al. if the electrode’s nanostructure composed of two mixed phases is of a macrohomogeneous nature. Furthermore. could relate the global performance of the cathodic or anodic layer to unmeasurable local distributions of reactants. because of the previous picture.R. It should be noted that if the percolating phase emerging from the current collector substrate is primarily a mixed ionic and electronic conductor. the complex prob- lem of an uneven distribution of electrical current and potential inside the elec- trode can be described analytically. The models that consider this approach are largely based on the assumption of effectively homogeneous local relaxation processes related to transport in each of the phases and electrical charge exchange between them. In addition. 203]. Ideal locations of elec- troactive particles are at the true two. so the finer details of electroactive layer structure and elec- trocatalytic mechanisms are moving to the fore. this macrohomogeneous medium can be seen as a mixture of two solid phases with- out compromising the result of the analysis. 3.132 P. and impedances can be calculated.. the macrohomogeneous theory can be extended to include concepts of percolation theory. Therefore. In this case. also extended the transmission line model to a noncylindrical pore [14]. which can present analytical or numerical solutions. Even for well defined and extensively . A macrohomogeneous electrode can be established in different dimensional structures and the resulting models. This approach is capable of and vital for showing that micropores inside agglomerates are filled with liquid water to keep the particles active. A useful concept is to consider agglomerates as structural units of the electroactive layer. Gabrielli proposal of porous electrode geometry. who consid- ered an effective macrohomogeneous mixture of two phases in the electrode region [101]. (5) can be used even if the pores have a noncylindrical geometry. the other phase (such as a liquid) that emerges from the elec- trolyte (which can be seen as an ion collector penetrating up to the current collector substrate) must be a purely ionic conductor. and reaction rates. the transmission line approach is easily used to envision a physical model based on frequency-dependent phenomena. Furthermore the models may be conveniently pictured as a double-channel transmission line (Fig. electrode potential.

Nanomaterials. it is im- portant to know the real effect of nanoparticles on the kinetics because extremely small particle sizes (below ∼3 nm) affect the electronic structure of the system and render the catalyst surface rather heterogeneous. The concept applies to both porous anodes and cathodes. The derivation of the model is illustrated by considering different chemical and electrochemical re- action schemes. Assuming that the Nernst–Einstein relation is obeyed. small particle sizes and highly dispersed electroac- tive sites lead to high specific activities (per total mass of electroactive sites such as Pt in the catalytic layer of fuel cells). the following questions should be addressed: What is the benefit of nanoparticles? Is it an intrinsic size effect or an effect of surface heterogeneity? What is the role of the substrate? All of these ques- tions can be addressed in the future by the use of the macrohomogeneous concept of electrodes and cells. For instance.3 Transport in the Solid and Electrolyte Phases ϕ1 . recent studies have revealed drastic differences in the kinetics of nanoparticle surfaces. 5. Generally. the solid channel (channel 1) consists of distributed resistances such as:   1 ϕ1 = r1 = . and des- orption) still constitutes a huge scientific problem involving the application of the macrohomogeneous concept. Therefore. De . and Nanostructures 133 studied electrode geometry. Therefore. Independently of the specific systems. the macrohomogeneous concept can also be adequately extended to the whole cell. the conductivity is related to the diffusion coefficient. This begs several questions: What is the optimum nanoparticle size? What are the best properties of nanoparticle ar- rays? Which substrate is the best? Ultimately. the general basic models can be obtained considering some reasonable and generally valid assumptions about the basic elements in the general transmission line. Moreover. ϕ2 and ζ elements must be specified in the context of (90) to be used as impedance measurements in a defined kinetic model. surface mobility. by the equation: . and electronic and ionic conduction. For instance. Each of the key steps (adsorption. featuring the transport characteristics in each of the phases and their interfa- cial behavior. a framework for macrohomogeneous modeling of porous SOFC electrodes is possible by taking into account multicomponent dif- fusion.Electrochemistry. the solid phase impedance ϕ1 can be simply treated as possessing an ohmic behavior (Ohm’s law). multiple electrochemical and chemical reactions. The framework is general enough so that additional chemical and electrochemical reactions can be accounted for. Considering fuel cell applications. charge transfer. (92) Aσe where A is the geometric surface of the phase and σe is its electronic conductivity. the essentials of the kinetic mechanisms are not totally settled.

(95) 1 + jω /ωi . This means that the dc behavior of the charge transport processes is independent of frequency.134 P. It can also be used to describe the space-charge polarization at the semiconductor–liquid junction if the spatial distribution of electrical charge as a function of potential is known. Therefore. which is useful mainly for very high conductive solid phases. For an ideally polarizable interface. Bueno and C. the distributed interfacial capacitance. This is the region of transition between the solid phase (electroactive material or electrode) and the electrolyte. where c¯ is the concentra- tion of ionic charge carriers and Dl is the diffusion coefficient of the ionic species in the liquid phase or electrolyte. kB is Boltzmann’s constant. ci . (94) jci ω The total capacitance in the walls of the pores is given by Ci = ci L. Gabrielli q2 n¯ σe = De . we obtain σl = (q2 c/k¯ B T )Dl . Therefore. In the same way. The impedance of the liquid phase or electrolyte can similarly be described by a resistive element and. q is the ele- mentary charge. An ideally polarizable interface with charge transfer can be described by considering the charge transfer as a resistance. offers many possibilities. so it is usually a function of the potential. Potential differences may sustain charge storage and charge transfer ki- netics in this region. the total resistance in the electrolyte contained inside the pores (electrolyte channel) can be given by R2 = r2 L.4 Polarization and Charge Transfer at the Porous Interface The interfacial impedance element. the conductivity is merely a function of the local concentration of the carriers and the diffusion coefficient of the material. (93) kB T where n¯ stands for the dc concentration of electronic charge carriers. ζ . in this region. charge transfer and double-layer effects are evidenced. and T is the temperature. In this simple model for electronic conductivity in the solid phase channel of the porous electrode.R. rct . An ideally polarizable distributed interface can be described by a ca- pacitance. the differential relationship between the charge at the boundary and the electrical potential is the interfacial capacitance. Furthermore. therefore. which goes in parallel to the capacitance so that the ζ impedance element yields an impedance such as: rct ζ= . similar to (8). the total resistance can be cal- culated easily based on the distributed resistance by R1 = r1 L. whose interfacial impedance is described by: 1 ζ= . 5. This capacitance is attributed to double-layer effects. in which A is now the geometric area of the liquid or electrolyte and σl is the ionic conductivity. the impedance-related element takes the form of ϕ2 = r2 = 1/Aσl .

In other words. EDLCs show frequency-dependent capacitance even though a capacitance should be independent of frequency. The latter assumption is not applicable to a rough surface with shallow pores. and Nanostructures 135 with the characteristic frequency of charge transfer defined as ζ = 1/RctCi = 1/rct ci . and no curvature of the equipotential surface in a pore is considered to exist. but among a variety of situations. It has been shown that the impedance of a porous electrode in the absence of faradaic re- actions follows the linear line with the phase angle of 45◦ at high frequency and then . surface reconstruction. This abnormal frequency dependency is called a distributed characteristic or frequency dispersion of elec- trical properties.g. it could be the concentration of reactant species in the electrolyte. diffusion length or penetration depth). It is not easy to interpret rct . and transformation in the layer. which are not the function of the location in a pore. which is known as capacitive dispersion.. This category includes diffusion in a diffusion-limited system [189. This is especially true when other heterogeneities are suppressed by careful experimental conditions. Distributed characteristics result from two origins [204]. First. etc. they appear nonlocally when a dimension of a sys- tem under study (e. 190]. Nanomaterials. This type of distributed characteristic exists even when all system prop- erties are homogeneous and space-invariant. The frequency dispersion of porous electrodes can be described based on the finding that a transmission line equivalent circuit can simulate the frequency re- sponse in a pore.Electrochemistry. a distributed characteristic is attributed to various heterogeneities: geometric heterogeneity such as roughness or distribution of pore size [205] and crystallographic heterogeneity such as anisotropic surface metal structure and a surface disorder of polycrystalline platinum or gold [192]. with Rct = rct /L being the total wall charge transfer resistance. double-layer charging of a porous electrode [92].5 Distributed Features and Dispersion Ideally. In any case. In many types of interfaces the capacitance of the interface has been found to be a function of the frequency. The assumptions of de Levi’s model (transmission line model) include cylindrical pore shape. A circuit element with distributed characteristics (distributed el- ement) cannot be exactly expressed as a combination of a finite number of ideal circuit elements except in certain limited cases. the elec- trical properties of real circuit elements only approach the ideal within a limited frequency range. characteristic reaction rates. Secondly.g. equal radius and length for all pores. the reaction or rct resistance originates the faradaic currents at the surface of the electrode. and interfacial impedance. which is a function of frequency. For instance. unlike rough surfaces (with shallow pores) [192]. Porous material with deep pores is an extreme example of the influence of geometry on frequency dispersion. electrolyte con- ductivity. electrode thickness or pore length) is longer than a charac- teristic length (e.. 5. the polarizable interface is the exception rather than the rule. and sluggish processes such as adsorption of anions.

one from pore lengths longer than the penetration depth of the ac signal and the other from the pore size distribution. but some ana- lytical solutions are being used to represent the pore size distribution of a porous electrode [171. In other experimental situations. the pore size distribution considers that the elements of the impedance of the layer are not constant along the length. A blocking capaci- tive interface response that takes into account a frequency dependency can generally be modeled by an interfacial impedance element such as: 1 ζ= ( jω )βi . and a few attempts have been made to consider the effect of pore size distributions (PSD) on the impedance of a porous electrode [171. the porous carbon electrodes widely used in EDLCs have two types of distributed characteristics mentioned previously. while a parametric study is dif- ficult because of too many parameters (sizes of different pores). Several particularized examples of blocking interface or nonblocking dispersive boundary conditions are studied in detail in different papers [190. the microstructure (represented as pore size distribution) of the porous electrode should be optimized to obtain the desirable energy and power density. it is possible to simulate the nonvertical behavior of impedance at low frequencies [93. a vertical line is shown at low frequencies.190. 207]. The impedance curve in the Nyquist plot is observed to change with the shape of a pore in the intermedi- ate frequency region.136 P. with a prefactor for the whole interface given by Qi = qi L. Some authors believe that the inclined line of impedance at low frequencies comes from the pore size distribution of porous materials [171. Gabrielli a vertical line at low frequency in the Nyquist plot [190. For instance. for ide- alized interfaces. In other words. 182]. the dispersive capacitance can be described by another interfacial element capable of dealing with such low-frequency dispersion. Therefore. which is shown as an inclined line in the Nyquist plot. Various origins of CPE behavior have been discussed. despite its similarity to a cylindrical pore at extremely low or high frequencies. 207. 182]. In contrast with the voltage dependence of the interfacial capacitance. Bueno and C. The PSD effect is difficult to take into account. irrespective of the shape of a pore [171. with regard to dispersive behavior. Some authors have reported that the real part of the reduced impedance (the ratio of impedance of a pore to electrolyte resistance in a pore) ap- proached one-third at low frequency. both porosity and re- sistivities can vary in the course of the preparation. although the PSD must contribute considerably to the distributed characteristics [171. the phase angle approaches 90◦ at low frequencies. many experimental data of impedance for porous materials show that the phase angle is not 90◦ even at very low frequencies.94. 209–212]. 182]. it is ex- tremely difficult to justify the observed frequency dependence on a theoretical basis. With the introduction of a CPE (96) into the porous model represented by (5). (96) qi which is known as constant phase element (CPE). In the Nyquist plot. . Thus. 195–199.189.208]. depending on different systems [189. particularly because of the time- consuming calculations required by this method. These models all state that. In this case.R. However. 182]. 182].206].

Electrochemistry, Nanomaterials, and Nanostructures 137

during the preparation of a nanostructured porous layer, the dependence of the po-
tential sweep (electrochemically prepared nanostructured porous layer) causes vari-
ation in the degree of oxidation, and this degree of oxidation can vary throughout
the layer, or variations in the composition may lead to gradients of resistivities, etc.
Such problems have been considered in several cases, e.g., in [189, 190, 213] by
using a CPE description.
Another way of dealing with such problems is by using transfer matrix meth-
ods [167, 193], which allow for their solution. Eloot et al. [214, 215] developed the
matrix method to calculate the impedance of a noncylindrical pore by extending
Keiser’s model [206]. According to these authors, it appears that the limit of the real
part of the reduced impedance depends on the geometry of a pore.
The matrix model was used recently as the basis for considering the elements in
the channels dependent on the frequency, and they can also vary across the layer
[167, 193]. The examples show clearly that, independently of the parameters of the
system, inhomogeneity can lead to qualitative modifications of the impedance re-
sponse, the most important of which is the influence on the low-frequency pseudo-
capacitive behavior of the impedance, which is transformed into a CPE-like form
(which, as discussed previously here, is usually introduced only phenomenologi-
cally by replacing j(ω /ωc ) to j(ω /ωc )β with β < 1). Some of the dependencies
demonstrated by the authors resemble those already obtained with simpler equiv-
alent circuits (but including the phenomenological CPE). Therefore, as discussed
earlier and as is well known for simpler models, the use of transfer matrix methods
and porous theory for data fitting and microscopic characterization requires further
experimental information (e.g., on porosity, changing composition) as well as the
impedance data itself. Therefore, experimental support is still needed to validate the
model and show what the influence of porous distribution is.

5.6 Charge Transport in Nanostructured Electrodes

The electrical response of nanostructured electrodes has been extensively studied, as
discussed earlier here. We know, from solid-state semiconductor physics, that dis-
ordered structures in polycrystalline film electrodes, for instance, normally perform
poorly compared with electrodes made of highly ordered materials such as single
crystals, a fact that raises several questions. How can electrons be collected and
transported efficiently through a poor and disordered structure such as a nanostruc-
tured film electrode? What are the mechanisms of charge transport? Although exten-
sive work has been done, there are still questions to be answered and the mechanism
of charge transport in mesoporous electrodes or disordered systems is currently un-
der intense debate in the literature [201, 202, 216–220]. Nanostructured compound
electrolytes or ionically conductive electrodes for lithium ion batteries may also
present nonpattern charge transport [210, 221, 222].
Furthermore, with regard to the ac electrical response, it is a well-established fact
that the conductivity in many solid materials displays a universal pattern consisting

138 P.R. Bueno and C. Gabrielli

of a power-law domain at high frequencies and a constant conductivity in the low-
frequency wing. The possible consequences of such behavior on the impedance re-
sponse of porous electrodes have been explored [223, 224]. Therefore, a description
of the anomalous transport effect is readily incorporated into the standard double-
channel transmission line model for porous electrodes, on the basis of a macroscopic
phenomenological theory for transport in disordered solids [223,224]. The influence
of the power-law behavior in the solid network gives rise to such familiar features
as a curvature in the Warburg part of the spectra, or to an arc at high frequency, de-
pending on the relative magnitudes of the conductivities in both solid and liquid or
electrolyte phases. It was suggested that a similar description could be attempted for
the ionic transport through fine pores, so the transport in solid and electrolyte phase
exemplified previously by (92) and (93) must be reviewed to consider the disorder
effects [24, 83, 222, 225–251].
Another aspect that should be taken into account in the interpretation of experi-
ments is the fact that the diffusion mechanism need not be unique at all the scales of
frequency–time. It has been observed that the normal behavior in many disordered
systems consists in an anomalous diffusion mechanism at high frequencies and short
times, which changes to ordinary diffusion as the frequency decreases or the time
scale increases [221]. So the resulting diffusion would be either anomalous or ordi-
nary, depending on whether the distance traveled by the random walker during the
observation time was shorter or longer than the cutoff scale of the structure [252].
These situations could be treated by introducing a characteristic crossover time or
frequency that separates the diffusion regimes. Such an analysis was presented for
impedance of porous electrodes [223].
Example of the uses of porous model approach in energy conversion porous elec-
trode is given by the use of general transmission line model of DSSC. From this
model it is possible to calculate, for instance, charge-transfer resistance of the charge
recombination process between electrons in the mesoporous TiO2 film, the chemical
capacitance of the electroactive film, transport resistance of the electrons in the TiO2
film, and Nernst diffusion in the electrolyte among other parameters. By using such
approach it is possible to understand characteristics of high efficiency of DSSC to
conclude, at this moment, that the high efficiency of the DSSC cells can be ascribed
to the high transport and low recombination rate of the electrons in TiO2 -electrolyte
interface [253].

6 Future Prospects

The development of alternative storage and conversion energy devices was shown to
be strongly correlated to and in some aspects dependent on nanotechnology. There-
fore, new components for these devices will continue to be designed in the coming
years, especially aiming for better performance and scale mass production. The fu-
ture economic development of our modern society will depend to a great extent on
such development, since the era of fossil fuel is coming to an end.

Electrochemistry, Nanomaterials, and Nanostructures 139

Conversion and storage of energy requires efficient energy capture, charge
separation and transport, and, finally, efficient utilization or storage by chemical or
electrochemical means. The high surface area of nanostructures has been proven to
enhance efficiency tremendously. In addition, to improve the performance of these
devices, the role of interfaces is crucial for highly efficient nanostructured elec-
trodes. The efficiencies of catalytic sequences for utilization and storage are also
enhanced by the high surface area. Thus, nanoscale systems are expected to advance
conversion, and any headway made in understanding the relevant charge transfer
process and the strongly related energy transfer will be central to this progress.
To produce materials and systems with improved properties we must be able
to modify the amount of interface and its properties in a controlled manner. The
engineering of nanostructured electrodes depends on a more in-depth understand-
ing of the nanoscale size effect properties of compounds and on the characteri-
zation and assembly of 2-D and/or 3-D nanostructured electrodes or cells. Any
strategy for modifying these nanostructured electrodes in a specific way should
involve the design of nanostructured electrodes with controlled electrochemical
Despite recent technological successes through the clever incorporation of the
use of nanosized materials in electrodes (nanostructured electrodes) in alternative
energy devices, we are still far away from possessing a solid scientific understand-
ing of what really goes on at the nanoscale. Many critical questions remain to be
answered. For instance, what are the characteristic dimensions over which energy
transfer or charge transfer reactions can effectively occur in devices? How does
the nanosize material surface influence this dimension? How exactly do kinetic
properties scale in small dimension? Is there more than simple surface area scaling
at work?
Because of these and other questions that are still open, the study of the kinetic
scaling behavior of nanostructured systems is quite complex and must be the focus
of further development of appropriate nanostructured electrodes.


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Fuel cells also derive benefits from the development of nanoparticles and nanotubes for catalytic application. c Springer Science+Business Media LLC 2009 . allowing also study of the molecular electrochemical behaviour. distribution and conversion. In this chapter we describe the impact of nanotechnology in the performance of the dif- ferent components of the fuel cell as well as the impact of nanotechnology in the electrochemistry process.).g. Germany e-mail: a.1 What Relevance Has Nanotechnology for Fuel Cell Systems [1]? Energy research is becoming increasingly important. Universit¨at Duisburg. Nanostructure Science and Technology. 1 Introduction 1. al- lowing also study of the molecular electrochemical behaviour. Nanostructured Materials for Electrochemical Energy Production 151 and Storage. particularly as regards the role it plays in support of a wide range of key policies (e. Lotharstr. A. Fuel cells especially benefit from electrodes and membrane electrolytes with nanostructured and therefore enlarged surfaces. DOI 10. security and diversification of energy supply. storage. sustainable development).heinzel@uni-duisburg. 47057 Duisburg. 1-21.R. Nanotech- nology shows promising potential in all segments of the energy sector: E. There are noteworthy developments in nanotechnology and its relevance to the energy field. Fuel cells also derive benefits from the development of nanoparticles and nanotubes for catalytic application. Heinzel () Fachgebiet Energietechnik. Fuel cells especially benefit from electrodes and membrane electrolytes with nanostructured and therefore enlarged surfaces. Leite (ed.Nanotechnology for Fuel Cells Angelika Heinzel and Uwe K¨onig Abstract There are noteworthy developments in nanotechnology and its relevance to the energy field.1007/978-0-387-49323-7 4. energy market liberalization.

These range from combined heat and power supply systems in the 100 kW to the 1-kW power segment. various applications are interesting. The costs of fuel cells were approximately 20. the fuel cell catalysts have drawbacks. a growing number of companies are confident that they are now on the verge of bringing prices for fuel cells down to levels where they can compete with conventional electric-power generating equipment. .g. which decreases strongly if water content is not sufficient. which consist of carbon-supported precious metal particles in the range of 1–5 nm. The main obstacle – the use of hydrogen as fuel – might be overcome by gas processing tech- nologies.2 Fuel Cell Technology and Nanotechnology Fuel cells as efficient energy conversion devices are one of the present R&D sub- jects in energy technology. most analysts do not believe that fuel cells will be widely used in the coming 20 years [1]. research work is being done in nanostructuring the carbon electrodes to avoid the deactivation of catalysts by e.and medium-temperature fuel cells. A further approach to nanostructured materials is the introduction of nanoscale hydrophilic (high affinity to water) inorganic materials such as silica into the polymer membranes being used as electrolyte to improve water retention of the membrane at elevated temperatures. converting fossil or biogenic fuels into a hydrogen-rich gas mixture. lifetime and reproducible properties have also to be solved. • Technical challenges such as thermal as well as mechanical expansion. seals. thus reducing the costs of the material. High efficiency val- ues are achievable even in the lower power range.152 A. Fuel cells for portable ap- plications are appraised as most promising. agglomeration and therefore reduce the amount of noble metals and increase the catalyst performance. As fuel cells can be operated continuously as long as fuel is available. Although the detailed problems depend on the type of fuel cell the main obstacles are the same: • The central problem inhibiting a wider market penetration of fuel cells is the high manufacturing costs. Thus.000 Euro per kilowatt power in 2002 [2]. alter- native membranes with defined properties in the nanometer range are intensively under development. The most prominent nanostructured materials in fuel cells are the electrocata- lysts of low. To solve this issue. However. In spite of the promising potentials of fuel cells. to mobile (electric traction) or even portable applications. Heinzel and U. • The problems are mainly caused by expensive materials used in fuel cell tech- nology. 1. they are both expensive and have limited efficiency. This structure is necessary to in- crease the surface to volume ratio of the noble metals. The functioning of the cell using sulfonated membranes such as NafionTM is related to the hydrogen ion conductivity of the membrane. K¨onig However. Hydrogen and oxygen from air may be converted directly by an electrochemical process into electrical energy and heat.

and a cell frame for gas distribution and current collection. For most of the cell types. SOFC solid oxide fuel cell Different material combinations for practical realization of fuel cells have been developed in the past few decades [3]. shown in Fig.5 V during operation are achieved. 1. Regular nanostructures are not typically used until now. . 2.23 V. cell voltages of 1 V at zero current (open circuit voltage) and 0. MCFC molten carbonate fuel cell. PAFC phosphoric acid fuel cell. a layered bipolar construction is state of the art. AFC alkaline fuel cell. catalytically active electrodes. The operation principle of the different fuel cells is depicted in Fig. The main electrochemical reactions for hydrogen-fed fuel cells are as follows: Anode: H2 → 2H+ + 2e− 1 Cathode: O2 + 2e− → O2− 2 1 H2 + O2 → H2 O 2 This reaction should theoretically lead to a cell voltage of 1.000◦ C. but nanomaterials for preparation of layers are frequently the best base materials. for the example of a polymer electrolyte membrane fuel cell. comprehensive overviews about the tech- nology have been published [4]. Some examples will be given in the description of the five types of fuel cells in this introductory chapter. 1 Operation principle of the various types of fuel cells: PEMFC polymer electrolyte mem- brane fuel cell. Possible operation temperatures of fuel cells range from ambient temperature to 1. These low-voltage values per cell lead to the requirement of series connection of various single cells to form a so-called cell stack.Nanotechnology for Fuel Cells 153 e− H2 AFC OH− O2 100 ⬚C H2O PEFC H' O2 80 ⬚C H2 PAFC H 2O 200 ⬚C H2 O2 MCFC CO2 H2O CO22− CO2 650 ⬚C H2 SOFC H2O O2− O2 1000 ⬚C fuel gas oxygen anode elektrolyte cathode Fig. practically. The main components are the same for all types of fuel cells and comprise an electrolyte.

GDLs are a porous system formed by hydrophobic and hydrophilic pores in the sub- millimeter range. the so-called flow field for the distribution of fuel and air evenly over the entire active electrode area of the anode and the cathode. the dimensions of channels and ribs are usually in the millimetre range. Chemical stability is achieved by using a fluorinated polymer . Various cooling concepts have already been realised. Heinzel and U. Proton conductivity is its most important property besides the safe separation of the fuel in the anode compartment of the cell and the air in the cath- ode compartment. lower loadings are envisaged for future elec- trode materials.154 A. In addition. For operation at low (ambient) temperatures. Another issue is CO tolerance of the electrocatalyst. if the fuel cell shall be operated with reformate generated from fossil fuels instead of pure hydrogen. The cell frames act as well as current collectors. K¨onig Fig. • The third layer is the electrode. Its compressibility is important for stack construction. the cell frames can contain cooling channels. This GDL protects the membrane from mechanical damages. because small deviations in thickness of sealings and bipolar plates can be compensated. The membrane is the elec- trolyte. ensures spatial electrical contact. and thus a good electrical conductivity is required. typically a carbon paper or car- bon cloth. 3). • The second layer is a gas diffusion layer (GDL).4 mg cm−2 . thus preparation processes are used leading to nanoparticles of noble metals on the larger carbon particles (see Fig. 2 Components of a membrane fuel cell The functions of the different layers are as follows: • Cell frames contain a system of gas channels integrated in the bipolar plate. A large electro-catalytically active surface area is important for achieving high current densities. and is important for gas distribution to the electrode parts under the ribs of the flow field and for removal of product water. • The fourth layer is the polymer membrane itself. noble metals are required as catalyst. then forming a so-called mem- brane/electrode assembly MEA. a thin catalyst layer that might be coated onto the GDL or in most cases onto the membrane. The goal of cost reduction led to the devel- opment of catalyst systems consisting of a carbon carrier material with a noble metal loading of about 0. either for air cooling or for liquid cooling.

4). Thus. This interface is a unique structure of the membrane fuel cell. Proton conductivity additionally requires the presence of a sufficient amount of liquid water [6] (see Fig. The third phase is the solid electrolyte material. even more complicating the facts. Part of the water is necessary to conduct hydrated protons from the anode to the cathode side. showing hydrophilic channels in a hydrophobic ma- trix. The fourth phase finally is the electrocatalyst. water management in the different layers is im- portant to be properly controlled. for membrane fuels cells. part of the water has to be removed in order to avoid flooding of the gas diffusion structure. containing either the hydrogen or the oxygen. The sec- ond phase is liquid water being generated as product and contributing to the ionic conductivity of the membrane. which shall be transported to the reaction zone. where ions are generated. 3 Electrocatalyst as prepared for use in PEMFC (source: MPI M¨ulheim) backbone. Proton conductivity is realised by sulfonic acid groups attached to side chains of this backbone. and much effort was undertaken to optimize it [7]. Another important aspect is the structure of the so-called three-phase boundary in a gas diffusion electrode. . ensuring a good humidity of the membrane but avoiding flooding of the porous GDL. The first polymer electrolyte of this type was developed in the early seventies [5]. The electrodes in PEMFC operating with gaseous fuel in fact constitute a four-phase boundary. necessarily being hydrated with liquid water and also being in close contact with the sites.Nanotechnology for Fuel Cells 155 Fig. The hydrophobic backbone and the hydrophilic acid groups lead to a structure. The first phase is the gaseous phase. also in close contact with the fuels in order to catalyse the electron transfer reaction and to conduct the electrons to the outer circuits.

which is thus also a matter for optimisation [8]. the requirements for the structure of the interfacial catalyst layer are different than for gaseous hydrogen as fuel. . A polymer membrane in contact with methanol shows significant transfer of methanol and water from the anode side to the cathode side of the fuel cell. but here in practice open circuit voltages of about 0. 4 Specific conductivity of NafionTM 117 as function of water content The same type of membrane fuel cell can be fed with a liquid solution of methanol in water instead of hydrogen or reformate as fuel. 5. where the variety of nanostructures is also pointed out. and CO tolerance also is an important issue. and higher noble metal catalyst loadings are required. But the advantageous simplicity of the fuel cell system and the high energy density of the liquid fuel make the DMFC attractive despite these mentioned drawbacks. For a liquid-fed DMFC. K¨onig 0.1 Specific conductivity [S /cm] 0.08 0.06 0.215 V. The electrochemical reactions are as follows: Anode: CH3 OH + H2 O → CO2 + 6H+ + 6e− 3 Cathode: O2 + 6H+ + 6e− → 3H2 O 2 3 O2 + CH3 OH → CO2 + H2 O 2 For methanol as fuel. the cell voltage calculated from thermodynamic data is 1.12 0.7 V are achieved and 0.156 A. Special MEAs have been developed for direct methanol fuel cells (DMFC). Typical MEAs are shown in Fig. Because of the formation of the poisoning intermediate adsorbate CO.04 0.4–0. the achiev- able current densities are limited. Heinzel and U. leading to losses due to formation of a mixed potential at the air electrode.02 0 0 5 10 15 20 25 30 water content = NH2O / NSO3H Fig.3 V is achieved during operation.

The practical use . carbon sup- ports or coatings for bipolar plates are examples.Nanotechnology for Fuel Cells 157 Fig. The alkaline fuel cell (AFC) with its liquid alkaline electrolyte KOH uses gas diffusion electrodes with a hydrophobic porous part. As the electrode potentials in alkaline electrolyte are shifted towards more negative values. corrosion is less prob- lematic. the realisation of special properties of surfaces and the enhancement of functionalities by nanostructures. which is not flooded by the alkaline electrolyte. nanotechnology plays a role in the development of micro fuel cells. Raney Nickel and silver are the state-of-the-art catalysts. Nanostructured electrolytes. nanolayers as coatings and nanoparticles raise increasing interest. 5 Scanning electron microscopy (SEM) pictures of DMFC electrodes: upper – E-Tek elec- trode. and a hydrophilic part containing electrolyte and thus leading to a three-dimensional three-phase boundary layer. lower – electrode made by DLR In addition to the earlier described state of the art.

usually the three layers. namely. the electrolyte is liquid phosphoric acid in an inert matrix. the cathode is NiO. The materials used mainly have structures in the micrometer range. . and the particle growth during tens of thousands of operational hours is well investigated [9]. Heinzel and U. Because of the high operation temperature. the same require- ments are valid as for the PEMFC – nanoparticles with a high surface area and a good dispersion on the carbon carrier material are required. A better long-term stability was achieved with a chan- nelled anode produced directly by solidification of a NiO–YSZ eutectic mixture. mainly sin- tering of the small Ni particles. and the liquid electrolyte is contained in a matrix (LiAlO2 ) and must be held there by capillary forces. Sr)CoO3 by metal- organic deposition. Summarising the activities using nanotechnology for fuel cells.158 A. Another approach to improve the anode using nanolayers was recently reported [12]. For realizing a long-term stable high surface area cathode. Changes of pore diameters during lifetime have to be avoided. The solid oxide fuel cell (SOFC) consists of solid components. anode. K¨onig of alkaline fuel cells is limited due to the sensitivity of the electrolyte towards CO2 . electrolyte and cathode. Single YSZ par- ticles are sintered onto the electrolyte. An increase in power density and in long-term thermal cycling stability was observed. resulting in a high surface area. by laser zone melting of rods or plates and subsequent reduction of NiO. a special preparation method was recently examined [11]. which is formed from Ni by in-situ oxidation of a porous Ni plate with pores of a size of 8 μm. mechanical stress due to different thermal expansion coefficients of the materials used is a major challenge. The phosphoric acid fuel cell (PAFC) has a quite similar construction and com- ponents as the PEMFC. For the catalyst properties. which leads to potassium carbonate precipitation. Material development for adopted physical properties and for electrolytes with high conductivity at reduced temperatures of about 500–700◦ C is the focus. submicron LiAlO2 is a nanomaterial used in MCFC. Thus. and a structural change of the cermet can be observed [10]. To achieve a good performance. The molten carbonate fuel cell (MCFC) with its operation temperature of 650◦ C is developed since the sixties. The operation temperature of 200◦ C avoids formation of liquid water and improves CO tolerance of the electrocatalyst. the membrane fuel cell is the most promising type. A lamellar thickness between 200 nm and 1 μm could be realised. The application of PAFC typically is the combined heat and power supply in the 200-kW power range. The pore size of the matrix must therefore be carefully controlled and be smaller than the mean pore size of the electrodes. the focus of the subsequent chapters will be on this type of fuel cell and will give more details on new approaches using nanostructured electrocatalysts and membranes. Operation at high cur- rent densities and at high fuel utilisation leads to a significant increase of anode resistance. Corrosion of the metallic cell frames in contact with the molten salt electrolyte and electrolyte loss during operation still limit the lifetime of the stacks. which are manufactured as MEA as it is the case for the membrane fuel cell. Thus. the anode is made of Ni/Cr or Ni/Al with a mean pore size of 6 μm. the anodes of SOFC are a well-defined micro-structural layer of Ni/YZS (Yttria-stabilised Zirconia). The surface then is covered by a thin layer (approximately 100 nm) of (La.

the nanoseparation into hy- drophobic and hydrophilic domains is well known. partially fluorinated ionomers. NafionTM was the first commercially available membrane. New types of polymers are also under development for better temperature stability. nonfluorinated ionomers. The main challenge for new membranes is the realisation of high proton . 14]. Today. several materials have been considered. better chemical and mechanical stability and reduced methanol crossover for DMFC operation. 20]. aiming at improved material properties. in which different materials contribute to specific advantageous properties. which usually is doped with phosphoric acid [18]. A significant improvement of the mechanical sta- bility was achieved by incorporation of a PTFE porous sheet as mechanical support for the membrane material [13. For NafionTM . The goals are less sensitivity towards elevated temperature and dry operation. Infiltration of a polymer car- rier material with various inorganic proton conductors is subject of a patent [16]. various companies are en- gaged in membrane development especially for this purpose. An overview on the state of the art of composite perflourinated membranes is given in [15]. The microstructure of NafionTM and sulfonated polyetherketones also was a matter of recent investigations [22]. For operation at elevated temperature. 6).2 Alternative Membranes There are tremendous efforts in developing alternative polymeric membranes for PEFC. one of the most advanced examples is the high-temperature material polybenzimi- dazole. Nanomaterials come into consideration for various composite materials.The development of new polymers for ionomer membranes including perfluorinated ionomers. In an early work. high-molecular/low-molecular composite membranes as well as novel polymer modification processes and novel membrane materials is summarised in [21]. with the hydrophilic domain being responsible for the transport of protons and the hydrophobic backbone pro- viding the morphological stability and preventing the membrane from dissolving (Fig. The sulfonated polyetherketones showed a less pronounced nanoseparation due to the less hydrophobic backbone and the less acidic sulfonic groups. NafionTM /H3 PO4 showed better conductivity at temperatures above 100◦ C compared with blank NafionTM and also reduced methanol permeability [17]. Another approach was the synthesis of inorganic/organic composite materials to influence the properties of the membrane.Nanotechnology for Fuel Cells 159 2 Nanostructures 2. 2.1 General Properties of Electrolyte Membranes The membrane in a membrane fuel cell fulfils several important functions as stated in the introduction. The use of low-cost basic polymers instead of NafionTM is an interesting alterna- tive [19. which lead to a breakthrough in fuel cell technology.

ACS Symp. Series No. 6 Structure of a NafionTM membrane according to H. Yeager. A. a defined nanostructure often is a key issue. A: hydrophobic fluorocarbon region. Yeager. Specially designed chemicals such as ionic liquids (ILs) allow the immobilisation and as a consequence the defined distribution of active particles such as catalysts. Eisenberg in Perflu- orinated Ionomer Membranes. Moreover.html). Nanoparticles will be incorporated into the membranes to enhance the in-situ generation of hydrogen from e. These kinds of chemicals can also be used to functionalise inor- ganic structures such as zeolites or molecular sieves. methanol as well as to increase the basic fuel cell reaction. O H2O O O A C B Fig. 41–63/ (source: http://www. Nanotechnological approaches will lead to defined structures on the molecular level by implementing active side groups or isolated particles as well as by crosslink- ing via side B: interfacial region. . C: hy- drophilic region with ionic exchange groups. Heinzel and U. counter ions (Na+ in this picture instead of H+) and water mobility in a robust polymer matrix. 1982) pp 1–6. usm. Furthermore. H. the proton conductivity can be improved by the incorporation of nanoparticles.psrc. Eds.160 A.g. A. Eisenberg. the contact to the catalysts is important. 180 (American Chemical Society. K¨onig O F O (CF 2) n C O (CF2)n H2O O O - SO3 SO3- CF2 Na+ F3C CF H2O O CF2 CF2 H2O H2O SO3- SO3. O Na+ H2O SO3.. Washington DC. Especially the transport properties of the protons and the water content have to be taken into account.

As opposed to the conventional membranes. e. imidazole. the high proton conductance does not rely on the presence of water. these systems are aprotic. Disadvantage: Agglomeration of particles possible.g. swelling. 2. Another possibility is to combine different monomers based on block co-polymers. The objective of this attempt is to take advantage of the high proton conductance in watery sys- tems and to control the proton conductivity by a sophisticated water management. Advantages: High thermal stability. More details are given in Sect. swellable by water uptake.g. where poison- ing effects of the used electrocatalysts are drastically reduced. Novel side-chain polymers with heterocycles such as imidazole attached to appropriate polymer backbones are used as proton-solvating moieties and for achieving high proton mobility at high temperatures (>100◦ C). humidity systems also to temper- atures above T > 100◦ C possible. • Dendrimer PTFE copolymers combining hydrophilic dendrimers with hydropho- bic linear polymers Advantages: High thermal stability and high conductivity. The conductivity can be controlled by the number of SO3H groups due to the depen- dence of the water uptake from the number of groups ([23] and references cited therein). often difficult to synthesize and expensive. swellable by water uptake. Nevertheless. Disadvantages: Problems may arise from oxidation of aliphatic bonds. high conductivity and lower permeability of methanol. Advantage: High variety of properties possible. . often dif- ficult to synthesise and expensive. from sulfonated polymers (sPEEK – sulfonated polyether-etherketone. polybenzim- idazole): The combination results in ionic cross-linked phases. the conductivity is strongly dependent on the water content.3. Disadvantages: Problems may arise from oxidation of aliphatic bonds. swellable by water uptake. which also influences the mechanical properties by e. often dif- ficult to synthesize and expensive. Commercially available polymers can be modified by different sulfonation reagents. sPPSU – sulfonated polyphenyl- sulfone) combined with alkaline components (amine.Nanotechnology for Fuel Cells 161 Several types of other proton conducting membranes that incorporate quaternary nitrogen atoms are presently under investigation: • Polymer blends leading to high-end polymers. • Composite membranes formed by incorporation of inorganic nanoparticles or polyacids Solvated proton conducting polymers and composite membranes should govern the transport of protons and water by micro structural control.

ceramic systems. Disadvantages: Ionic liquids have to be supported by e.1 S cm−1 [26].5. • Ionic liquid mixtures such as a 4:6 mixture of methyl and dimethyl ammonium nitrate: The incorporation of imidazol derivates results in a better stability up to T = 180◦ C with a conductivity of 0.g. 7 Cationic polymerisation of IL . from organic amines with (trifluoromethanesulfonyl) amide (HTFSI). 7). e. no water content. operation at temperatures above T > 100◦ C possible. Disadvantages: Ionic liquids have to be supported by e. no swelling.162 A. 2.28].g. The resulting polymer form a cationic structure where the anions can move at (Fig. In all cases disadvantages arise from the possibility of oxidation of the aliphatic bonds and the fact that the systems are often difficult to synthesise and the costs are high. K¨onig Novel Brønstedt acid–base ionic liquids [24. e.g.or allyl backbone. Advantages: High variety of properties possible. no water content. high conductivity. Detailed information about the state of the art of ionic liquids is given in Sect. R + R + N N (CH2)n N N N N − − RX X Kat. ceramic systems. often difficult to synthesize. high chemical and mechanical stability.g. X R⬘ R⬘ R + R + N N N N (CH2)n N N − X − X n = 0 und 1 Fig. electroactive for H2 oxidation and O2 reduction at a Pt electrode under non-humidifying conditions at moderate temperatures (ca. A typical liquid is the 1-butyl-3-methyldiazonium derivate with addition of BF−4 and H3 PO4 to fit the acidity. The stabilisation of the ionic liquids is possible by introducing the substances into a porous silica matrix [27. the addition of alkylimidazilium to a vinyl. operation at temperatures above T > 100◦C possible. Advantages: High variety of properties possible. Heinzel and U. high conductivity. no swelling. The system shows a thermal stability up to T = 300◦C with a conductivity up to 80 mScm−1 [29]. often difficult to synthesize. presently expensive due to scientific state. 25]. presently expensive due to scientific state. Functional monomers are added to an adequate backbone. 130◦C).

The resulting hybrid materials can have quite different properties than a linear combination of the individual bulk properties. as hydration of the composite could be maintained at a high level. improves the water retention of the membrane. The performance of Nafion-composite membranes at an elevated temperature of 110◦ C could significantly be improved. The or- ganic and inorganic components were hydrolysed at a nanoscale. The molecular design of the nanocomposites was achieved by nanosized interfusion among organic. As membranes.3 Nanoparticles for Improved Membrane Properties – Composite Membranes The modification of membrane properties by inorganic materials raised increased interest in the past few years. It is important to maintain the nanoscale platelet structure of the inorganic particles. An increasing interest exists in adding heteropoly acids (HPA) as proton- conducting components to the sulfonated polymers [35]. The hybrids can be structurally and chemically modified to form nanosized interconnecting networks. a reduced methanol crossover could also be a desired re- sult. It finally leads to a slightly reduced proton conductivity but at the same time to a smaller influence of temperature on conductivity so that the conductiv- ity values for 130◦ C are nearly the same for the composite membrane and blank NafionTM . The incorporation of hydrophilic compounds into recast NafionTM films was intensively investigated. Facilitating the water management especially for low-humidity operation conditions and improving the mechanical and thermal prop- erties usually is the goal. The inorganic addi- tive was reported to increase the stiffness of the membrane and reduce the methanol transfer. Thus. Two main preparation procedures are known [30]: the in-situ growth of inorganic materials and the polymer in-situ sol/gel reaction. Nanocomposite membranes consisting of SiO2 /polyethlenoxide (PEO) have been synthesised [34]. layered phosphates of titanium and zirconium were prepared and investigated with respect to proton conductivity. due to reduced conductivity of the latter at elevated temperature caused by drying out of the NafionTM membrane. such as for example silica. manufacturing proce- dures leading to nanoparticles are typically used. Different approaches have been pursued in the past. and it was found that the improve- ment of membrane properties for polyetherketones was less pronounced than for composites with NafionTM . Because of their structural . inorganic and acidic molecules. Tailor-made layered structures of vari- ous zirconium phosphates and zirconium-sulfophenyl phosphates as oriented lamel- lar structures were also investigated [33]. The homogeneous dispersion of small particles in the polymer matrix is of outstanding importance for good membrane properties. Zir- conium phosphate is one of the most prominent inorganic compounds that exhibit proton conductivity and a layered structure. The addition will enhance the proton conductivity and the acceptance of CO. NafionTM and sulfonated polytherketones were used as polymer materials. Hybrid membranes can be produced [31]. The incorporation of inorganic nanoparticles with a high affinity to water into the electrolyte polymers.Nanotechnology for Fuel Cells 163 2. For example in [32].

Membranes with a porosity of less than 1 nm allow the uncomplicated separation of propylene/propane. Intensive efforts are made in the field of gas separation of industrial gas mixtures.g. shrinkage or expansion. The mechanical stress can induce changes in the distribution of the catalytic nanoparticles by e. The temperature stability reached 250◦ C. the pore diameter mainly being below 2 nm. agglomera- tion at fissures. The effect of the enhancement of proton conductivity by overlapping electrical dou- ble layers was intended to be used to fabricate an improved micro fuel cell. which is one order of magnitude larger than the thickness of the electrical double layer.4 Nanostructured Membranes A first attempt to use an array of nanochannels as an electrolyte is described in [39]. membranes with nanosized pores were cast. benzene/cyclohexane and high-pressure CO2 /CH4 mixtures . The HPA have interesting redox and catalytic properties. With monodecylphosphate and phosphotungstic acid. The effect was even ob- served with channels of depth 1–2 μm. K¨onig diversity these materials can be incorporated into a wide variety of membrane ma- terials.164 A. A concise scientific explanation of the observed results still is lacking. Nanosized ceramic powders with good adsorption capacity for acids together with a polymer binder – not an ionomer – were also reported to be developed by Tel Aviv University [37]: silicon dioxide (150 nm). which are not fully understood yet. Heinzel and U. The use of such a membrane consisting of PVDF. and it was expected that this high permeation leads to a high back-diffusion of water to the anode side. SiO2 and triflic acid in a DMFC led to high power densities of up to 500 mW cm−2 [38]. Differences in the local gas and water distribution would lead to different processes in chemical reactions. The presence of nanoparticles of metal phosphonates in the electrode interface Nafion/Pt already improves the electro- chemical characteristics of fuel cells in the temperature range 80–130◦ C [36]. During fuel cell operation the membranes are stressed mainly by mechanical in- terference. 2. The proton conductivity in some cases reaches values even higher than 0. transparent and homogeneous hybrid membrane materials could be synthesised. flexible.1 S cm−1 . thus avoiding the flooding of the cathode catalyst and GDL. and the conductivity of the humidified membrane reached ∼1 × 10−3 S cm−1 at 80◦ C. First ex- periments with micro channels of depth between 50 nm and 50 μm were investigated using diluted aqueous HClO4 as electrolyte. The addition of superacid metal (IV) phosphonates is particularly suitable for the preparation of hybrid membranes. All these membranes still have to prove their practical applicability. With PVDF as polymer binder. The membrane material had 10– 20 times higher water permeation than NafionTM . Normalising the experimental results showed an increase in apparent proton conductivity for the low values of channel depth and being higher than the bulk proton conductivity. alumina (50 nm) and titanium diox- ide (21 nm) were used as nanopowders.

5 Ionic Liquids (ILs) The use of ionic liquids in fuel cells is a further attempt to develop new types of membranes. In fuel cell systems.3-methyl imidazolium triflate (BMITf) and BMI tetraflouroborate (BMIBF4 ) as ionic liquids show excellent con- ductivity at elevated temperatures up to 200◦ C. which requires a well-defined modification of the membrane in the nanometer range. the transport of water throughout the membrane will be hindered. These membranes using 1-butyl. this approach can be used to enhance the catalytic oxidation of hydrogen by improved immobilisation. Furthermore. The general advantage of the ionic liquids is that the conductivity is independent of the water content. The systems are intensively studied for proton transfer towards fuel cell applica- tions under water-free conditions ([44] and references therein). Dow) even show higher conductivity values in a temperature range from 40 to 180◦ C. The application of these types of membrane is also useful for fuel cells since they allow a molecular transport of the fuel gas and water [41]. The reported ionic conductivity is sufficient enough. even though the values of 100 mS cm−1 are based on the IL itself. The main advantage is that such a system is independent of the water content formed during the fuel cell reaction. These ILs are known as Brønstedt acid–base ILs and require certain conditions in preparation. The combination of nanoparticles. The first evaluation of ILs as electrolytes for fuel cells has just been done [25]. ionic liquids and solid surface showed excellent synergistic effects to enhance the activity and durability of the catalyst. and a sophisticated water management is not necessary. Huang et al. The water produced during the reaction will not diffuse through the membrane. The reaction takes place via a solution-diffusion mechanism. Adequate hydrophobic properties of the ionic liquids are necessary to realize the three-phase boundary necessary for the fuel cell operation. BMITf-imbibed membrane samples (Nafion. this material class is a promising alternative to the other attempts of polymer materials. 2. Another approach is related to the functionalisation of nafion membranes by replacement of water by ionic liquid used to realise a suffi- cient proton conductivity of NafionTM membranes. immobilised Pd nanoparticles on molecular sieves by ionic liquids [42]. The catalytic system was used for solvent-free hydrogenation. .Nanotechnology for Fuel Cells 165 [40]. Ionic liquids are considered more and more as alternatives for conventional elec- trolytes [44]. This appears to have been the first attempt to apply ILs under aprotic conditions. they do not include the target ions such as protons and the primary charge carriers are still not known yet and are under discussion. Because of the current development in the field of ionic liquids. The main nanotechnological approach of the ionic liquids is the opportunity to immobilise the catalysts by covering the nanoparticles with a liquid phase onto a solid surface. A first approach was published [43] in which NafionTM was swollen in ionic liq- uids instead of water.

166 A. Heinzel and U. K¨onig

One of the most interesting systems is the class of imidazoles. They are self-
dissociation compounds with high proton conductivity (>100 mS cm−1 ) without any
acid doping. Further enhancement of the conductivity and also the thermal stability
of the system can be realised by the addition of acidic components [45]. This is due
to the proton transfer via the Grotthuss mechanism.
Two other types of ionic liquids are very promising candidates for conducting
polymers. They are ionic liquids based on choline chloride, which have already
shown superior properties in electrochemical processes (e.g. metal finishing) [46],
and single-ended or double-ended diallylammonium ionic liquids, which are protic
compounds with a high potential for excellent proton conductivity [47].
Furthermore, the solubility of the fuel gas oxygen and hydrogen has to be as
small as possible but not completely insoluble. In general, the experimental results
indicate a very small solubility [44,48]. Nevertheless, it is possible that the solubility
of the gases influences each other [49].
It is important to realise a low pH value to enhance the proton conductivity. This
can be done by an adequate anion such as PO4 3− . The challenge in preparing the ad-
equate ionic liquid is the realisation of the Grotthuss mechanism in the proton trans-
port. For example it is shown by Kerr et al. that the linkage of aliphatic chains to the
imidazole molecule results in a decrease in conductivity [50]. This is explained by
the hindering of the N-substituted imidiazole to participate in the Grotthuss mecha-
nism by a structural effect. Kerr et al. also indicate that due to possible volatility the
IL must be fixed to a matrix. Current models developed using Hole theory [51] will
be used to design the compounds with optimum conductivity and viscosity.
The requirements of an adequate liquid are as follows:
• Broad electrochemical window
• Thermal stability up to 300◦ C
• Stable against hydrolysis
• Hydrophobic
• Free of halogen
• Recyclable
• Cheaper than NafionTM
For structuring, the IL has to be immobilised. This can be done using i.e. zeolitic
structures or molecular sieves. It is obvious that with increasing surface area of the
solid phase, the motion of the liquid and the proton transport will be hindered. From
polymerisation experiments it is known that the stiffening of polymers by cross-
linking can be compared with the polymer–surface interaction. Electrode surfaces
and solids such as silica, carbon black or cathode powder also stiffen the polymer
[52]. This can be explained by different transport properties at the interfaces. As a
consequence it must be expected that at the surface of the added particles the ionic
liquid will behave in a different way than in the immobilised liquid phase.
Studies of the use of molecular sieve exhibit that Pd nanoparticles can be immo-
bilised by the combination of molecular sieves and ionic liquids. The results indicate
that the nanoparticles immobilised onto the molecular sieve by ionic liquids were
very active and were stable catalysts for the solvent-free hydrogenation of olefins
[42, 53, 54].

Nanotechnology for Fuel Cells 167

Another nanotechnological approach is the use of a metalorganic chemical va-
por deposition (MOCVD) process. This process will be used for producing highly
nanodispersed platinum particles on GDL allowing the decrease of overpotential re-
sistance of oxygen reduction reaction. The interest of the MOCVD process is linked
with vapour penetration inside the first ten μm of the substrate (carbon layer for ex-
ample) allowing a 3D repartition of the catalytic element inside the carbon network.
MOCVD process brings then a rational approach of the platinum loading inside
the active layer in terms of platinum accessibility and electroactivity. This MOCVD
process will be developed on a range of catalysts in order to immobilise the catalytic
phase on electrode (carbon support) or on membrane support, and to select a highly
stable catalyst in contact with the ionic liquid [55].
Table 1 compares the relevant properties of various alternative materials.

Table 1 Comparison of conductivity data and values of glass transition temperature for various
membrane materials
Material Test conditions Conductivity Glass transition Remarks
T (˚C) RH (%) mS cm1 temperature RH = relative
T (˚C) humidity/water

Aqueous systems
FS-PEEK [56] 120 50 30 >140 κ = f (RH)
BPSH [56] 120 50 55 135 κ = f (RH)
F-PES [56] 120 50 20 140 κ = f (RH)
F-PES [57] 120 50 3–30 90 κ = f (RH)
HPA – Nafion [56] 120 50 30 90 κ = f (RH)
Nafion 117 [57] 120 50 30 90 κ = f (RH)
Nafion 1100 [58] 120 50 30 κ = f (RH)
3M [56] – perfluorinated 120 0 40
sulfonic acid
Dupont [56] 120 50 >150 κ = f (RH)
Ionic liquids
Nafion [26] 3-methyl 180 0 100 200
imidazolium BF4
PBI [58] (polybenzimidazol) 200 30 50 200 κ = f (RH)
EMImBF4 [59] – 1-ethyl-3- 120 <5% 100 κ = f (RH)
methylimidazolium BF4
BMImBF4 [59] – 1-butyl-3- 120 <5% 50 κ = f (RH)
methylimidazolium BF4
BMIm [29] – 1-butyl-3- 200 <5% 80 300 κ = f (RH)
BMPBETI [59] – 1-butyl-3- 120 <5% 20 κ = f (RH)
pyrazolium BETI
Gel-type membranes [60], 150 100 κ = f (RH)
various polyether
Silica gel stabilised [27] – 230 30–80 κ = f (RH)
imidazolium (IONOGEL)

168 A. Heinzel and U. K¨onig

3 Electrocatalysts in Polymer Electrolyte Membrane Fuel Cells

The electrocatalysts for PAFC and PEMFC are quite similar; the increase in op-
eration temperature from 80◦ C being typical for the PEMFC to 200◦ C for PAFC
is not so significant that the use of expensive noble metals could be avoided. The
CO tolerance of the PAFC anode is much better with a tolerable level of approx-
imately 1 vol% of CO compared with 10 – maximum 100 ppm in short transients
for the PEMFC. Thus, there were a lot of parallels in the catalyst development, and
PEMFC developers could make use of the insight gained by PAFC development
and vice versa. Therefore, the following chapter refers to the PEMFC but uses re-
sults being generated for PAFC.

3.1 General Properties

Possible fuels for PEMFC are besides pure hydrogen, mainly reformate and
methanol. Other alcohols and organic fuels may also be converted but with much
lower current densities. At the low operation temperature of the PEMFC, noble
metal catalysts still can not be replaced, though a lot of research is going on for
developing non-noble metal catalysts [61]. Because of the high cost of noble metals,
the loading of platinum, ruthenium or other noble metals is a focal point: the first
PEMFC prototypes operated with 2–4 mg cm−2 of pure noble metal, but a reduction
to a tenth of this value was soon achieved by preparation of supported catalysts –
noble metal nanoparticles on a carbon carrier material. In the same time, current
densities were improved, leading to remarkable lower cost in respect to power
per m2 . The manufacturing methods of supported precious metal catalysts made
significant progress. The first well-known preparation method was impregnation of
the carbon carrier material with a solution of a salt of the respective noble metal.
Drying, reduction and sintering led to an even distribution of nanoparticles on the
carbon surface. Commercial catalysts and catalyst-coated membranes were man-
ufactured. An improvement was achieved by introducing the sol/gel preparation
method to the manufacturing of fuel cell electrocatalysts, leading to even finer
particles [62].
Especially at elevated temperature small particles tend to agglomerate, therefore
a spatial separation is important. It was found [31] that the platinum surface area
correlates with the BET surface of the carbon carrier material. This is easily under-
standable as a better dispersion of the noble metal particles leading to higher elec-
trochemical activity. But as soon as the platinum particles reside in very small pores,
smaller than 40 nm, they do not contribute to the electrochemical reaction anymore
[63]. Thus, optimisation of the carrier material as well as of the composition and
dispersion and manufacturing of the catalysts still is going on.

Nanotechnology for Fuel Cells 169

Because of the importance of this topic, several research groups have investigated
the possibilities for further improvement [64].
In the electrocatalytical field the main challenge is the control of the particle size.
On the one hand the optimum size for e.g. oxygen reduction has to be controlled.
Different values of optimum size are reported ranging from 1.5 up to 50 nm ([65]
and references cited therein). It is supposed that this is related to the different an-
alytical range for particle characterisation and electrochemical measurements. The
former is carried out over a small region of the electrode of some hundreds of nm
whereas the latter is performed on a high surface area of cm scale. Therefore, mi-
croelectrodes have to be used to guarantee a comparable measuring range.
On the other hand the stability of the nanoparticles during the fuel cell reaction
is important. The Pt particles can corrode within the system and will be deposited
at different locations [66]. This effect will lead to an agglomeration of the particles
at fissures [67] (Fig. 8). Furthermore, it is well known that dispersion and surface
area of Pt particles will change during the application of high electrical fields. The
details are reported recently by e.g. Antolini [68].
Since the electrical properties of the nanostructures will govern the catalytic
properties, their change in the nanoregion is important. The quantum size effects tak-
ing place in this regime become more and more important even though the electronic
conducting materials in the quantum confinement regime have not been described
yet [69].

3.2 Relevant Reactions

3.2.1 The Oxygen Reduction Reaction

The reduction of oxygen is the main reason for the overvoltage occurring in a fuel
cell. Thus, lot of emphasis was put into improving the catalyst activity by different
means such as alloying the noble metals or accurate particle size control during the
preparation processes. Some Pt alloys with transition metals showed higher oxygen
reduction activity compared with pure Platinum [70]. Gas diffusion electrodes with
Pt/Co as catalyst are commercially available (E-TEK), showing slightly inferior be-
haviour compared with the platinum gas diffusion electrodes.

3.2.2 The Hydrogen Oxidation Reaction

The hydrogen oxidation is a much faster reaction, and is usually not limiting the
fuel cell performance. Platinum is the optimal catalyst, but nevertheless, loadings of
0.45 mg cm−2 are state of the art of commercial available fuel cell electrodes. A fur-
ther reduction and thus a better use of the noble metal loading should be possible
and has been investigated.
The more important challenge is to maintain catalyst activity, when reformate
is used as fuel. Reforming of natural gas, gasoline or diesel leads to a gas mixture

CO is a catalyst poison [71] even in the low concentrations being achieved by the methods for fine purification of reformate (selective catalytic oxidation or selec- tive catalytic methanisation of CO). most well known for this purpose is Ru. The removal of CO from Pt catalyst sites can successfully be achieved by oxygen-containing species. The Pt/Ru ratio and the degree of alloying have been varied to develop electrodes with optimal CO tolerance. a EDX mapping of a freshly prepared PtO2 /NafionTM layer. . Heinzel and U. K¨onig Fig. b Pt-EDX mapping of a PtO2 /NafionTM layer after electrochemical cycling containing CO2 and CO in addition to the hydrogen being generated. 8 Agglomeration of Pt particles on a PtO2 /NafionTM layer after electrochemical treatment [66]. At low temper- atures. Tin and molybdenum are other possible candidates. which is present as RuOx under fuel cell operation conditions [72].170 A.

a layer of the catalyst is covered by silica sol. Preliminary investigations have been performed on using C60 -fullerenes as car- rier material [76]. . but current density in general was low due to the low platinum loadings (maximum 100 μg cm−2 ). improved preparation methods include alloy formation. Electrophoretically deposited C60 nanoclusters were deposited onto electrically conducting glass sheets. Various procedures have been investigated to prepare active DMFC anode cata- lysts. which are stiff state of the art. electrodeposition of Ru on Pt. Pt deposits on the carbon particles maintaining their initial size (∼2 nm). The basis is platinum and ruthenium: platinum is the most electroactive metal. By adding the carbon carrier stirring and removing the solvent. catalyst samples were prepared. in a second step. In a first step. high noble metal loadings are required according to the state of the art. At the high loadings in the mg/cm2 range. First electrochemical measurements proved their activity in principle. For the increased noble metal loadings on carbon carrier materials being usually necessary for good methanol oxidation performance. dry oxygen and 2 molar methanol solution). the noble metal coating on the membrane usually has a sufficient thickness and lateral electronic conductivity. it is important to avoid the initiation of agglomeration of the deposited nanoparticles [73].7 nm. A carrier material was alter- nately immersed into the Pt/Ru solution and into phosphodecatungstate solution. The main factors for catalyst ac- tivity are alloy formation. the reduction of this high amount of noble metal in the electrodes is a focal point for development. Pt–Ru codeposition and adsorption of Ru on Pt. By this layer-by-layer preparation method a network film can be realised. The reduction of metal salts (PtCl2 . With a loading of 3 mg cm−2 of noble metal on the anode side a relatively high activity was achieved (160 mW cm−2 at 70◦ C.08 mg cm−2 ) for direct comparison with com- mercial catalysts.Nanotechnology for Fuel Cells 171 3. The simplest approach is physical mixing of Pt and Ru powders. and platinum particles were deposited by electrical reduction of a solution of H2 PtCl6 . RuCl3 ) in solution by LiBH4 and their sub- sequent dispersion and stabilisation in THF to form a colloidal solution were used in [74] to synthesize electrocatalysts for DMFC anodes with a well-defined parti- cle size of 1. and ruthenium at least partly covered with hydroxides is used for removal of CO by transfer of oxygen. For DMFC also. being then transferred into a gel and finally to aerogel by supercritical processing.2. The samples show a BET surface of 731 m2 g−1 and a mass normalised current for methanol oxidation of 60 mA mg−1 . a carrier material is not necessarily required.3 Oxidation of Methanol The degree of catalyst utilisation is even lower in DMFC. An increased activity of the so- prepared electrodes compared with platinum was observed. surface structure and good dispersion of the comparable small particles. but the noble metal loading was too low (typically 0. Sol/gel techniques to prepare modified Vulcan XC-72 electrodes by applying a platinum sol and a silica sol to the graphite material have recently been reported to lead to electrodes with a tenfold higher activity towards methanol oxidation [75]. Another approach is the synthesis of Ru-covered Pt nanoparticles and their fixation to anionic phosphodecatungstate PW12 O3− 40 [77].

The carbon black Printex XE2 showed to stabilise the precipitated PtOx nanoparticles during the elec- trochemical reduction process. The investigation of carbon carrier materials from the Sibunit family being prepared by pyrolysis of natural gas followed by an activation process to achieve the desired surface area and pore vol- ume was carried out [80]. K¨onig Because of this diversity in investigated preparation procedures future improvement of catalytic activity and reduction of noble metal loading for DMFC anode can be expected to be realised. The utilisation of the noble metal is the highest with 10% catalyst low loading on low BET surface area carbon (∼70 m2 g−1 ). A recent systematic comparison of the suitability of various commercially avail- able carbon carrier materials as electrode for fuel cells [79] using exactly the same preparation method for platinum loading led to the result that surface roughness has a superior positive influence on stability of nanoparticles. For PAFC it was reported [31] that these ungraphitised carbon materials are not stable on the cathode side and graphitising led to a remarkable loss in surface area of the carbon. The catalysts were characterised in a DMFC half cell. In this work it was shown that the positive effect of a low loading of Pt/Ru catalyst dominates the positive influ- ence of a high carbon surface area. the long-term stability of catalyst nanoparticles will also be a future issue. the pore volume and size. . which was applied to the catalyst material. These early investigations already showed that the carbon carrier material significantly influences the activity of the deposited noble metal particles. As higher temperatures are extremely favourable for DMFC operation. The goal was to design the optimal carrier material for a DMFC anode. The carbon particles do not contain micro pores: pore diameter ranges from 3–100 nm. It fulfils the most important general requirements of chemical stability and electrical conductivity.3 Optimise Carrier Material In membrane fuel cells and PAFC as well. Four out of 15 samples showed these advantageous properties. This example shows that various factors influence the activity of a fuel cell electrode. high electrical conductivity and consisting of uniform spherical particles could be pro- duced. Heinzel and U. Carbon materials with 1–500 m2 g−1 of high purity. the distribution of noble metal particle size as well as the manufacturing process for the MEA. usually carbon is used as carrier for the noble metal catalyst. The effect of platinum loading on the electrochemical activity mainly for oxygen reduction under PAFC conditions was thoroughly investigated [78]. One of the first and very commonly used carbon carrier materials was Vulcan XC-72 (Cabot Corp. the BET surface of the carrier material.) with a BET surface area of about 250 m2 g−1 . 3.172 A. either by diffusion hindrance or by blocking of small pores for example by ionomer due to the fabrication process of the membrane/electrode assembly. The result is explained by the negative influence of small pores <20 nm – being present in high surface area carbon carrier materials – on electrochemical activity.

forming a surface structure with very dense whiskers. 9. Recently. the mean pore size could be varied by this preparation method – the mean diameter being either 50 nm.3. the development of carbon-free materials has been published [82]. Again. carbon nanotubes and carbon aerogels are investigated for the improvement of electrode properties. The activity of this new electrode is higher than that of carbon supported electrode and shows even better electrochemi- cal stability.2 Nanocomposites Another option is the replacement of carbon as electronic conducting carrier ma- terial and the proton-conducting NafionTM in the electrode layer as well by a conducting polymer. achieving higher surface areas for improved fuel cell performance is the goal. As electronically conduct- ing polymers.3. The manufacture of a Pt/Ru–polymer nanocomposite was successfully carried out and first samples were tested in a DMFC.Nanotechnology for Fuel Cells 173 In new approaches. poly(N-vinyl-carbazole) and poly(9-(4-vinyl-phenyl)-carbazole were Fig. The organic material Perylen red serves as a conductive and stable support. 3. Large pores and especially the micro-porous structure with a large surface area led to a good metal dispersion and a high activity in a DMFC. The structure of this electrode material is shown in Fig. 3. by which an improvement of the interfacial properties was ex- pected [83]. 90 nm or a mixture of both. 9 Whisker-like carrier material . which means carbonizing a polymer silica composite and removing the silica [81].1 Nanostructured Carrier Material Another approach to synthesize carbon carrier material with defined structures is the silica template method.

K¨onig used. 86]. see [88] or [89]. Kim et al. The doping of hydrides with carbon shows an improvement of the hydrogen sorp- tion kinetics. and this depends on the moisture [87]. By increasing the operating temperature the second main problem of the PEMFC will be solved.3. For a review of recent work. The process is based on the high catalytic activity of gold nanoparticles for CO . High hydrogen adsorption capacity was reported for various carbon nanotubes. the catalyst poisoning through carbon monoxide (CO). NHE). In case of the DMFC carbon monoxide exists even more. One important issue is the use of these materials for hydrogen storage [85. because they will dry out and then they are not anymore ion-conductive. The electrochemical data were slightly lower than with carbon-supported cat- alysts. XPS measurements show in comparison to conventional Pt/graphite electrodes an enhanced surface concentration of OH–. It is assumed that the CNT surface groups make the substrate more hydrophilic and therefore they speed up the transport of the protons from the reaction site. so that the catalyst stays active. used gold nanostructures such as nanotubes or nanoparticles to oxidise CO [91].g. electrochemical stability against potentials U > +1 V vs. and on the other hand they will become gas permeable. CNT surface groups act as a co-catalyst and make the kinetics of the oxidation reaction more efficient.e. The capacity can be significantly increased by doping with e. CO– and CO2 H–groups. because it is produced as a by-product during methanol oxidation. It is not known yet if the particles will agglom- erate during the fuel cell process.3 Nanotubes Up to now the operating temperature is limited by the perfluorined membranes used as electrolyte.174 A. Heinzel and U. Nanotubes show also very promising properties in the fuel cell reaction. They can not be used above temperatures T = 120◦ C. i. The nanoparticles deposited on the CNT with a diameter of 2 nm agglomerate on the CNT surface. Conductivity measurements and cyclovoltametric investigations (CV) confirm their suitability as fuel cell electrodes (high electronic conductivity. because they will be operated above their glass transition temperature. 3. which confirms the catalytic role of the carbon structure [90]. The application of carbon nanotubes (CNT) sensitised with metal clusters (Pt. The newly developed electrodes exhibit improved exchange current density in H2− and also in DMFC operation by the factor 5–10. On the other hand the. Ru) opens new possibilities to enhance the fuel cell process [84]. but it is expected that an improvement of the electronic conductivity of the polymer used would lead to even better data. Beginning at an operation temperature of T > 150◦ C the carbon monoxide will be oxidised by thermal energy to carbon dioxide and will leave the cell with the gas stream. Even though the mechanism of hydrogen adsorption is not clarified yet. Li-doped mate- rial adsorbs up to 20 wt% and K-doped nanotubes up to 14 wt%. forming clusters of about 20–40 nm. the increase in catalytic adsorption is proven. Li or K.

and thus the bipolar plate shall not significantly contribute to this value.4 Structure of the Interface The most sophisticated task is the preparation method to realize a layer with suffi- cient porosity. 3. The ink is used to coat the membrane by pasting. spraying or similar methods. The performance of an electrode with a lower loading of 0. The most impor- tant properties are the electrical and thermal conductivity. With NafionTM ionomer solution and low loadings of 0.16 mg Pt/cm2 thin electrodes <10 μm were prepared and a good electrochemical performance was achieved. many attempts to improve the structure and thus the performance of the catalyst layer were undertaken. The reduced POM can be reoxidised in fuel cell systems that contain simple carbon anodes. Besides the bulk resistance of the material the contact resistance be- tween bipolar plate and GDL has to be considered. The resistance of a PEM fuel cell usually is dominated by the membrane electrolyte. A number of catalysts do not have a sufficient contact to the carbon and can not participate in the reaction. A second important aspect is . It was proven that the efficiency of the catalysts in- creases by the factor 2–3 up to 100% [95]. the phase boundary between electrolyte and collector electrode system will be specif- ically nanostructured [93. 3. Starting from this basic method. This problem can be overcome by depositing the catalysts by an electrochemical reaction from adequate precursors. 94].3. A review about the present state is given in [97]. hydrophobicity and good access for the reactants to the catalyst parti- cles. The performance of these systems in PEFC and DMFC systems is at least comparable to that of conventional systems.1 mg/cm2 was found to be optimal due to the use of an optimised carbon car- rier material and improved preparation process leading to a finer dispersion of the coagulated ionomer.12–0. A mixture of the supported catalyst with liquid ionomer in a solvent is usually the basis forming a so-called ink. As a consequence. 4 Bipolar Plates The materials for bipolar plates have to fulfil several requirements. One example is the formation of a colloidal dispersion of the perfuorosulfonate ionomer [96] – FlemionTM in this case – cross-linked to Pt- loaded carbon particles. screen printing.Nanotechnology for Fuel Cells 175 oxidation [92]. A reducible polyoxometalate (POM) such as H3 PMo12 O40 serves as a strong oxidizing agent for CO and as an energy-storage agent for electrons and protons.4 Electrochemical Deposition of Catalysts The deposition of catalysts onto the carbon takes place usually by mechanical mix- ing.

176 A. K¨onig the chemical stability.2 Carbon Composite Bipolar Plates Thermoplastic carbon composite materials are a favourable material combination for bipolar plates because they can be manufactured by the mass production pro- cess of injection moulding [102]. but needs at least an im- pregnation to show the required gas tightness. The influence of operation temperature was shown to be crucial [99]. the air and the fuel plate. research with focus on metallic materials and cheaper coating processes was continued. The electrical re- sistance (voltage drop at the single plates. Electrical conductivity of a carbon composite re- quires a high content of carbon. corrosion- resistant metals and carbon composite materials can be used. In principle. Metals are the first choice for high power density applications. hydrogen on the anode side as reducing agent and air on the cathode side causing an oxidising environment combined with the presence of water and elevated temperatures are the main operation conditions. but as well material cost as cost for the coating process should be avoided. 4. It is well known that uncoated stainless steel bipolar plates exhibit high transition impedances due to formation of an oxide layer by corrosion under fuel cell operation conditions. hot pressed or injec- tion moulded carbon composite materials – either with duroplastic or thermoplastic binder materials – will be the options. but published results are scarce. leading to direct contact between graphite particles. Additionally. usually a mixture of graphite and active coal. According to the state of the knowledge. embossed or hydroformed metal plates. Thus. respectively) and the accumulation of metal cations in the MEA during cell operation have been investigated and taken as a measure for the quality of the coating [101]. State of the art is a corrosion-resistant coating with gold. The development of electrical conducting coatings included oxides. Heinzel and U. 4. Graphite is corrosion resistant. Physical vapour deposition and chemical vapour deposition have been con- sidered to be feasible coating processes for metallic bipolar plates. V or Fe [100]. W. ni- trides and borides of the metals Cr. a basic conductivity of the polymer matrix by the smaller active carbon particles is achieved. Ti. as their conductivity is superior to that of all carbon composites. First results were promising but long-term measurement showed that all the commonly used stainless steels show severe corrosion damages after several thousands of hours of operation at elevated temperature.1 Corrosion-Resistant Coatings for Metallic Bipolar Plates The investigation of use of stainless steel as metallic bipolar plates started quite late [98]. The injection . carbides. The percolation limit of the graphite in the polymer binder has to be exceeded. Mo. In addition to that possible impu- rities of carbon have to be taken into account as catalyst poison.

Ex-situ methods such as diffraction methods show details about the electronic properties of nanostructures [104]. 5 Analytical Challenges To improve the development of nanostructures and their application adequate ana- lytical methods are required. . 10 [103]. and thus the most important criteria for use in a fuel cell are fulfilled. 10 View of a section through an injection moulded bipolar plate moulding process leads to a favourable orientation of graphite particles in the direc- tion of the current flow and to a thin and gas-tight skin. which is necessary for the high activity of this material as a co-catalyst for CO-tolerant Pt-RuOx fuel cell electrocatalysts. Understanding the relationship between the nanoscale structure and electrochem- ical properties in materials will also lead to the design of other active materials for electrochemical power sources.Nanotechnology for Fuel Cells 177 Fig. Catalysts made of electronically conducting RuO2 are surrounded by hydrous proton-conducting regions [105]. A picture of a section through an injection moulded bipolar plate is given in Fig.

It can be expected that in due time the resolution reaches the nm scale and important information about the water distribution during the fuel cell reaction can be obtained.178 A. It is well known that the electrochemical kinetics are strongly dependent on the crystallographic orientation of the metal surface [107. Conventional electrochemical methods require the use of a reference electrode to control the potential. Other methods like neutron imaging are very complicated. A spatial resolution in the 1-μm scale can be reached [116]. Especially the performance of the metallic catalysts is governed by the orien- tation. To sup- ply these applications with constant energy. neutron imaging is a valuable in-situ method to explore the two-phase flow phenomena in fuel cell systems with relatively mean interference with the cell [115]. The realization of miniaturised devices is largely due to the use of advanced materials and/or fabrication methods. Heinzel and U. Sufficient results can be obtained from scanning electrochemical experiments. The number of miniaturised applications especially in the electronic and medical region will increase even more in the next periods of time. there is a limit in the scaling of the total system because of the burden of . Furthermore. 108]. the fuel cell has to be miniaturised as well. One important aspect is related to fabrication. Nevertheless. From the results specific preparation routes for new catalytic systems can be derived [114]. Nanotechnology will provide the miniaturization of this development with important aspects. To avoid as much disturbance of the fuel cell process as possible the diameter of the capillary has to be less than 1 mm [112]. K¨onig More complicated are in-situ methods to analyse the electrochemical behaviour of fuel cell systems since the reactions analysed separately can differ significantly from those taking place in a real fuel cell system [106]. such as integrated chip-battery/fuel cell systems or active implants for biocontrol. Even though the disturbance of the water management and the conductivity of the membrane can be minimised a change in the distribution of the electrical potential has to be taken into account. the porosity of the system dominates the transport properties within the electrolyte [109–111]. however. Since the thickness of the membrane electrolyte is about 50–200 μm. By the use of the scanning electrochemical microscope (SECM) the electrochem- ical properties of catalytic materials can be achieved with high spatial resolution [113]. A direct monitoring of degradation processes of membranes by means of ESR spectroscopy allows the development of better materials with adequate nanostruc- tural properties [117]. 6 Future Application – Power Sources Based on Fuel Cells for Nanotechnological Applications [118] Fuel cells are especially promising for long-term application with constant energy consumption. the implementation of a Haber-Luggin capillary is complicated.

Ing. C. The stream flows over the anode and the cathode electrodes placed on opposing side walls within the channel. The examples described earlier show the high importance of nanotechnology for the fuel cell devices. Steele. Microfuel processors have also been designed for converting methanol into hydrogen using 5-mm2 -sized reformers and combustors [121]. Nature 414. 345–352 4. Even though theoretical calculations predict an increasing fuel cell power density increase with decreasing channel size due to the reduced diffusion blockage of ribs and increased convection in micro channels. In these membraneless laminar flow-based fuel cells (LF-FC) two or more liquid streams merge into a single microfluidic channel. A. This is explained by the generation of cracks in larger catalyst particles.. The reaction of fuel and oxidant takes place at the electrodes while the two liquid streams and their liquid–liquid interface provide the necessary ionic transport [122. Handbook of Fuel Cells. H. Wiley. A. Eds. the experimental observation revealed an optimum channel size with maximum power density. Grot. Nanoforum Energy Report. Gasteiger. Furthermore. 47. The advantage of nanoscale fuel cell devices is that a direct electrochemical reaction can be used for electricity production. From these kinds of micro fuel cell devices. W. The potential fuels might include reagents in blood or water. MS 260/75 . A successful design requires an adequate understanding of how the performance is influenced by the design and manufacturing process [119]. VDI-Nachrichten. April 2004 (nanoforum. which serve as triple-phase boundaries. Micro fuel cell designs without polymeric membranes can overcome some PEM- related issues such as fuel crossover. One approach has been re- ported for a biofuel cell operating in a glucose-containing buffer solution [124]. The characteristic feature is that the interconnection of electrodes from two different cells is located on the same side of the membrane realizing a planar design.H. 2003 5. and/or metal nanoparticles. Also the molecular application of nanodevices and the necessary fuel support will finally lead to smart refuelling systems. 1975. Carbon fibres are coated with catalysts for the selective oxidation of glucose (glu- cose oxidase) and reduction of oxygen (bilirubin oxidase). Technology and Applications. 2001. 123]. Fundamentals. Tech. W. 2002 (VDI-nachrichten. References 1. Miniature fuel cells with a peak power exceeding 40 mW/cm2 [120] have been designed utilizing a clever flip-flop design and advanced etching and deposition techniques.Nanotechnology for Fuel Cells 179 their auxiliary components. which produce 50 nW per mm of fibre. Lamm. Chem. Vielstich. anode dry-out or cathode 2. the particle perimeter dependency of Faradic impedance changes to particle area depen- dency as the particle size increases. opportunities arise in the field of nanoscale power sources where the fuel can be delivered directly to the point where the energy is 3. Heinzel.

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This approach represents a significant depar- ture from more traditional materials involving micron-sized powders. These high surface area ma- terials have a large pore volume and exhibit lithium capacities much higher than B. Dunn () Department of Materials Science and Engineering.Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials Winny Dong and Bruce Dunn Abstract Aerogels constitute a unique class of nanostructured materials. University of California. c Springer Science+Business Media LLC 2009 . Research on cathode materials has also led to interesting results.1007/978-0-387-49323-7 5. Leite ( E. DOI 10.). There are in- dications that the use of nanostructured materials may lead to advantages in both discharge rates and cycle life of lithium-ion batteries. They possess a three-dimensional network of nanometer-sized solid particles within a continuous mesoporous volume. Another route to nanostructured cathode materials is to tune the morphology of the solid as occurs in the synthesis of aerogels. USA e-mail: bdunn@ucla. Results obtained with vanadium oxide aerogels are highlighted as these materials exhibit a number of de- sirable characteristics for secondary lithium batteries. CA 90095. Los Angeles. sulfides. and nitrides leads to in situ formation of nanos- tructured materials with excellent properties as anodes in lithium cells [2]. Nanostructured Materials for Electrochemical Energy Production 185 and Storage. decreasing the crystal size in anatase-type TiO2 extends the solid solution domain and leads to improved re- versibility because of better accommodation of the structural changes that occur upon lithium insertion/deinsertion [3].R. This chapter reviews the importance of aerogel nanoarchitecture in achieving high-performance electrochemical properties. Nanostructure Science and Technology. The reaction of lithium with simple 3d oxides. 1 Introduction Nanostructured materials have emerged as an increasingly important direction for electrochemical energy storage [1]. The materials have low density and high surface area and only recently have they begun to be explored as electrochemically ac- tive materials. fluorides.

in addition to the intercalation capabilities. etc. Since oxides have inherently defective surfaces. Several transition metal oxides (MoO3 . the de- fect chemistry associated with high vacancy concentrations is likely to influence the electrochemcial properties. The high porosity also enables the electrolyte to penetrate the entire cathode or anode structure. In this chapter. the large amount of surface area means that the electrochemical properties are dominated by surface properties and surface defects and not the bulk material. This morphology is especially interesting to researchers working on batteries with high rate capabilities – the ability to deliver a large amount of capacity over a relatively short period of time. The large volume of free space allows for the easy transport of ions and the large surface area provides an electrochemically active surface that is not constrained by diffusion limitations. 1. 2 Materials Synthesis 2. The layered structure intercalates lithium while the mixed valence transition metal centers allow for electron transfer. After a brief intro- duction to aerogels and their synthesis methods we give an overview of the elec- trochemical characterization techniques employed when dealing with nanostruc- tures. Aerogels processed through the sol–gel method have another interesting characteristic: they are often amor- phous or nanocrystalline. Aerogels constitute a unique class of nanostructured materials. The ability to prepare oxides in this metastable phase provides another aspect where battery performance can be modified and potentially enhanced [7]. This chapter concludes with a case study on how aerogel nanostructures have improved the electrochemical properties of vanadium pentoxide. Aerogels pos- sess a three-dimensional network of nanometer-sized solid particles surrounded by a continuous macroporous (> 50 nm) and mesoporous (2–50 nm) volume as shown in Fig.186 W.1 Transition Metal Oxide Aerogels Through Sol–Gel Synthesis Transition metal compounds are important materials for electrochemistry due to their ability to exist in various valence states. One such surface effect is the large amount of double- layer capacitance. V2 O5 . . Known for their low density and high surface area. aerogels provide both molecular accessibility and rapid mass transport and have been part of the heteroge- neous catalytic materials field for over 50 years [6]. as well as larger molecules [5]. we focus on the importance of nanoarchitecture in determining the electrochemical properties of transition metal oxide aerogels. Dunn polycrystalline. Additionally.) have gained additional attention in the field of secondary lithium batteries due to their layered structure. nonporous V2 O5 . observed for V2 O5 aerogels [4]. These layers can be propped open by in- tercalated species such as solvated lithium and sodium ions. Dong and B. MnO2 .

the ability to produce metastable phases is also of importance. The field is largely based on silica and other insulating oxides such as alu- mina. etc. . ethyl.and mesoporos- ity (reprinted with permis- sion from Royal Society of Chemistry) Although the main characteristic and advantage of aerogels is its high surface area. propyl. The sol–gel process is based on the hydrolysis and condensation of molecular precursors [11]. the rate of gelation. It is evident. Aerogels are produced when the liq- uid byproducts of the sol–gel process can be removed without collapsing the solid network of the wet gel. or kinetically trapped. n is the va- lence of the metal. This pro- cess offers a different approach to the preparation of transition metal oxides which generally are based on high-temperature heat treatment of powders. metal alkoxides. dip-coating. Because of the lower preparation temperatures. The resulting gels can be formed into fibers. The most versatile precursors are the metal organic compounds. and the drying method. phases can be produced [9]. Following is a brief discussion on the basic chemistry of the sol–gel process. however. films. Some of the other advantages of the sol–gel method include the ability to ob- tain homogeneous multicomponent systems and better control of the entire synthe- sis process. Sol–gel processing is a room temperature synthesis method in which liquid chem- ical precursors react to form inorganic ceramic and glass materials [8]. 10]. unusual amorphous materials or ceramics with metastable. or impregnation. or composites by spinning. type of catalysts used. The synthesis of tailor-made materials is possible through changing the composition of the precursors. The sol–gel technique has been thoroughly described in review articles and books [8. 1 Schematic of the nanoscale solid network of an aerogel interspersed with both micro. Amorphous metal oxides of vanadium and manganese have demonstrated higher specific capacities and reversible lithium-ion insertion capacity than do the crystalline forms. Metastable phases are frequently present due to the low synthesis temperatures involved. M(OR)n . The transition metal is represented by M. and R is an alkyl group such as methyl. that considerable attention is being given to the transi- tion metal oxides [11].Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials 187 Fig.

most transition metal alkoxides must be handled with great care. H2 O + MOR → MOH + ROH (1) This reaction follows a nucleophilic substitution mechanism [8]. With the notable ex- ception of silicon. the faster the substitution reaction. Solvate formation. The resulting wet gel is an amorphous. the solid phase is between 5 and 10% of the total volume. This reac- tion must be slowed in order to form a transition metal oxide with bridging oxygen bonds throughout the structure. the less electronegative the metal atom due to steric hindrance (shielding of the metal atom by the alkyl group). The rate of reaction will depend on the coordination unsaturation and oxidation state of the metal atom. Therefore. Hydrolysis of the alkoxide occurs when water is added and a reactive M–OH hydroxo group is generated [11]. and are often stabilized by chemical modification to prevent precipitation upon hydrolysis. porous metal oxide with water and alcohol in its mesoscopic pores. most transition metals are extremely reactive to water. Condensation occurs as bridging bonds between M and O are formed and alcohol and/or water are generated. Dong and B. causing precipitates rather than a 3-D network. Such is the case with forming vanadium pentoxide (V2 O5 ) gels. 11]. Typically. Solvate formation is another way of expanding the coordination and slowing down the hydrolysis rate. The larger the alkyl group. To prevent precipitation (by slowing the hydrolysis and olation rates). a very small . or dilution with a chemically inert solvent can lead to lower association. bridging hydroxo groups can be formed in place of bridging oxygen.188 W. which can present problems such as the formation of precipitates. leading eventually to terminal instead of bridging oxygen bonds. Dunn Transition metal alkoxides are versatile precursors for sol–gel synthesis because they are known for almost all transition metal elements [12]. The higher the unsaturation and lower the oxidation state. metal hydroxides can form very quickly. Reaction rates can be controlled through several methods. MOH + MOR → M − O − M + ROH (2) MOH + MOH → M − O − M + H2 O (3) After a significant amount of hydrolysis and condensation has taken place. As condensation continues. M − OH + M − ROH → M − OH − M + ROH (4) M − OH + M − HOH → M − OH − M + H2 O (5) Since the coordination for most transition metals is not saturated in the alkoxide. in a dry environment. a three- dimensional network of metal and oxygen forms within the sol (metal–oxygen col- loids suspended in a liquid) and the viscosity of the sol increases. the sol transforms into a nonfluid gel and an interconnected and fairly rigid 3-D network extends throughout the entire sample container. When the full coordination of the metal atom is not satisfied in the alkoxide. It has been found that the rate of hydrolysis decreases with increasing size of the alkyl groups [8.

cellulose. . This results in very low thermal conductivity and heat capacity. and gas filters [14–16]. Another unique property is the extremely high porosity (80% to >99%) of the aerogel. Capillary pressure = (4γL cos θ )/d. As mentioned previously. diluted in copious amounts of acetone. This characteristic is in sharp contrast to metal oxides prepared through traditional synthetic methods that have surface areas <10 m2 /g. Once the wet gels are formed there are two general methods for removing the solvents. the dry gel will have a porosity of approximately 50% and be termed a xerogel. γL is the surface tension of the liquid.2 Aerogels Aerogels are highly porous nanostructured materials with low density.. transparent aerogels are obtained. To prevent capillary forces from developing. Fig. The temperature and pressure inside the autoclave are raised until the solvent is in its supercritical phase. aerogels can be made from a va- riety of oxides. d is the pore diameter.e. 2] produced by the surface tension of the solvents will cause some of the wet gel network to collapse. acoustics. (6) In (2. Not many systems can sustain this kind of force. Although silica aerogels are the most widely studied system. However. The amount of surface area differs from one metal oxide to an- other and can depend on the synthesis process. 11]. The final. The combination of high surface area and high porosity has led to aerogel applications in thermal in- sulation. The rate of solvent evaporation can be controlled by varying the temperature and the amount of surface area exposed to the ambient atmosphere. Capillary forces [(6). Additives such as solvents. When the metal oxide is an insulator and the pore diameter is <100 nm.Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials 189 amount of water is added. the aerogel) exhibits minimal shrinkage when drying. or stabilizing agents can react with the alkoxide. 000 m2 /g have been observed. Another method is to chemically modify the metal alkoxides by using additives. acidic or basic catalysts.6).500 atm. One is by exposing the wet gel to ambient atmosphere (under ambient pressure) and al- lowing the solvents to evaporate. one being their high surface area. these materials possess a number of interesting and unique properties. supercritically dried gel (i. They were first reported by Kistler in the early thirties [13]. catalysts and catalyst supports. supercritical drying is used. 10. The synthesis of aerogels is based on the formation of a gel. giving rise to a less reactive molecular precursor [8. and θ is the contact angle at the liquid–vapor interface. 2. preserving the highly porous nanostructure of the wet gel [17]. resulting in significant overall shrinkage. Water at 25◦ C leads to capillary forces of around 1. and even rubber [13]. in virtually every case the surface area is at least 200 m2 /g and values of >1. This two-phase material consists of solvent molecules trapped in a solid network. In the super- critical drying process the wet gel is placed inside an autoclave. After complete solvent removal.

d.190 W. 2 Schematic of a pore of diameter. Dunn Fig. in a wet gel r vapor liquid q d Supercritical drying Liquid ≈ 300 m2 /g 1 Solid Pressure 2 Ambigel 100 − 200 m2/g Freeze-drying Gas 280 m2/g Temperature Fig. in its supercritical phase. the liquid no longer exists but is in a supercritical vapor or gaseous phase. Therefore. 3). is then vented from the autoclave and the sample returns to ambient pressure . The solvent. a liquid–vapor interface never develops and no capillary forces are exerted on the solid network (6). Dong and B. 3 Methods for synthesizing V2 O5 materials with aerogel-like morphology (reprinted with permission from The Electrochemical Society) Above the critical point (Fig.

Stainless Steel Stainless Steel Mesh Mesh Carbon Black Carbon Black Carbon Black Particles Particles Transition Metal Oxide Powder Buried Transition Buried Transition Metal Oxide Particles Metal Oxide Particles Solvent Fig. retains the high porosity. the electrochem- ical properties of aerogels received relatively little attention until the mid-1990s. it is necessary to combine aerogels with other components (carbon conductor and binder) to form a composite electrode structure (Fig.1. and high surface area of the wet gel. Removing the pore liquid without collapsing the microstructure preserves both the solid and porous networks so that the resulting solid. Despite the apparent benefit of high surface area. low density. In addition to supercritical drying. This traditional electrode fabrication route is inappropriate for aerogels. Since transition metal oxide aerogels do not exhibit very good electronic conduction. 4 Traditional preparation route for transition metal oxide electrodes. molybdenum oxide.1 Sticky Carbon The vanadium oxide. While the surface areas and densities are slightly different. it is possible to use ambient evaporation methods (ambigels) and freeze-drying techniques to achieve mesoporous materials with high surface area [18]. This reluctance was mainly due to the incompatibility of traditional electrochemical characterization techniques with high surface area materials. These processes are distinctive because they are based on different methods of solvent removal as shown in Fig. 4). 3. an aerogel.1 Circumventing the Conductivity Problem 3. and the ruthenium oxide/titanium oxide systems have all shown that aerogels serve as amplifiers of surface-dominated ef- fects [19–21].Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials 191 and temperature. It should be appreciated that there are several routes for developing aerogel-like morphologies for V2 O5 . 3 Characterization Techniques 3. The aerogel morphology is not retained . The aerogel particles are subsequently agglomerated. the electrochemical prop- erties are all very similar.

it is possible to prepare a con- ductive electrode that effectively holds the finely dispersed. demonstrated that the aero- gel structure indeed contributed to enhanced electrochemical properties.2 Nanocomposites Efforts to enhance the conductivity of transition metal oxide electrodes have included the preparation of composites of the oxide with a conductive material. This was approximately 25% higher than the value measured using a composite electrode structure. 3. Dunn Stainless Steel Stainless Steel Mesh Powders are pressed Mesh onto the wax substrate Sticky Carbon Sticky Carbon Transition Metal Oxide Particles Transition Metal Oxide Particles Fig. The removal of this dispersion solvent can also cause partial to complete collapse of the aerogel structure. the metal oxide/carbon/binder composite is mixed in a dispersion solvent to ensure good mixing and minimize agglomeration. 5). such as carbon black. exposes these particles to the electrolyte. The sticky carbon method was successfully applied to V2 O5 aerogels and the sweep voltammetry curves were significantly dif- ferent from those samples prepared with traditional electrodes. As discussed later. but rather the behavior of an ag- glomerated aerogel system. are characterized by aggregation of the carbon black particles [23]. the results reported initially for V2 O5 aerogels did not represent the electrochemical properties of the actual aerogel. making quantitative analysis of surface area and porosity difficult if not impossible. In this case. and provides electrical contact. Work to enhance the conductivity of the transition metal oxide . Frequently. 5 Fabrication of the sticky carbon electrode in which the aerogel particles are in contact with both the electrolyte and the carbon current collector their surface area is reduced. The sticky carbon electrode described by Long et al.1. these results suggest a different mode of intercalation in aerogels. and their porous structure is altered.192 W. [22] circumvents these lim- itations (Fig. Dong and B. By mixing acetylene black and wax. They were able to measure the theoretical specific capacitance value for hydrated ruthenium oxide gel (900 F/g). Using the sticky carbon approach. Thus. Long et al. Traditional composite electrodes. These aggregates are typically on the order of hundreds of nanometers in diameter and may occlude the oxide aerogel surface. high surface area parti- cles. These particles have not been altered and maintain the original aerogel structure and sur- face area. the liquid electrolyte may not be able to penetrate the pores and access all of the par- ticles. however.

The XANES region of XAS provides information with regard to the oxidation state and local symmetry of the absorbing atom. The level of core electron exci- tation is measured indirectly through electron decay. If the photon energy is high enough. Aerogels for this experiment are prepared as nanocomposites of vanadium oxide and SWNTs where both com- ponents are incorporated during the sol–gel process [24]. especially through the study of ex- tended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) [25]. it is often difficult to correlate Li capacity with the oxidation state or the local structure of the transition metal. show that intimate contact between the V2 O5 aerogel and SWNTs is established as several aerogel fibers are intertwined with sev- eral SWNTs. bond lengths. The EX- AFS region contains information with regard to local structure parameters such as coordination numbers. photons of uniform energy impinge on a sample and are absorbed.1 EXAFS/XANES Although it is often assumed that lithium intercalation in amorphous or nanocrys- talline aerogels occurs between layers of the oxides and results in the reduction of the transition metal. Thus. the V2 O5 /SWNT nanocomposite performed much better (310 mAh/g) than the traditional V2 O5 /carbon black composite (150 mAh/g) [4]. giving rise to fluorescence light or Auger electrons. These experiments can be performed at synchrotron ra- diation facilities where high-intensity. In an XAS experiment. have demonstrated that this can be accomplished through X-ray absorption spectroscopy (XAS). clearly plays an important role in deter- mining electrochemical properties. This contact was observed between the two phases at the nanodimen- sional level at multiple points along the ribbons. 3. and disorder. The nanostructure of the aerogels. core level electrons may be- come excited and move into unoccupied states.Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials 193 aerogels by replacing the carbon black conducting additive with single wall carbon nanotubes (SWNTs) has shown great progress [4].800 mA/g). along with their often amorphous nature. monochromatic X-ray sources are available. it is highly desirable to be able to study the local structure and valence of the transition metal in relationship to Li intercalation. the SWNTs can provide electronic conduction in the electrode without blocking the electrolyte access to the aerogel material [24]. The results show that at high specific currents (2. The macroscopic conductivity of electrodes prepared with carbon nanotubes as the conductive network is substan- tially higher (by more than four times) than that of electrodes containing the same weight fraction of carbon black. Results of the study by Sakamoto et al. For these reasons.2 Deciphering Mechanisms of Charge Storage 3.2. Mansour et al. with its element specificity and ability to monitor changes in the electronic . where kinetic limitations become a factor. XAS. SWNTs consist of bundles of nanotubes in which the characteristic bundle diam- eter is in the order of 10 nm.

(7) where ε is the molar absorptivity. a is the electrode area. These spectroelectrochemical methods measure the voltammet- ric response described by the differential capacitance (∂ Q/∂ E) and the optical re- sponse by the change in absorbance (∂ A/∂ E) at a given wavelength. Dunn and atomic structures without the requirement of long-range order. 35]. Dong and B. the long-range order (interplanar distances) and the extent of reduction of the pentavalent V appear to be influenced by the synthesis parame- ters and the total surface area of the V2 O5 [26]. z is the number of electrons produced or consumed. XAS is not only applicable before and after intercalation. Pre. Pentavalent vanadium is reduced to tetravalent V in the intercalation range 0 < x < 2 and then tetravalent V is reduced to trivalent V upon insertion of more Li (x > 2) [27]. In addition to the V2 O5 aerogel studies reported in the follow- ing paragraph.. 3. but in situ experiments have also been successfully demonstrated [26]. Lix V2 O5 ). For V2 O5 . 31]. this technique is useful because the optical absorbance of V2 O5 is a function of the degree of Li+ insertion and concomitant electron insertion into the oxide [36]. For an elec- trochromic process that can be described by the Beer–Lambert law. The nondestruc- tive nature of XAS also avails itself for monitoring the structural and electronic changes in the oxide system during Li intercalation. In situ XAS studies have established that the oxidation state of V in the V2 O5 aerogel is consistent with the amount of Li inserted (i. Monitoring the rel- ative absorbances at specific wavelengths can provide insight into changes of the local structures during lithium insertion and deinsertion. .2.194 W. For in situ data. Al- though the local structure of the V2 O5 aerogel does not seem to be affected by the preparation method [28].33]. we previously used the XAS technique to show that nanocrystalline MoO3 intercalates greater amounts of Li than either the crystalline or the amorphous forms [20]. is uniquely suited for investigating amorphous and nanophase materials [25]. the cation-insertion process can be monitored through the si- multaneous current and optical response during the charging and discharging pro- cess of the cathode. This technique has been referred to as derivative cyclic voltabsorptometry [30. and F is the Faraday constant [32. This method has been used successfully to investigate cation-insertion reactions in sol–gel-derived nanos- tructured vanadium oxide and manganese oxide [34.2 FTIR and Spectroelectrochemistry Fourier transform infrared (FTIR) spectroscopy and spectroelectrochemistry are two other techniques that have been used with great success at deciphering the charge storage mechanism in aerogel electrodes. the differential absorbance A can be related to the electrochemical current i by dA/dt = a z F i ε .and postintercalation along with in situ FTIR experiments have been used in the determination of valence states of the transition metal and in characterizing local bonding [29].e.

and carbon aerogel anodes [37]. this system clearly shows the ability of nanostructured materials to exhibit electrochemical properties that far exceed those of other amorphous V2 O5 gels that do not have the nanoarchitecture of aerogels [5]. Reversible electrochemical intercalation of Li+ ions into V2 O5 gels (V2 O5 · 1. Many of these transition metal oxide gels retain the electronic properties of the traditionally prepared crystalline counterparts or show moderate improvements. leading to crystalline V2 O5 . the dehydration becomes irreversible. In the following paragraphs. . Comparisons to xerogels are especially fascinating since the differences between aerogels and xerogels are morphological (primarily porosity and surface area) and not chemical. These ma- terials possess a characteristic ribbon-like morphology. the water content of V2 O5 · nH2 O gels corresponds to n = 1. There is an inherent difference in properties due to the nanostructured nature of the aerogel. Since then. One motivation for synthesizing V2 O5 gels is for the application of cathodes in sec- ondary lithium batteries. Amorphous V2 O5 has been reported to have specific capacities in excess of 500 mAh/g with 4 Li/V2 O5 [42]. considerable study has been conducted on this subject [40]. Among the aerogel systems that have been exam- ined for battery applications include SnO2 -based anodes. thin films of V2 O5 have demonstrated electrochromic behavior. to a composition of V2 O5 · 0. the electrochemical results for vana- dium oxide aerogels are distinctly different. However. Vanadium pentoxide gels can be ei- ther amorphous or crystalline and they exhibit semiconducting behavior. In addition to battery cathodes.Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials 195 4 Case Study: Effects of Nanostructure on the Electrochemical Properties of V2 O5 A number of nanostructured materials are being investigated as cathodes and anodes for secondary lithium batteries. The increase in specific capacity for the V2 O5 aerogels is not just related to mor- phology. This particular property has made them the subject of intense study for a variety of different applications. While aerogels have shorter diffusion distances and the mesoporous vol- ume leads to greater accessibility of the ions. Vanadium oxide belongs to the well-known family of mixed-valence compounds [38].5H2 O. MnO2 cathodes. The specific capacity for lithium is greater with V2 O5 aerogels than it is with ei- ther the corresponding xerogels or crystalline V2 O5 [43].8 [41]. The vanadium ions generally exhibit several valence states so that electron transfer can occur. 44]. the materials differ only by the manner in which they are dried [6. especially as battery electrodes. This water can be removed reversibly upon heating. Aerogel materials of- fer considerable promise for battery applications as prior research has shown these materials to possess a specific lithium capacity in excess of 300 mAh/g at a C/4 discharge rate [42]. these are not the only considerations. MoO3 cathodes. Below this water content. we will focus on how nanostructure enhances the electrochemical properties of V2 O5 aerogels in order to shed some light on how nanostructures can be used to enhance electrochemical performance for other materials. Under ambient conditions.6H2 O) was first reported in 1983 [39].

1 Pseudocapacity and the Importance of Pore Architecture Cyclic voltammetry studies with V2 O5 aerogel powders on sticky carbon have yielded evidence of pseudocapacitance not observed in crystalline V2 O5 nor V2 O5 xerogels [4]. When the high surface area V2 O5 aerogels are completely accessi- ble to the Li+ ions. As shown in Fig. has demonstrated that various temperature–atmosphere treatments can significantly affect the Li-ion capacities of micrometer-sized V2 O5 polycrystalline powders by controlling the nature of vacancies [46]. The high surface area and short diffusion length in the solid also contribute to the ability of V2 O5 aerogels to reversibly intercalate ions with larger radii and/or valences greater than that of Li+ [45]. Tang et al. K+ . Dong and B. Rhodes et al. Besides the pseudocapacitance of V2 O5 aerogels. Instead. 4.300 F/g (1. the Faradaic features are broad and capacitive and the intercalation peaks appear superimposed on the capacitive response [19]. spectroelectrochemical methods were used to deter- mine the nature of specific insertion sites within the V2 O5 gels and to monitor how . Dunn 4. This behavior highlights the importance of pore architecture and of lithium ion accessibility to the high sur- face area V2 O5 aerogel. 6. The charge storage mechanism for these ions is most likely related to pseudocapacitive behavior. Heating polycrys- talline V2 O5 under O2 /H2 O atmosphere formed proton-stabilized cation vacancies and increased the Li-ion capacity by >20%. Mg2+ . In the work by Rhodes et al. Anion vacan- cies created by heating polycrystalline V2 O5 under Ar (low partial pressure of O2 ) lowered the Li-ion capacity relative to the as-received powder. and Ba2+ can all be reversibly inserted into the V2 O5 aerogel structure. electronic conductiv- ity.196 W. 480 μF/cm2 ) and a lithium capacity of 650 mAh/g were reported. This is the first time such behavior has been observed for V2 O5 materials and occurs in combi- nation with the lithium intercalation typically seen for V2 O5 . there is a fairly linear trend between specific capacitance and pore volume. electrode potential. have demonstrated that controlled disorder can be created through various atmospheric treatments as a way to improve electrochemical performance [36].2 Effects of Surface Defects In addition to the large surface areas of V2 O5 gels. Work by Swider-Lyons et al. The high surface defect concentration contributes to the amplification of these electrochemical properties. A specific capacitance of 2. Aerogel surfaces tend to be more defective than those of crystalline materials. evidence of pseudocapacitance is observed. and ionic transport in metal oxides. have shown that Na+ . another important observation of this study is that the capacitance did not vary directly with surface area. Pore diameters less than 5 nm may not be accessible to the solvated lithium ions and therefore do not contribute to the overall capacitance of the sample.. surface defects have also shown to have significant influences on the electrochemical capacity.

a Sticky-carbon elec- trode. The arrows refer to the intercalation/deintercalation peaks in b (reprinted with permission from the Electrochemical Society) the distribution of these sites changes due to the different temperature–atmosphere treatments. . 6 Voltammetric sweeps for V2 O5 aerogels using different electrodes. while changes in the relative absorbance at 800 nm suggest that insertion occurs into the vanadium–oxygen structure in the vicinity of vacancies and defects [36].Vanadium Oxide Aerogels: Enhanced Energy Storage in Nanostructured Materials 197 Fig. The changes in the relative absorbance of the disordered V2 O5 gels at 400 nm suggest that electron insertion occurs into stoichiometric V2 O5 states that are locally defect-free. b traditional composite electrode.

1 (1998) 8. Kinser AJ. Sci. Chem.1. Van Schalkwijk W. Eng. nonporous V2 O5 or xerogels of V2 O5 . Pajonk GM. 366 (2005) 2. Mater. Dupont L. References 1. 35. Tarascon J-M. there are both advantages and disadvantages for using nanomaterials in energy storage [1]. Chem. Catal. Poizot P. Hench LL. Adv. New York. Owens BB. Bruce P. Metal Alkoxides. Electrochem. Assem- bling aerogels into hierarchical electrode structures is one direction that offers the prospect of overcoming this limitation. Iacobucci PA. 1978 13. Sakamoto J. 83 (1976) 6. 1986 15. 741 (1931) 14. Sudant G. Bradley DC. Aerogels offer excellent gravimetric capacity. Livage J. Ayen RJ. J. Res. Gaur DP. 341 (1988) 12. 157 (1988) 16. Kistler SS. Fricke J. Scherer GW.198 W. The aerogels exhibit significantly better electrochemical properties than either crystalline. Solid State Chem. A unique surface effect observed with the V2 O5 aerogels is the large amount of pseudocapacitance. Academic Press. Smyrl WH. Berlin. Larcher D. leads to greater amounts of charge storage for V2 O5 aerogels. there is a trade-off to consider. 3 (2003) 5. Mater. Baiker A. Rev. 319 (1997) 7. 496 (2000) 3. Tarascon J-M. Mater. Sol–Gel Science. 37. 515 (1995) . J Non-Cryst. 1263 (2005) 4. but poor volumetric capacity. Sci. The high porosity also enables the electrolyte to penetrate the entire cathode structure. Solids. Rev. Laruelle S. Besenhard JO. Nat. West JK. Schollhorn R. Prog. this accessibility en- sures high utilization of the aerogel material. 15. Baudrin E. Eng. Catal. Kuhlmann R. 4. Brinker CJ. Nature 127. Arico AS. Dong W. Finally. Tarascon J-M. 90. Scrosati B. Mehrotra RC. In particular. Nature 407. Schneider M. Acknowledgments The authors are grateful for the support of their research by the Office of Naval Research. Springer. As for disadvantages. 4. structural changes over time are a concern. Bull. Academic Press. Solid State Lett. Chem. London. Dunn 5 Conclusions Aerogels represent a novel nanostructured material for advanced energy storage. Today. The interconnected porosity allows for the easy transport of ions and the large surface area provides an electrochemically active surface that is not constrained by diffusion limitations. 33 (1990) 11. Henry M. Dong and B. 5. Xu JJ. 18. 1990 9. The fact that the V2 O5 aerogels support high discharge rates makes these materials attractive for electrical actuation systems in micro.and nanoelectromechanical systems (MEMS and NEMS). 73. Technol. in combination with the excellent lithium intercalation behavior. 11. Aerogels. Mater. Rev. This chapter has shown how vanadium oxide aerogels represent a very attractive electrode material for secondary lithium batteries. Dunn B.. As an earlier publication has indicated. there are unresolved questions concerning the cyclability of V2 O5 aerogels. The reason for this differ- ence is that there are a number of features that become prominent in aerogels but are absent with the other forms of V2 O5 . Sanchez C. Grugeon S. Mackenzie JD. which. 631 (1985) 10.

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nl E. Box 5045. Ti and their oxides. 1 Introduction In the past decades there has been a world-wide growing interest in innovative design. 2600 GA Delft. Sn. AFM.O. i.. The structure. P. because of a broad spectrum of applications. Properties. for advanced in- novative devices for the conversion and storage for renewable energy sources. and properties of these composite materials have been studied by X-Ray diffraction. The properties of selected composites will be discussed with focus on the nanos- tructured TiO2 /PPX composites as an anode material for a rechargeable lithium-ion battery. production. and chemical gas sensors. Delft Institute for Sustainable Energy. A simple. Schoonman () Delft University of Technology. The Netherlands e-mail: J. and Applications in Electrochemistry Joop Schoonman. TEM. containing PPX and nanoparticles of Al.1007/978-0-387-49323-7 6. An important aspect of these composite materials is the nature of the inter- facial properties of the nanostructured particles and the PPX material. microstructure. Leite (ed. and electrical measurements.Nanostructured Composites: Structure. storage.e. and application of nanocomposite materials. and Alla Pivkina Abstract Hybrid metal/metal oxide–poly-para-xylylene (PPX) nanocomposites have attracted great interest.).Schoonman@tudelft. active lithium-ion rechargeable battery materials. Anticipated applications of the present composites are photanodes for hydrogen production. DOI 10. Nanostructure Science and Technology.R. c Springer Science+Business Media LLC 2009 . This co-deposition technique has been applied to synthesize nanocomposites. Nanostructured Materials for Electrochemical Energy Production 201 and Storage. low-cost preparation technique has been developed and comprises a cold-wall vac- uum co-deposition technique. Such composites open up new possibilities for tailoring the fundamental properties of the J. Zn. com- posite materials having spatially organized nanosized components. Sergey Zavyalov. Important is the oxidation kinetics of the metal clusters to their oxides in relation to the percolation threshold.

and for creating unique new properties because. the distance between the vapour source and the substrate. . which leads to mechanical disintegration of the elec- trode. and Ti as a metal source and poly-para-xylylene (PPX) as a polymeric matrix.1 Formation of Nanocomposites The flux of metal atoms in vacuum (Pd. electrical properties. Schoonman et al. Sn. The use of the polymeric matrix could stabilize the nanoparticles within the nanocomposite. Manipulation of the synthesis conditions. Samples of Ti(TiO2 )/PPX nanocomposites were investigated as anode material for rechargeable Li-ion batteries. for example. Al. Zn). Sn. evaporated from a bulk sam- ple condenses onto a cooled substrate together with the monomer. Nanostructured materials comprising 3-d transition metal oxide nanoparticles or alloys have been investigated extensively for their potential application as anode materials in lithium-ion batteries. Ti. referred to as the Gr¨atzel solar cell [3]. 2 Experimental Aspects 2. It has been shown also that the nanostructured anatase material exhibits an enhancement factor of about 3 × 106 compared to the mean lithium-ion intercalation time of a dense layer of this Li-battery anode material [4]. A wide range of metal (metal oxide)/polymer nanocomposites has been syn- thesized. using Al. 1). A serious drawback of such systems is the substantial volume change of the active phase (up to 300%) during the charge/discharge process.e. The condensate consists of nanoparticles of the metal and the monomer (Fig. where nanoparticles reveal specific interparticle interactions and interactions with the matrix in which they are dispersed [1. the tilt angle of the beam. and the deposition time allowed for optimising the deposition regime. of self-assembling processes during the synthesis. The properties of the nanocomposites were studied by comparing the structure. Zn. 2].202 J. Upon heating the substrate to ambient temperature the monomer polymerises to PPX. Measuring the electrical resistance of the condensate and composite permitted the control of the film formation in relation to the oxidation behaviour. Addition of components with a high electronic conductivity could increase the efficiency of the synthesized materials as anode for rechargeable Li-ion batteries. morphology. materials to reinforce considerably the useful properties of their components.. oxidation kinetics. Pd. The structure thus obtained is a porous matrix with dispersed nanoparticles in it. and a conventional two-electrode cell was employed. and electrochemical parameters. i. Nanostructured anatase titanium dioxide has attracted widespread attention as a photo-electrode in an advanced regenerative dye-sensitized solar cell. The properties of these nanocomposites containing metal and/or metal-oxide nanoparticles in the polymeric matrix are presented. Examples of such materials are metal (metal oxide)/polymer nanocomposites.

Properties. 1 Schematics of the cold-wall vacuum co-deposition process CH2 CH2 400K 930K 2CH2 CH2 CH2 CH2 Para-xylylene Di-para-xylylene 2CH2 CH2 CH2 CH2 CH2 CH2 Bi-radical CH2 CH2 CH2 CH2 n Poly-para-xylylene Fig.2 PPX Vacuum Co-Deposition The schematic of the para-xylylene monomer polymerization [5] is presented in Fig. the condensed monomer polymerises into PPX as indicated in Fig. . With heating up to room temperature.Nanostructured Composites: Structure. 2 Pathway for pyrolysis of di-para-xylylene to form PPX 2. which then evaporated (without destruction) in the temperature range 350–400 K. Under these conditions the C–C bond shows destruction with almost 100% output of bi-radical. 2. and Applications in Electrochemistry 203 Fig. The monomer thus obtained condenses onto the cooled substrate. Di-para-xylylene was introduced into the evaporation zone. The monomer beam was introduced from the source consisting of the zone of evaporation of di-para-xylylene and its pyrolysis zone. 2. Then the molecules of di-para-xylylene reached the pyrolysis zone with a temperature of 930 K.

6 V vs. 2. The metal content of the composites was calculated by atomic ab- sorption analysis using a Perkin-Elmer 503 spectrometer. .9 V. (2) a polished NaCl single-crystalline substrate of the same size and thickness for TEM analysis. Specific capacity and cycling measurements were performed at room temperature using a Maccor battery test system.4-cm diameter electrodes. NT-MDT) with silicon cantilevers having a tip radius less than 10 nm and 20◦ apex angle (NSC11.0005 mA. Estonia. i. The optical spectra of the films were recorded with a spectrophotometer (Shimadzu UV-3100) in the wavelength range 200–2. For electrochemical measurements. The surface morphology. we used Al-foil and Cu-foil as substrates for nanocomposites. Schoonman et al. The typical initial open-circuit voltage for these cells was about 2. temperature) was measured after cooling of the synthesized composite from 293 to 77 K. a conventional two-electrode cell was employed using 1.. lateral forces. metallic lithium at a constant current in the range of 0. and (3) a polished quartz substrate of size 10 mm × 20 mm and 2-mm thick for optical and AFM investigations.e. Mikro- masch) and conductive cantilevers (silicon coated with Ti–Pt) having a tip radius of 40 nm and 30◦ apex angle (CSC21. To obtain identical samples both types of substrates were fixed close to each other onto a cooled surface of the sample holder (4). Five types of substrates have been used in the experiments reported here. and spreading resistance were studied by AFM (P47-SPM-MDT.1–0. film thickness. Topographic and spread- ing resistance AFM images were obtained in tapping and contact modes in air. Estonia. The electrolyte consists of 1 MLiClO4 in a 1:2 molar ratio of ethylene carbonate to propylene carbonate solvent. The morphology of the nanocomposites was studied with Transmission Electron Microscopy (TEM JEM-2000 EX-II at 200 kV). The deposited thin film was the work- ing electrode and metallic lithium was used as the reference and counter electrode. Additionally. Mikromasch). The cells were cycled between 0.08 and 2.000 nm. including separation of the nanocomposite layer from the NaCl substrate in water and the film deposition onto a Cu grid for further derailed investigations. Samples for TEM were prepared by standard procedures. A porous polyethylene sheet was used as an elec- trolyte separator. The cells were sealed in a coin cell casing (Hohsen) in an Ar-filled glove box.204 J. The temperature coefficient of the electrical resistance in vacuum (the slope of Rv (T )/Rv (293 K) vs. (1) a polished quartz substrate of size 5 mm × 5 mm and 1-mm thick with Pt contacts for electrical measurements.3 Methods of Nanocomposite Analysis Oxidation kinetics during air exposure after vacuum synthesis was measured using the data acquisition board L-1250 connected to a PC. Russia.

and spreading of interconnected chains. the amorphous phase is converted into a crystalline film. As a rule. formation and growth of nanoparticle chains.. Properties.1 Pd/PPX Nanocomposites Samples of nanoporous composites of a metal and the polymer PPX have been synthesized in the form of thin films. The in- terfacial regions between neighbouring polymeric spherulites contain nanoparticles of inorganic filler. while the samples with a tin content beyond 10 vol% do not change their colour during several months (Fig. the epitaxial contact between two phases is the most energetically favourable. Within the composite the polymer forms more or less spherical globules with a maximum size of about 200 nm (Fig. 4). Profile maximums correspond to Pd particles embedded into the boundary surfaces between the polymeric globules . isolated nanoparticles localized on the polymer spherulite surfaces. three different types of surface morphology are distinguished. Experimental data [6] reveal that for the metal Fig. Depending on the metal content in as-prepared samples. b Cross-section A-A. 3).Nanostructured Composites: Structure. 3. On contacting with the ambient air during 2 min the samples became trans- parent for composites with Sn concentrations below the percolation threshold of 10 vol%. and Applications in Electrochemistry 205 3 Results and Discussion 3.2 Sn (SnO2 )/PPX Nanocomposites Freshly synthesized tin-containing samples exhibit a grey colour with a metallic lustre. The study of the thin film deposition process shows that the film structure is strongly dependent on the crystal and energetic properties of the surfaces in con- tact. 3 AFM image of Pd/PPX nanocomposite: a Phase-contrast image: dark regions are poly- mer spherulites and light spots are Pd nanoparticles located at the boundaries between polymer globules. but because of the high deposition rate of the thin films an amorphous structure is formed instead of an epitaxial layer. i. With increase of the film thickness or at higher temperatures. The AFM study reveals the metal nanopar- ticles to have a size of 7–30 nm.e.

localization on the polymer spherulite surface 2 10 880 Ohm Formation and growth of 3 12 45 Ohm nanoparticle chains 4 16 13 Ohm Chains exhibiting percolation content in as-prepared samples below or at the percolation threshold (samples 1 and 2. b sample 3 (12 vol% of Sn) Table 1 Properties of Sn(SnO2 )/PPX nanocomposites Sample no. 4 Sn-containing samples of nanocomposites after air exposure: a sample 1 (8 vol% of Sn). Fig. Beyond the percolation threshold (sam- ple 4). Table 1) the inorganic particles are isolated and the interparticle distance varies from 5 to 20 nm.206 J. Slightly above the percolation threshold (sample 3) the particles form continuous filaments of varying diameter. Hence. wherein the inorganic particles form structured sub- systems with respect to the polymeric matrix. Analysis of the Sn(SnO2 )/PPX composites reveals that for the metal content in as-prepared samples below or at the percolation threshold the inorganic particles . but the maximal diameter never ex- ceeds that of the single metal nanoparticle. the nanoparticles form aggregates located on the boundaries between the polymer spherulites. Further increase in the metal content gives rise to aggregation of nanoparticles and their coalescence. Sn vol% Resistivity in vacuum Morphology 1 8 6 MOhm Isolated particles. the metal–polymer and metal oxide–polymer nanocom- posites are the components. Schoonman et al. the nanoparticles localize along the borders of polymeric spherulites accompanied with the formation of conducting chain structures. In increasing the metal content.

It has been shown that the nanocomposite structure de- termines the oxidation behaviour of Al nanoparticles within the polymeric matrix under air exposure. Properties. the electrical resistivity of sample 7 increases dramatically during several . Freshly synthesized Al-containing samples (Table 2) exhibit normally a dark colour with a metallic lustre in vacuum. and Applications in Electrochemistry 207 Fig. Substantial differences in oxidation behaviour exist between the inves- tigated samples. 3. 5 TEM image of sample 1 – SnO2 /PPX nanocomposite (8 vol% Sn) (SnO2 ) are isolated and the interparticle distance varies from 5 to 100 nm (Fig. Figure 7a–c shows the resistivity change of freshly synthesized samples 5–7. Beyond the percolation threshold. A sample with a metal content just at the percolation threshold contains metal nanoparticles of 10 nm and alumina aggregates of 28 nm in diameter (Fig. The inorganic phase is homogeneously dispersed within the polymeric matrix in all of the investigated samples. but the maximal diameter never exceeds that of the single metal nanoparticle. the nanoparticles form aggregates located on the boundaries between the polymer globules. sample 7 became transparent. 6a). 6c).3 Al(Al2 O3 )/PPX Nanocomposites TEM analysis of the nanocomposite with an Al content beyond the percolation threshold reveals spherical pure metal nanoparticles with a mean diameter of about 10 nm (Fig. while below the percolation threshold the composite contains ag- glomerates of rhombohedral Al2 O3 (corundum) with a mean size of 55 nm (Fig. 6b).5%). if exposed to air at 1 atm. which are clearly reflected in the minor increase of the electrical resistance (Fig. 5).Nanostructured Composites: Structure. On contacting the composite with the am- bient air. whereas samples 5 and 6 do not change their colour. According to the above TEM results. However. nanoparticles in sample 5 are Al crystallites. 7a) during air exposure (ΔRmax = 5. Slightly above the percolation threshold the metal particles (Sn) form continuous filaments of varying diameter.

6 TEM images of Al(Al2 O3 )/PPX nanocomposites with different contents of the inorganic phase: a sample 5 (12 vol%). Schoonman et al. c sample 7 (8 vol%) Table 2 Parameters of synthesized Al(Al2 O3 )/PPX nanocomposites Sample number Crystal phase dm (Al) (nm) dm (Al2 O3 ) (nm) 5 Al 10 – 6 Al + Al2 O3 6 28 7 Al2 O3 – 55 . Fig.208 J. b sample 6 (10 vol%).

7b). TEM micrographs of sample 6 revealed alumina and Al crystallites within the polymeric matrix. The dramatic increase in resistivity is followed by a sharp decrease after 84 s of air ex- posure (Fig. In fact. 7c).Nanostructured Composites: Structure. The high resistivity of the nanocomposite is caused by the high resis- tivity of the alumina particles and large distance between them. and Applications in Electrochemistry 209 Fig. 7 Kinetics of oxidation during air exposure at room temperature of Al(Al2 O3 )/PPX nanocom- posites with different contents of the inorganic phase: a sample 5 (12 vol%). b sample 6 (10 vol%). c sample 7 (8 vol%) seconds (Fig. nanoparticles in this sample comprise pure alumina dielec- tric material. . Properties.

8 AFM topography images: a sample 12 (14 vol% Ti/PPX). Schoonman et al. Optical absorption measurements prove that synthesized nanocomposites are containing TiO2 and Ti phases.210 J. DTA analysis revealed that the heating of amorphous TiO2 nanoparticles up to a temperature of 480◦ C leads to a phase trans- formation to anatase. 3. which are homogeneously distributed between the polymer globules (Fig. 8). just an amorphous phase. For a metal content below the percolation threshold the metal particles became insulator within several seconds. b sample 8 (8 vol% TiO2 /PPX) . AFM analysis shows that the inorganic phase com- prises nanoparticles of 10–20 nm in diameter. XRD studies show that synthesized composites do not contain any crystal phase. The same result was obtained: XRD analysis shows that the synthesized films only contain the amorphous phase. whereas heating up to 580◦ C results in the anatase transfor- mation to the rutile structure. whereas for the samples beyond the threshold the observed resistance in- crease is per cents within several hours.4 Ti (TiO2 )/PPX Nanocomposites A series of samples of nanocomposites of Ti and PPX with different Ti content has been synthesized (Table 3). Kinetics of the electrical resistance increase with the air exposure of Ti/PPX nanocomposites (after synthesis under vacuum) is similar to that of the Al/PPX ones. Table 3 Freshly synthesized Ti(TiO2 )/PPX nanocomposites: inorganic phase content Sample Inorganic phase Inorganic phase content (vol%) 8 TiO2 7 9 TiO2 9 10 TiO2 10 11 Ti 11 12 Ti 14 Fig. For comparative analysis the pure Ti containing thin film was deposited onto the cold substrate (77 K) and onto the substrate at room temperature.

e. Simultaneously with topography acquisition under scanning of TiO2 /PPX nanocomposites. 9 UV–visible spectra of synthesized titanium/polymer nanocomposites: Samples 8. 9. 11a) could be approximated by the dependency ln(R)∼1/ ln(t). which is typical for free electrons in the Ti metal in the composite films. 1. According to data [7]. and 10. whereas the resistivity of sample 11 increases much slower. The resistivity of sample 8 increases fast. According to literature data [8. i. Two types of inorganic filler are stabilized by the polymeric matrix. 9. i.e. and samples 11 and 12 contain amorphous Ti The optical absorption spectra of five different samples are shown in Fig. and for sample 11 the R(t) dependency reveals R−0.5 times for 20 min. 9] for the early stages of the low-temperature metal oxidation.5 ∼ ln(t) (Fig. With the metal content growth. The optical spectra of samples 11 and 12 show the non-selective absorption over the entire wavelength span of 220– 620 nm. one can see some other characteristics of the investigated sam- ples. 10). Figure 11 shows the electrical resistivity vs. The polymeric matrix does not absorb in the range 200–600 nm as shown by Zavyalov et al. for the 20 s of oxidation. the strongest absorption band of the nanocomposite samples 8–10 at 360 nm is assigned to TiO2 particles.. and amorphous Ti in samples 11 and 12 (Table 3). when the oxide layer thickness is below 2–3 nm.. 9. the oxide layer growth depends on the oxygen and metal ion diffusion and on the electron diffusion towards the reaction surface. and Applications in Electrochemistry 211 Fig.e. 11b). and 10 contain amorphous particles of TiO2 . lateral forces. [6]. and spreading resistance images allows to understand that the high-conductivity points are localized in between the polymeric globules (Fig.Nanostructured Composites: Structure. The chemical potencial field is formed by the ad- sorbed oxygen on the oxide surface and by the induced oxygen activity at the metal– metal oxide boundary. Superposition of topography.. Kinetics of the curve for sample 8 (Fig. the conditions of diffusion via . amorphous TiO2 in samples 8. resis- tance (R) grows three orders of magnitude. Properties. time history for sample 8 with the metal content below the percolation threshold and for sample 11 above this thresh- old. i.

212 J. Ohm 100 800 90 400 80 0 70 0 5 10 15 20 25 0 5 10 15 20 25 t. b sample 11. Scan sizes are a 250 nm × 250 nm. Ohm R. 11 Kinetics of oxidation of Ti/PPX nanocomposites: a sample 8. experimental data follow to the function ln(R)∼1/ ln(t). Fig. min t. experimental data follow to the function R−0. 10 AFM of sample 12 (14 vol% TiO2 /PPX): superposition of topography and spreading resistance images. min Fig.5 ∼ ln(t) . Schoonman et al. b 550 nm × 550 nm a 1600 b 120 110 1200 R.

3. The composites with a lower metal content show a semiconductor-like negative temperature coefficient. If the metal particle density increases. The composites with a metal content of 12 vol% reveal a pos- itive temperature coefficient. This indicates a loss of metal-like contacts between par- ticles of the metal phase. when the metal concentration is 8 vol%. This is typical for porous films comprising islands of conducting 0 Cu 2 7 12 −0. and Applications in Electrochemistry 213 the oxide layer are changing because of the change in the charge transfer mechanism within the ensemble of metal nanoparticles.04 −0. Figure 12 presents the temperature coefficient (the slope of R(T )/R(20◦ C) vs.Nanostructured Composites: Structure. the temperature coef- ficient increases. This indicates a loss of metal-like contacts be- tween metal particles. Previously. In contrast. we reported about a sign changing of the temperature coeffi- cient of metal/polymer nanocomposites once the metal content is close to the per- colation threshold. the temperature coefficient be- comes semiconductor-like. Properties.% Fig.03 Pd −0. reciprocal tem- perature) of the electrical resistivity of as-prepared composites with metal contents ranging from 7 to 12 vol%. metal content . As a result. This is to be expected from percolation behaviour of the 0. 12 Temperature coefficient of the resistivity of synthesized metal(metal oxide)–polymer nanocomposites vs. Vol. indicating an electrical conductivity determined by a continuous network with metal-like contacts between the metallic nanoparticles. the logarithmic oxidation law transforms to the inverse logarithmic one.01 Al −0.05 Metal content.01 Sn Temperature .02 Ti −0.5 Electrical Resistance in Vacuum The mechanism of the charge transfer processes within an ensemble of ultra-fine metal particles (in a composite of non-conducting particles) depends on the ratio of the particle’s conductivity and the conductivity of the barrier regions between them and also on the ratio of the particle size and the interparticle distance. These samples were deposited on quartz substrates with Pt contacts.

This indicates that the PPX polymer has some re- versible capacity and that at 10 vol% TiO2 the active component is still the PPX polymer matrix. As a note. since the electrode areas for all cells were the same. the electrical conductivity in vacuum is limited by (a) the non-conducting polymer layer. Since the reduction and oxidation potential of TiO2 is flat vs. the cell resistance may account for this difference. i. In Fig. The reversibility of the 14 vol% TiO2 film seems Fig. the currents are directly comparable. 14 this potential is shown in the flat part of the potential curve. TiO2 seems to be active in the 14 vol% TiO2 film. 10 vol% TiO2 /PPX matrix (sample 10). Li metal at 1. The percolation threshold can be determined by the variation in the temperature dependence of the electrical resistance. By comparing these potential curves with the potential curve of the 14 vol% TiO2 /PPX film.e. Schoonman et al. composites on the metal filler content. 13 Percolation of TiO2 vol% in the PPX matrix . 3.8 V.6 Electrochemical Characterization Figure 13 shows the cell potential as a function of the specific capacity for pure PPX. the performance of the PPX and 10 vol% TiO2 /PPX matrix electrodes is the same. Since the reduction and oxidation po- tential of TiO2 lies at a flat potential of approximately 1. Al- though the flat potential is slightly off of what has been reported. This observation is seen despite the fact that this sample is thicker than the other films and the current at which this cell was tested was greater than that of the 10 vol% TiO2 film. which is for the present case 10 vol% of metal.8 V. the 14 vol% TiO2 film was cycled at lower currents in order to observe the intercalation of TiO2 . and 14 vol% TiO2 /PPX matrix (sample 12) electrodes. the curve differs in that the potential for the 14 vol% TiO2 is higher on discharge and lower on charge. The synthesized nanocomposites demon- strate two types of electrical conductivity. and (b) the conductivity of the metal nanoparticles..214 J. From this figure.

4 Concluding Remarks Thin-film metal (metal oxide)/polymer nanocomposites with different inorganic phase contents were obtained by using the cold-wall vacuum co-deposition tech- nique. i. surface morphology.e. 14 Reversibility of 14 vol% TiO2 /PPX nanocomposites at different current densities Fig. It is found that in . A range of metals was shown to be applicable to form nanocomposite thin films with PPX. Ti.28 μA/cm2 . and Applications in Electrochemistry 215 Fig. However. opti- cal absorption. electrical conductivity. for the very low rate of 0. 15. and Sn.Nanostructured Composites: Structure. AFM studies show the metal nanoparticles to have a size of 7–50 nm. Properties. and Li-ion conductivity have been investigated. Al.03 μA/cm2 . 15 Specific capacity of sample 12 (14 vol%TiO2 /PPX) vs. The interfacial regions between neighbouring polymeric spherulites contain nanoparticles of the inorganic filler. the efficiency decreases as shown in Fig. The chemical composition. Within the composite the polymer forms more or less spher- ical globules with a maximum size of about 200 nm. cycle life to be good even though the capacity is low for current rates up to 0.. Pd.

. 2000 2.S. TiO2 . M. A. Zavyalov. Russian Academy of Science) for the atomic force microscopy characterization. to Dr. Metal-polymer nanocomposites: formation and properties near the percolation threshold in Nanostructured Materials: Selected . E. This indicates a loss of metal-like contacts between particles of the metal phase. Ti. Radmir Gaynutdinov (Shubnikov Institute of Crys- tallography.004). M. We have found experimentally that the composites with a metal content beyond the percolation threshold show a positive temperature coefficient indicating a conductivity determined by a continu- ous network of metal-like contacts between the nanoparticles.2003. Roco. In contrast. Kluwer Academic. and Ti nanoparticles within the polymeric matrix under air expo- sure.e. S. B. Schoonman. Dan Simon (Delft University of Technology. the inorganic phase consists of nanoparticles of the metal oxide (Al2 O3 . Schoonman et al. Nature. a relatively narrow concentration range of the inorganic phase. Vision for Nanotechnology R&D in the Next Decade.C. 1991 353 737 4. Gr¨atzel. O’Regan. Nanostructured Materials in Solid State Ionics. grant no. i. and A. Below the percolation threshold. from 7 till 14 vol% within the polymeric matrix. Sn. Szwarc. i.. whereas for the samples above the threshold the observed resistance growth is several per cent and full oxidation takes several hours.P. when the metal concentration is below the percolation threshold. References 1. Eng. For the metal content below the percolation threshold the metal particles be- came insulators within several seconds. Alivisatos. Acknowledgements We are grateful to Dr.216 J. The percolation threshold can be determined by the variation of the temper- ature dependence of the electrical resistance. Solid State Ionics. The synthesized nanocomposites demonstrate two types of electrical conduc- tivity.e. Timofeev. M. and to The Netherlands Organization for Scientific Research for financial support of the project (NWO.011. Polym. and J. Advances of Physical Science (in Russian). R. SnO2 ) and beyond this threshold. J. 2000 135 5–19 5. Pivkina. 1976 16 473 6.. and (b) the conductivity of the metal nanoparticles. the electrical conductivity in vacuum is limited by (a) the non-conducting polymer layer. Nagaev. Nanotechnology Research Directions: IWGH Workshop Report. 1992 162(9) 49–124 3. of nanoparticles of the metal (Al.L. Sn). It has been shown that the nanocomposite structure determines the oxidation be- haviour of Al. the temperature coefficient is negative indicating a conductivity determined by a network of semiconductor-like contacts. Small Metal Particles. Schoonman. the properties of these thin-film nanocom- posites critically depend on content. Sci. Williams. The different mechanisms of charge transfer within the composites are found to be responsible for the differ- ent oxidation behaviours of the metal nanoparticles. A. which is found to be about 10 vol% of metal. The synthesized thin films of nanostructured TiO2 /PPX composites exhibit a high specific capacity and good cycling performance as anode in Li-ion batteries. The Netherlands) for electrochemical character- ization. 047. Dordrecht.

Boston. Mott. Theory of oxidation of metals. Schoonman. Properties. Pivkina. Phys. Cook. Kinetics of oxide films growth on metal crystals: electron tunneling and ionic diffusion. N. 2002. Knauth and J. editors P.T. 1948–1949 12 163–184 . Phys.L.F. Formation and characterization of metal–polymer nanostructured composites. A. Prog. 92–117 7. Rep. Zavyalov.Nanostructured Composites: Structure. Solid State Ionics 2002 147 415–419 8. Kluwer Academic. Schoonman. Fromhold and E. Cabrera and N. Properties and Applications.. 1967 158 610–612 9. and J. Rev.. A. and Applications in Electrochemistry 217 Synthesis Methods. S.

201. See Nanostructured carrier 177–178 material. 81 Building blocks. vi Bulk electrochemistry. 93. 187 fuel cells v. for conventional electrolytes. of nanotechnology. corrosion-resistant coatings for. of DSC. 193 Amorphous nature. See Alkaline fuel cell membrane fuel cell relating to. efficiency of. ionic Bulk junctions. 210. 186. 83 nanoscale materials and electrochemistry Bulk electrolytes. high-end polymers relating Carbon aerogel anodes. 91 with low density. 82 108 Alternative. in B nanostructured materials Band diagram. 175–177 sol-gel synthesis. 53. 35 Aerogel nanoarchitecture. 91 synthesis of. 185. 193 Basic quantum mechanics. 82. See also Vanadium oxide aerogels: enhanced energy storage. 212. See Sticky carbon. 161 Carbon black. 189 solid-state. 194 transition metal oxide aerogels. rechargeable. 195 to. 165 Alternative membranes. 4 amorphous nature of. of nanocrystals. 56 Alternative energy conversion and storage of wet chemical nanocrystal synthesis. 161 Capacitive current. 207–210. 83 characteristics and advantage of. 95 electrochemical properties of. 96–100 as highly porous nanostructured materials. 193 Carbon composite bipolar plates. 56 devices. 56 Aerogel-like morphology. 34. 38–39 Aerogels. 191 Li ion. 162 Carbon. vi. v. 176–177 AFC. 189 Beer-Lambert law. 34. vi quantum size effects relating to. 189–191. 159–162 C composite. ionic electromigration in. 205. Bottom-up method 211 of synthesis. 157 176 Al(Al2 O3 )/PPX nanocomposites. 215 metallic. 46 dendrimer PTFE copolymers. 60 Alternative energy devices. 1 liquids as. needed for. 33.Index A Anisotropic growth. synthesizing V2 O5 Atoms materials with. Optimise carrier material 219 . Alkaline fuel cell (AFC). 113 ionic liquid mixtures. 176–177 Analytical challenges. 59. 191 nanoparticles surfaces relating to. 204. 192. 161–162 Calorimetric measurements. 186–189 carbon composite. Carrier material. 38 carbon aerogel anodes. through Bipolar plates. 195 Batteries. 190. of aerogels. 55. 154 AFM studies. SWNTs polymer blends.

152 in nanostructured electrodes. long-term testing of. 156. vi. 23 bipolar plates. Solar cells process of. criteria for long-term stability of. 176 kinetic measurements. 29 electrochemistry advantage of. 120 Charge transfer resistance Rt . metal oxide nanocrystals. 94 D galvanic. 165 solar light harvesting relating to. See Constant phase element electrochemical deposition of. 197 Density. alternative. 41. v. 50–51 Catalytic studies. 175 Critical nucleus. Diffusion-convection. of nanoparticles surfaces. materials 58–59 circumventing conductivity problem. 151–152 correlation between. 3. spectroelectrochemistry and. applications. 4 Ti(TiO2) /PPX. 10 Conversion efficiencies. 3. deciphering mechanisms of. Crystallization 36–37 phase stability and transformation. 21 alternative for. of synthesis. 136. 86–87 energy conversion. 22–26 Corrosion-resistant coatings. 1 polarization and. v. 2 Constant phase element (CPE). 193–194 Characterization techniques. of porous Colloidal stability. 191–192. 117–119 Di-para-xylylene. circumvention of. 24–26 . 94. 110 134–135 Diffusion layer two-step. 22 Conversion. 63 operation of. fuel cells as. transport by. DSSC. 82 challenges of. See Direct methanol fuel cells Composite membranes. of Cation-insertion process. 81. 163–164 Double-layer structure. See also Carbon composite DSC. 4 191–193. for enhanced FTIR. 27. See also Storage devices Charge transfer energy. 45. See also Electrocatalysts. 201. of nanoparticles surfaces. 137–138 solid state p-n junction. 109 Chronoamperometry. nanostructured materials with. 214–216 conversion efficiency of. 100 Debye temperature. of solar cells. 3. See also Fuel cells. transport by. 122 124–126 of infinite thickness. 197 Distributed features and dispersion. aerogels as highly porous deciphering mechanisms. fuel cell. 120 Diffusion. of change storage 193–194 EXAFS/XANES. at porous interface. low. 197 mesoscopic film relating to. Deciphering mechanisms. See also IPCEs solid-state. 194 nanoparticles. 24 Coulombic repulsion. relating to. 83 Change storage. 137 molecule used by. 62–66 electrochemical. in Dye-sensitized solar cell (DSC). 5 Controlled hydrolysis. problems of. of photons. 57. electrode geometry. of finite thickness. 10–14 stability of. Nanocomposites. Dendrimer PTFE copolymers. for metallic criteria for. 94 electrolytic. 33 Charge carrier collection. of change storage. 7. 14–17 Devices. 14. 111 Composites.220 Index Catalysts. 202 band diagram of. 57 recent experimental results on. 42 and PAFC CPE. in nanostructured Decomposition method. Dye. 159. 203 Circumventing conductivity problem Direct methanol fuel cells (DMFC). 61. 3 Conductivity problem. 161 191–193. 23 ture. 18 Conventional electrolytes. 3 TiO2 /PPX. 9. 48 Cells. ionic liquids as performance of. in PEMFC Coulomb interaction. See Dye-sensitized solar cell bipolar plates. 186. 192–193 171–172. See Dye-sensitized solar cells Nanostructured composites: struc. 189 193–194 Device efficiency. 135–137 37–38. 47. 194 energy storage. 84 DMFC. 210–212. 175 sticky carbon. with adsorbed intermediate. 173. nanocomposites. 28. surface energy and. 161–162. properties. 20.

See Electrochemical double-layer definition of. 138 structure. 104. 103 Electrochemical properties free. interface structure. 85. See also Nanoscale storage devices. 82–83 fuel cells. 96. 82. 87 Electrostatic stabilization. 93. 100–102 nanomaterials. nanomaterials and 159 nanostructured films as. 213–214 tured films as. 106–108 Electrochemical double-layer capacitors Electron transfers. properties. quantum size effects relating to. 94 nanoscale materials and electrochemistry operation of. at interfaces. porous effect relating to. in bulk electrolytes. 90. of aerogels. time history v. 195–198 levels of. 102–103 . 105–113 operation principles of. 89 Electric current. energy conversion and storage in. reactions of. of sol-gel technology used materials. 211. and nanostructures. 15. light-induced charge sepa. 104–126 Energy conversion and storage devices. 82 electrochemical double-layer capacitors. 57. mass transport enhanced storage of. vi basic principles of. 94 general properties of. 81–82 103. 61–62 Electrochemical impedance. investigating techniques for. See also Porous electrode Ecole Polytechnique F´ed´erale de Lausanne. 2 nanomaterials. 94–97 definition of. correlation bulk. 81 relating to. 88. future prospects for. general properties of. 81–150 lithium ion batteries. fundamental. 175 108 optimise carrier material relating to. and applications in. 185–200 phenomena involved in. 81 techniques for. efficiency of. 119–124 Electrochemical measurements. investigating alternative. 59. 86 Electrochemical characterization. ionic liquids as alternative for. 10–14 113–126 Electric double layer at interfaces. critical nucleus and. electrode reactions. 2 geometry.Index 221 structure of. 81 surface. 93 of V2 O5 . 111–113 Electrolyte membranes. electrochemistry and for. 87–90 Electrolytes Electroactive materials. 97–100. and nanostructures. 86 (EDLC). of low.and medium-temperature fuel cells. 108–111 Fermi. 168–169 Electromigration. ionic electromigration in. 88 capacitors electroactive. 87 Electrochemical cells. 204 Energy Electrochemical process. Scanning electron 172–175 microscope views relevant reactions of. Electrons. 113–126 Energy conversion and storage devices. See also IPCEs. 102. nanomaterials and nanostruc- Electrical resistance. of electricity. 40. metal oxide nanocrystals relating to. 93–94 104 interfacial. 169–174 kinetics of. Electroactive electrodes. 90 ration and conversion of photons to. 83 between. Dye-sensitized solar cells (DSSC). 91–92 in PEMFC and PAFC Electrolytic cell. 212 nanostructured. 165 152 nanomaterials as. in vacuum. Electrochemical deposition. 191 38–40 Electrochemistry. 201–217 E Electrodes. 108 Electrocatalysts conventional. of catalysts. ionic. 135 Electrochemical generation. Porous electrodes EDLC. 81–82 photoelectrochemical solar cells. 87–91 Electrical resistivity. 128. introduction to. 50–51 concepts of. 175 kinetics of. 214–215 Electron transfer reaction. 138 202 introduction to. 90 bulk.

166 194 Impedance. 28 Maxwell’s. 111–113 MCFC. 115 Free energy. 33 Fourier transform infrared (FTIR) spec. formation of. 119–124 FTIR. nanostructured materials’ EQE. 93–94 lysts of. 96 133–135 as efficient energy conversion devices. 100 Ostwald-Freundlich. alternative. 20 reaction rates of. 152 materials. Imidazoles. v Equations Future prospects. 120 Fuel cell catalysts. 10. low. vi. electrocata- chemistry. 178–179 Enhanced red and near IR responses. diffusion layer of. See Heteropoly acids F Hybrid metal/metal oxide-PPX. 3. I troscopy. of nanostructured Heteropoly acids (HPA). solution of. 102 Ionic electromigration. 52 Gas diffusion layer (GDL). 100 Energy devices. 96. 188 Fossil fuels. in nanostructured potential of. PPX vacuum co-deposition. of GDL. spectroelectrochemistry and. 65 125 EXAFS. 93 electrochemical. 114. 154. 40. 11. 151–152 Interface Fuel cells. by light technology and nanotechnology of. 102 Experimental results. 10 orbital HPA. 28 evolution. 185–200 power sources based on. 152 low-temperature. 120. 42 Galvanic cell. 203 Highest occupied molecular orbital (HOMO). See External quantum efficiency impact on. 47. v. 163–164 composites High-end polymers. diffusion layer of. 121. 175 energy conversion and storage devices Interfacial electrochemistry. 123 spectroscopy. 26. 204 to. drawbacks of. 152–158 containment. 15.and medium-temperature. for solar cells. See Fourier transform infrared Warburg. steady-state solution of. 98 Equilibrium. Nanotechnology. 202. electric double layer at. batteries v. 152 Energy conversion devices. See Fluorine-doped tin dioxide Infinite thickness. polarization and charge transfer at. for fuel cells. 188 developments. 152 Interface structure. 161 nanocomposites. electron transfer reaction at. SOFC. 41 lithium ion batteries relating to. 121 Hydrolysis First large-scale field tests and commercial of alkoxide. steady-state solution of. high-temperature. 26–28 controlled. methods of. 93. 100 108 . 203–204 10. in electro. 19 FTO. 38. 18. PEMFC.222 Index Energy conversion and storage. 175 phase stability and transformation. of solar cells. See Highest occupied molecular External quantum efficiency (EQE). 94. 24–26 HOMO. 50–56. DMFC. 103 Hydrogen oxidation reduction. 63 Fluorine-doped tin dioxide (FTO). Growth. 153–156 Enhanced energy storage. 127–138 Evolution equation. 82 membrane. 9 technology of. 169–170 Finite thickness. See X-ray absorption fine structure H Experimental aspects. polymer blends relating nanocomposite analysis. 201 Fermi energy. nucleation and. See also AFC. fuel cells as. See Gas diffusion layer nanoparticles relating to. 106–108 PAFC. 49 G linearized nonsteady-state. SPEFE porous. 44–49 Geometry Schr¨odinger’s. 82–83 relating. on DSC stability. 125 Laplace-Young’s. in bulk electrolytes. spectroelectrochemistry Incident photon-to-electron conversion and efficiencies (IPCEs). 37 porous electrode. 125 G24 Innovations. 61. 17.

195 aerogels. DSC’s use of. 35 requirements of. 93. 131–133 Molecule. 86 semiconductor. 102 MIE theory. transition. See also Nanostructures conversion efficiencies composite. of solar cells. to electric current. 57. 7 Metalorganic chemical vapor deposition Laplace-Young’s equation. 154–155 IPCEs. 60–61. 159. 59. enhanced red and near IR Metal oxide electrodes. 165. 45 evaluation of. 59–67 Light-induced charge separation and con- controlled hydrolysis relating to. 195 Metal (metal oxide)/polymer nanocomposites. 154 Ionic transport. 9 Metal oxide nanocrystals. at interfaces. solution 61–62 of. 2 of electrons. See Nanoscale electronic. 175 relating to. nanoparticles surfaces mixtures. 187 K Mesoporous TiO2 film. of. 152. 97 Micrometric-scale materials. 138 Kinetic measurements. in nanostructured materials. 47. 63 version of photons. 186 polymer membrane. 108–111 Molybdenum oxide. 61. 98 Methanol. See also types of. 7. development of oxidation. 3. oxidation of. 186–191 Nanoarchitecture. 62–66 Li ion batteries. 10. involved in Molten carbonate fuel cell (MCFC). 2. 173. 154 Ions. 154 transport and GDL. 166. 9–14 crystallization process of. 163–164 Mesoporosity. ionic electrode. 64–66 Lithium. 195 orbital MnO2 cathodes. 6. See Lowest unoccupied molecular Mixed-valence compounds. Lithium ion batteries. 47 Metallic bipolar plates. 42 as alternative. components of. monolayer absorbed on. See Incident photon-to-electron Membranes. 8. 167 Light containment. 96–100. storage. 187 10. 24 vanadium oxide aerogels: enhanced energy NafionTM . Microporosity. 12. 125 sol-gel process relating to. 1 212 Mesoscopic TiO2 layer. 165–166 PEMFC use of. easy transport of. See Molten carbonate fuel cell 165 Mean particle radius. 162 relating to. for conventional electrolytes. 8. 117 synthesis of. 61 Linear sweep voltammetry. 171–172 reactions of. Linearized nonsteady-state equation. 161–162.Index 223 Ionic liquids. of Ti/PPX nanocomposites. 170. 160. 24 Mesoscopic film Kinetics DSC relating to. 202 202 geometry relating to. 195 MOCVD process. 186–189 N3 dye. 42 LUMO. MCFC. 165–167 Maxwell’s equations. 186 . 163. vi. corrosion-resistant L coatings for. 166 Membrane fuel cell. 5 Mass transport phenomena. 158 electrochemical process. See Metalorganic chemical M vapor deposition process Macrohomogenous concept. See Lithium ion batteries electrostatic stabilization relating to. light harvesting by sensitizer of electron transfer reaction. 49 (MOCVD) process. 191 Materials synthesis MoO2 cathodes. 165 bipolar plate. 191 responses by. 83 Lowest unoccupied molecular orbital (LUMO). 6–9 106–108 Mesoscopic solar cell variants. 165 Melting temperature. 176 Lambert Beer’s law. through N sol-gel synthesis. 19. 189–191 transition metal oxide aerogels.

23 electrochemistry. Al(Al2 O3 )/PPX. 205–215 across interfaces. 35 Nanostructured anatase titanium dioxide. importance of. 1 metal (metal oxide)/polymer. synthesis of. 44. design and properties of. 84 Nanostructured composites: structure. solar cells. 9 as electrolytes. physicochemical introduction to. 50–56 absorbed on. 22 Nanoparticles surfaces Nanoscience. 86–87 Nanocrystalline solar cells. 34–35 Nanostructured cathode materials. 18. 137–138 . size of. new sensitizers and redox systems. 204 Nanoscale inorganic or organic semiconduc- formation of. 173 characteristics of. 38–44 and operational principle of. 43. 211 152 analysis methods of. band diagram and electrons relating to.5 standard reporting condition. 202 Nanoscale materials. 202. 82 59–60 charge transfer challenges relating to. 59 Nanoscale materials. 92 charge transfer in. introduction to. 19–20 SnO2 . 47. 202–204 Nanoscale effect. by light 81–150 containment. 65 stability of. 4–5 size effects of. 91–92 first large-scale field tests and commercial nanostructured films and. 36–37 Nanostructured carrier material. 59. 7. 54. 192–193 Nanoscale hydrophilic inorganic materials. Transition metal nanocrystals. 44–49 nanocrystalline solar cells. 163–164 overall conversion efficiency under global production of. 84 kinetic measurements of. 17–18 sodium. 83–84 introduction to. 81 experimental aspects of. increase in.224 Index Nanocomposites. 5–6 transition metal nanocrystals. 34–38 harvesting by sensitizer monolayer nucleation. 37–38. 205–207 33–34 Ti/PPX. 63. melting of. 22–26 Nanomaterials dye. open circuit photovoltage. recent applications of: Nanocrystals. ionic transport and results and discussion about. electrochemistry and Nanocrystalline metal oxide semiconductors. nanostructures and. 207–210. 55. 185 colloidal stability of. examples of. 1–4 properties of. 85. 82–86 Nanocrystalline TiO2 layers. 81 atoms relating to. 87–91 future prospects for. AM 1. synthesization methods for. 21–22 for improved membrane properties . charge carrier collection. 201–202 Nanoscale electronic. 54 quantum dot sensitizers. 59–67 mesoscopic semiconductor film. 33–80 conversion of photons to electric current. vi. as electroactive developments of. 35 erties. 86 operational principle of. 4–5 synthetic methods. 56–59 development of. 6–9 phase stability and transformation. 203 tors. 34–35 201–217 Nanoscale architectures. 212 Nanoscale materials. 20 50 photocurrent action spectra. Sn (SnO2 )/PPX. 36 solid-state DSCs. 28 Nanometric-scale materials. enhanced red and near IR responses. 64. 202 catalytic studies of. strategies for. 24 Nanoparticles. alternative energy devices dependent on. band diagram quantum size effects. nanotechnology and. applications. light nanoparticles surfaces. v light-induced charge separation and assembly and properties of. 89 along interfaces. 173–174. prop- melting temperature relating to. 33–34 9–14 metal oxide nanocrystals. growth and. 14–17 synthesis of DSC anisotropic growth of. 1–32 tals. 49–66 nanostructure. 18 SnO2 . 56 photovoltaic performance of. 92 Nanostructured electrodes. in electrochemistry. See also Metal oxide nanocrys. criteria for long-term stability of. 26–28 electrodes. 34. 21 composite membranes.

102–103 for fuel cells. AM 1. 158. light Pd/PPX nanocomposites. 9 Oxygen reduction reaction. effects of. increase in. under global future application of. 1 bipolar plates. 53. fuel cell technology impacted by. nanomaterials. 159–162 Ostwald ripening model. 164–165 Nucleation. 159 of Ti/PPX nanocomposites. 159–167 ionic liquids.5 standard reporting condition. open circuit photovoltage. 90 crystallization relating to. increase in. 50–56. 47–48 Nanotechnology Phosphoric acid fuel cell (PAFC). 45. 48 Nanotechnological applications. 186. 19–20 emerging field of. 86 containment. 113. 99 nanocomposites. kinetics of. 6–9 fuel cell nanoparticles. of DSC. 205 harvesting by sensitizer monolayer PEMFC. 196–197 Optimise carrier material. 185–200 New sensitizers and redox systems. See Purpose-built materials mesoscopic semiconductor film. as nanostructures. 53 current. and. increase in. 152–158 Photovoltage.5 standard reporting condition. 175 0-D. 87–91 relevance of. 9–14 PBM. 214. See Phosphoric acid fuel cell conversion of photons. nanomaterials and. 173 2-D. 65 Nanostructure. 151–158 photocurrent action spectra. 99 nanostructured. 164–165 Phase stability and transformation. in PEMFC and PAFC. 14–17 Overall conversion efficiency. 178–179 model for. 151–152 Nanostructured materials. 174–175 alternative energy devices improved by. 202 nanoscience and. 189 Nanotubes. 5–6. 17–18 nanoparticles. 85 Photoelectrochemical solar cells. 44–49 Nanostructuring. 52 alternative membranes. 84 Photocurrent action spectra. by light Oxidation-reduction reactions. 21 surface defects. 2. of TiO2 vol%. 19–20 . 52. v development of. open circuit. 81 aerogels as. 21 analytical challenges of. power sources equations relating to. 99 Ostwald-Freundlich equation. 174–175 3-D. 165–167 P light-induced charge separation and PAFC. 56 charge carrier collection. 215 163–164 Perkin-Elmer 503 spectrometer. 5 enhanced energy storage in. 169 for fuel cells. in PPX matrix. 114 Nanostructured membranes.Index 225 Nanostructured films. See Polymer-electrolyte-membrane absorbed on. 175–177 Photovoltaic performance. under global electrochemistry. v. 21 168–175 overall conversion efficiency. 172–175 Nanostructures. 171–172 of. 45–49 based on fuel cells for. growth and. for improved membrane Percolation. general properties of methanol. 83. 196 Open circuit photovoltage. 159–167 electroactive electrodes. 173–174 1-D. properties . 21–22 new technologies developed with. 20 introduction to. 88–89 electrochemical deposition. 20 81–150 Oxidation electrolyte membranes. vi. 18 electrocatalysts. v 168–175 definition of. v Nonsteady-state techniques. interpenetrating. electrochemical properties of V2 O5 impacted by. vi Network junctions. 204 nanostructured membranes. 178–179 AM 1. 212 enhanced red and near IR responses.composite membranes. 47. of quantum dot sensitizers. to electric Particle radius. 99 architecture. 177–178 Photovoltaic cells. of catalysts. of electroactive materials. basic principles of. 99 nanotubes. 195–198 O pseudocapacity and importance of pore 1-D nanostructures.

transport in. 128–131 Silica. See Semiconductor quantum dots relating to. 90 Salt reduction method. 186–189 Quantum size effects. 10 Q Sol-gel process. of synthesis. 135 nanoscale inorganic or organic. 158 . 86. 206–207 214. 135–137 Schr¨odinger’s equation. percolation. polarization and charge nanocrystalline metal oxide. 133 semiconductors relating to. 215 Rechargeable batteries. 91 Pore architecture. 59. 57–58. transport in. 135 65 Power sources based on fuel cells. polarization and charge SnO2 nanocrystals. development of. 210. 61 Quantum dots. 64. 202. in PEMFC and PAFC. Nanoscale architecture. 203. analysis of. 188 Polarization and charge transfer. 54 nanotechnological applications. metal oxide nanocrystals QDs. 203–204 Sodium nanoparticles. 195 transmission line description of. 134. 178–179 SnO2 nanoribbon. 43. 3. 50 SOFC. of synthesis. transition metal oxide Quantum dot sensitizers. 201. 1 solid and electrolyte phases. R scale materials. See Poly-para-xylylene Sn (SnO2 )/PPX nanocomposites. 84 Sol-gel synthesis. vi energy levels relating to. 127–128 SnO2 -based anodes. 154–155 oxidation-reduction. Polymer-electrolyte-membrane fuel cell 113–126 (PEMFC). energy storage devices’ atoms relating to. 36 Precipitation reactions. 196 materials. 206 PPX vacuum co-deposition.226 Index Physicochemical properties. 158. of hydrolysis. at porous Reactions. 44. 54. at interfaces. 127–138 Scanning electron microscope views. mesoscopic. 55 Porous interface. 205–207 PPX matrix. 47. 131–133 Semiconductor film. quantum size effects relating to. 128–131 SnO2 colloidal suspensions. 56 cells photoelectrochemical. 59 Porous electrode geometry. 63. in. 101. 41 macrohomogenous concept of. 8 distributed features and dispersion. pseudocapacity and Ruthenium oxide/titanium oxide. charge transfer Semiconductor quantum dots (QDs). 59–60 transfer at. precipitation. Polymer blends. 9. 40 133 Sensitizer. 159 electron transfer. recent applications of: solar Purpose-built materials (PBM). DSC relating to. 136 S Porous effect. 97 Polymer membrane. See also DSC. See Pore size distributions Solar cells. 102–103 Solar light harvesting. 38. 134. 152 Porous electrodes Single wall carbon nanotubes (SWNTs). 101. 38–39 use of. of TiO2 vol%. 193 theory of. See also Kinetics interface. 84 Reaction rates. 215 properties of. 86 Polyol process. See Solid-oxide fuel cells PSD. investigating techniques for. 134–135 of electrocatalysts. 40 Solid-oxide fuel cells (SOFC). melting of. 6–9 nanostructured electrodes. high-end polymers relating to. 155. 169 Poly-para-xylylene (PPX). 38–40 Solid and electrolyte phases. 17 in. 50 214. of nanometric. 58 oxygen reduction. 54 PPX. 38–44 Sol-gel technology. for SnO2 nanoparticle. See DSC transmission line description of. 169–174 161 of electrodes. Mesoscopic solar Pseudocapacity and importance of pore cell variants. 196 Pore size distributions (PSD). 191 importance of. 106–108 electrocatalysts in. 168–175 of lithium ion batteries. 153. transfer at. electrodes relating to. 17–18 aerogels through. 137–138 Semiconductors porous interface.

202 by diffusion-convection. 8 101 TiO2 polymorphs. 204. 58 84 salt reduction method of. V2 O5 /SWNT. See also Materials synthesis of metal oxide nanocrystals. 81 Transport. 214. 59–66 V nucleation. of linearized nonsteady-state 215 equation. 214. 194 Toyota dream house. 1 TiO2 vol%. of synthesized ti- Synthesization methods. Testing. 196–197 of ions. 212 introduction to. efficiency of. 186 Surface energy. 194 aerogel-like morphology for. of nanoparticles electrostatic stabilization relating to. 59 of DSC. 191 T electrochemical properties of. 197 Transmission Electron Microscopy (TEM). 91 TiO2 /PPX composites. percolation of. See Single wall carbon nanotubes intermediate. 44. 49–66 metal oxide nanocrystals. 187 U of transition metal nanocrystals. 187 sticky carbon relating to. 207. effects of. 93–103. 24 materials synthesis relating to. sol-gel synthesis. critical nucleus and. 11. 10. synthesis of. 211. 139 characterization techniques for. 99. 27 Spectrometer. 89. for nanoparticles. V2 O5 relating to. 190. 56–59 UV-visible spectra. correlation in solid and electrolyte phases. 57 colloidal. 193 152–158 Vanadium oxide aerogels: enhanced energy TEM. XAS Transition metal nanocrystals. 212 Spectroelectrochemistry. of DSC. 211–213. 192 201. with adsorbed SWNTs. See Nanoparticles surfaces. synthesis of SPEFE. 124–126 Synthesis. Solution. 58–59 transformation. 195–198 Tailor-made materials. 92. See also Phase stability and decomposition method of. electrical resistivity v.Index 227 Solid-polymer-electrolyte fuel cell (SPEFE). 57. 92 Surface defects. in nanostructured materials. See also Mass transport phenomena. 37–38. 60–61. 13. 188 Spectroscopy. See FTIR. growth and. of evolution equation. of fuel cells. 50 211 Synthetic methods. 191–194. 12. 128–131 alternative. 210. 92 Ti/PPX nanocomposites. of porous energy conversion and electrodes. Perkin-Elmer 503. long-term. 92 Surface and transformation enthalpies. TiO2 Two-step charge transfer. 57–58. 202 Solid-state DSCs. FTIR and. 108 of. 22 TiO2 surface. 10. fuel cells relating to. 4 185–200 3-D nanostructures. 11. 201. 208. 50–51 2-D nanostructures. of nanoparticles surfaces. 56 Stability. vi across interfaces. production. 102–103 involved in electrochemical process energy conversion and. 185–186 TiO2 conduction band. 191–192. 59. 50–56 V2 O5 . 22–26 Transition metal oxide aerogels. in PPX matrix. 192 Technology and nanotechnology. 12 197 Time history. 64–66 of tailor-made materials. See Solid-polymer-electrolyte fuel cell bottom-up methods of. 186–189 124 Transition metal oxide electrodes. 186–191 . 191 Sticky carbon. 90 Surfaces. 45 Solid-state batteries. 46 along interfaces. 209 Storage devices Transmission line description. 216 Space-charge region. 21 Solid state p-n junction devices. 133 between. Ti(IV) ions. 186. 108 of sol-gel technology. through Steady-state solution. See Transmission Electron Microscopy storage. TiO2 particles. operation principles by diffusion. 204 Transition metal alkoxides. for nanoparticle tanium/polymer nanocomposites. polyol process relating to. 125 Ti(TiO2) /PPX composites.

See X-ray absorption spectroscopy X-ray absorption fine structure (EXAFS). 193. 138 X-ray absorption spectroscopy (XAS). on electrochemical XANES. Wet chemical nanocrystal synthesis. 95 . 124.228 Index Vanadium oxide aerogels (Continued) X nanostructure’s impact. 193–194 Warburg straight line. 121. See X-ray absorption near edge properties of V2 O5 . 15 X-ray absorption near edge structure Warburg impedance. 56 0-D nanostructures. 186 XAS. bottom-up 194 methods of. 195–198 structure Vanadium pentoxide. 120. 123 (XANES). 137. W 193–194 Warburg diffusion resistance.

4 dicarbo-xylate) .2-bipyridyl-4.Color Plates Fig.1 Structure of the N3 dye cis − RuL2 (SCN)2 (L = 2. 1.

Conducting glass TiO2 Dye Electrolyte Cathode Injection S* −0.0 S /S+ e. 1. which is immersed in the dye solution.4 Uptake of N3 dye by a nanocrystalline TiO2 film. The electrons diffuse across the oxide to the transparent current collector made of conducting glass. The resulting deeply red-colored film is the photoactive part of the DSC . Light absorption by the dye (S) produces an excited state (S∗ ) that injects an electron into the conduction band of a wide band gap semiconducting oxide. The reduced form of the mediator (red) regenerates the sensitizer closing the cyclic conversion of light to electricity Fig. 1. such as TiO2 .5 Maximum Voltage 0 hν E vs NHE Red Mediator Ox (V) 0. e- Fig. From there they pass through the external circuit performing electrical work and re-enter the cell through the back contact (cathode) by reducing a redox mediator (ox).5 Diffusion 1.2 Energy band diagram of the DSC.

Japan) Side view Top view Fig.8 Side and top view of the RuL2 (NCS)2 (N3) sensitizer anchored to the (101) TiO2 anatase surface through coordinative binding of two carboxyl groups to surface titanium ions.7 Scanning electron micrograph showing anatase crystals of ca.64 nm2 . 1. Co. Catalysts & Chemicals Ind. The green and red spheres present titanium and oxygen. Ltd.Fig. Tsuguo Koyanagi. employed as light scattering centres to enhance the red response of the DSC (courtesy of Dr. 400 nm size.. Note that the left carboxylate group straddles two Ti(IV) surface ions from adjacent surface titanium rows while the right one forms an ester bond. The structure shown represents the lowest energy configuration derived from molecular dynamics calculations and the area occupied by one adsorbed N3 molecule being 1. 1. respectively.


Two transmission lines are used to model the motion of the conduction band electron motion through a network of mesoscopic semiconductor particles and the charge compensating flow of redox electrolyte. The latter is defined as the electric charge (measured in Coulomb) that is required to move the Fermi level of the of the semiconductor nanoparticles by 1 eV. 1. Zd is the Warburg dif- fusion resistance describing the motion of triiodide ions through the porous network to the counter electrode while RCE and CCE are the charge transfer resistance for the reduction of triodiodide and the double-layer capacitance of the counter electrode. The electrical equivalent circuit treats each particle as a resistive element. Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye RS rtrans rtrans rtrans rtrans Dye Dye Dye rct rct rct Dye Dye RFTO/EL cch cch Dye cch RCE Dye Dye CFTO/EL Electrolyte Zd Dye Dye CCE Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Dye Fig. respectively The red dots present cations from the electrolyte . Interfacial electron transfer from the conduction band of the nanoparticle to the triodide is modelled by a charge transfer resistance rct connected in parallel with their chemical capacitance cch .12 Equivalent electric circuit diagram of a solar cell based on a nanocrystaline semiconduc- tor film in contact with an electrolyte.

13 Photo-induced processes occurring during photovoltaic energy conversion at the surface of the nanocrystalline titania films. red dots: sensitizer. Grey spheres: titania nanoparticles. green and blue dots: oxidized and reduced form of the redox couple Fig. 5: recombination of the conduction band electrons with the oxidized form of the redox couple regenerating the sensitizer and transporting the positive charge to the counterelectrode. 1. 2: radiative and nonradiative deactivation of the sensitizer. e− + * 3 S /S − 1 2 Oxidation − e Potential 5 + 4 Red/Ox TiO2 S+/S Couple Fig.14 Cross-sectional view of the embodiment of DSC used in the laboratory for photovoltaic performance measurements . 1: sensitizer (S) excitation by light. 3: electron injection in the conduction band followed by electron trapping and diffusion to the particle surface. 1. 4: recapture of the conduction band electron by the oxidized sensitizer (S+ ).

17 The two coupled redox cycles involved in the generation of electricity from light in a dye-sensitized solar cell .1 K-19 sensitizer with an extended p-system in one of its ligands Light Conduction – Band I S S* e – e– e– e– e– 1 2 I2 S+ Semiconducting e– Membrane Electrical Work Fig. COOH O HOOC N N N Ru N N C N S C S O Scheme 1. 1.

For details see web announcement http://www. 2 .20 The Toyota “Dream House” featuring DSC panels made by Aisin Seiki. 4 tricarboxylic acid The Toyota Dream House DSC made by AISIN -SEIKI Fig. Note the monolithic design of the PV modules and the use of carbon as interconnect and counter electrode material. 1. .jp/jp/news/04/Dec/nt04 1204. The red dye is related to N-719 while the black dye has the structure RuL (NCS)3 where L = 2.19 Production of DSC prototypes by Aisin Seiki in Japan.Fig. 2 -terpyridyl-

considering a cathode composed of a lithium cobalt host and an anode composed of a crystalline structure of hexagonal graphite . 3. 1. The layered host lattice in the cathode and anode is also illustrated. The lithium ion is intercalated in the anode during charging and in the cathodes during discharging.21 First commercial flexible lightweight cell produced by G24 Innovation on a large scale for us as telephone chargers CHARGE Power supply e− Load O DISCHARGE Co Li ELECTROLYTE Carbon CATHODE ANODE Li1-xCoO2 Graphite Fig.3 Schematic of a rechargeable lithium battery in discharge/charge mode.Fig.

H + e− Fig.5 Schematic cross section of the simplified planar anode–electrode–cathode structure of two typical fuel cells: a polymer-electrolyte membrane fuel cell and b solid oxide fuel cell . 3.a Load b Load H2 O2 H2 O2 H2 H2 O H2 O O2 ANODE CATHODE ANODE CATHODE diffusion path diffusion path H O O2.