ELECTROCHEMISTRY FOR A CLEANER ENVIRONMENT
M. Aulice Scibioh and B. Viswanathan* Department of Chemistry, Indian Institute of Technology Madras – 600 036, INDIA.
A status report of electrochemical processes and devices that could offer cleaner technology for environmental compatibility is presented. Electrochemical processes for treatment of wastewater Emerging
solutions/effluents, flue gases and contaminated ground water and soil are discussed.
electrochemical power sources for cleaner generation of electricity in fuel cell power stations and for electrically driven vehicles are also given. An overview of the contributions that battery-powered The role of
devices have made in medical science towards modern health care is given.
electrochemical sensors in monitoring toxic substances and the role of photoelectrochemistry with its interesting possibilities for treatment of pollutants and energy conversion as well as storage is discussed. The beacons and barriers in each strategy are viewed critically and suggestions for
improvements of existing electrochemical processes or products in order to minimize the environmental impact are also provided.
Keywords: Electrochemical processes, cleaner technology, electrochemical sensors, fuel cells, power sources, photoelectrochemical devices, solar energy conversion, energy storage systems, batteries, effluent treatment.
ELECTROCHEMISTRY FOR A CLEANER ENVIRONMENT CONTENTS 1. Introduction 2. Electrochemical processes for effluents and waste treatment Anodic oxidation of toxic species 2.1.1. Direct oxidation at the anode 2.1.2. Indirect/mediated electrochemical oxidation Cathodic processes Removal of heavy metal ions Electrochemical decholorination Electrodialytic processes Electrochemical remediation of soils Electrochemical gas purification 3. Electrochemical power sources Electrochemical capacitors Batteries for electric vehicles 3.3 Batteries for modern health care 3.4. Fuel cells 4. Electrochemical sensors Potentiometric sensors Amperometric sensors Coulometric sensors Pump-gauge devices Conductometric sensors 5. Photoelectrochemical methods 6. Conclusion & Outlook
The rapidly growing world population, increasing number of reports on detrimental effects on the environment and the concern for its protection is major issues today. The strategy for environmental protection in industry necessitates the processes for waste treatment as well as the development of new and alternative processes and products, which have no or less harmful effects on environment. Electrochemistry offers promising approaches in both types of strategies. The inherent advantage is its environmental compatibility, due to the fact that the main reagent, the electron, is a ‘clean reagent’. Electrochemical processes can be used for recovery or treatment of effluents from Industrial electrochemistry has undergone a remarkable development towards Electrochemistry offers unique ways to These
cleaner processes and environmentally friendly products.
generate pure electric power at high efficiency in fuel cell systems or to store it in batteries. power sources found their role in stationary power systems.
The use of batteries in tackling Electrochemical sensors
problems related to human health has a proud heritage and a bright future.
are particularly attractive because of the chemical species, which are directly measured and transuded into electrical signals. As for electrical components, two types can be distinguished:
active sensors, which give a voltage (potentiometric sensors) and passive sensors, for which an electrical source is necessary to impress a signal, the response of which is analyzed afterwards (amperometric, coulometric and conductometric sensors). Photoelectrochemical cells for electricity
production offer a sustainable way to generate electricity e.g., for charging batteries in electric vehicles. Compared to conventional photovoltaic cells, photoelectrochemical cells is less expensive
since it uses inexpensive raw materials, easily fabricated and does not require expensive crystal purification processes.
Attractive advantages of electrochemical processes include: (1) Energy efficiency: Electrochemical processes generally require lower temperatures than their equivalent non-electrochemical
counterparts e.g., thermal incineration.
Electrodes and cells can be suitably designed and organized
to minimize power losses cost by inhomogeneous current distribution, voltage drop and undesirable side reactions. (2) Cost effectiveness: Cell constructions and peripheral equipments are generally (3) Automation: The
simple and, if appropriately designed and assembled, also less expensive.
systems are amenable to automation emerging from inherent variables of electrochemical processes i.e., electrode potential and cell current are suitably adjusted for facilitating process automation. (4)
Versatility: Direct or indirect oxidation and reduction, phase separation, concentration or dilution, biocide functionality, applicability to a variety of media and pollutants in gases, liquids and solids, and the treatment of small to large volumes from microliters up to millions of liters are also possible.
The applications of electrochemistry for the protection of environment have already been exclusively discussed in number of books and reviews1-9. Many of the concepts discussed in early
publications are still of interest today but progress in material science (new electrode materials and membranes) and aspects in electrochemical engineering (new and effective cell design) have offered possible effective and appealing solutions. This review provides a broad perspective on the use of Electrochemistry can be used both in the
electrochemistry for the future of human beings.
electrolytic mode (electrolytic processes for purification and recovery) and in the galvanic mode (for electrical energy production and storage in fuel cells and batteries respectively).
2. ELECTROCHEMICAL PROCESSES FOR EFFLUENTS AND WASTE TREATMENT
Electrochemistry, dealing with oxidation or reduction of compounds at well-controlled electrode potentials by adding (at the anode) or withdrawing (at the cathode) electrons, offers many interesting possibilities in environmental engineering. Anode processes can be used to oxidize organic Cathodic
pollutants to harmless products and to remove toxic compounds from flue gases.
In both types of electrode processes. New electrodialytic processes using such membranes have been developed. The upper limit is set by the stability of the anode material and the onset
of side reactions such as oxygen evolution or chlorine evolution in chloride solutions. titanium exhibits better activity but is expensive. This The
than the efficiency observed on a Pt anode. evolution reaction.1. which was five times higher No interference with the cathode was found. Similar results were obtained for the
The efficiency was ~30-40%. oxidative treatment of waste water11. Therefore.
electrolysis processes do not provide high oxygen overpotentials.
the electrochemical cell can be used in purification processes.
Anodic Oxidation of Toxic Species
It is essential to set high electrode potentials to achieve oxidation of toxic compounds at the anode of an electrochemical cell. which lower the current efficiency. but also the ion-selective membrane(s) that are often placed between the electrodes can help in selective transfer of anions or cations. the anode material must have a high overpotential for oxygen For example.
indicates irreversible oxidation to reaction products that cannot be reduced at the cathode.
2. lead dioxide posses this property and extensively used in Dimensionally stable anodes used in chlor-alkali plants or in water In this context. which can be useful for a variety of environmental problems.
oxidations at high potentials.
reaction phenol oxidation was carried out on these three electrodes and it was found that the rate of phenol removal was higher at SnO2 than at PbO2 and Pt.
Doped SnO2 – coated Ti electrodes were As a test
developed10 exhibiting significantly higher oxygen overpotentials than both PbO2 and Pt. the operating conditions must be Not only the two electrodes of
carefully chosen and controlled in order to avoid the side reactions.processes using effective cell designs can remove heavy metal ions from wastewater solutions down to very low concentrations.
A special case of indirect oxidation frequently called mediated electrochemical oxidation (MEO) is the use of metal ions with high oxidation potential (e. hypochlorite. S[OH] + H2O = S[ ] + O2 + 3H+ + 3e(3)
Phenol and derivatives are the most studied examples. which could be further oxidized to CO2 as well as with small amounts of CO.
Main intermediates are found to be
benzoquinone. Ag (II) and Co (III)) which can be electrochemically generated in a closed cycle. Fenton’s reagent. ozone. chlorophenols. Different anodic
. A voltammetric study at a platinum rotating ring disk electrode with phenols. diminishing the current efficiency. peroxide.attempts for electrochemical treatment of wastewater or wastes can be sub-divided into two categories: (1) Direct oxidation at the anode and (2) Indirect oxidation using appropriate anodically formed oxidants (Cl2.. Direct Oxidation at the Anode For the direct oxidation two properties of anode are prerequisites for its suitability: high oxygen overpotential and stability towards corrosion. maleic acid and hydroxy diphenyls. organic acids and a surfactant (fluorinated octanic acid) was carried out by Huang et al13.1.g. molecule assume the following major steps:12 Step I: Discharge of water with the formation of an adsorbed hydroxyl moiety S[ ] + H2O = S[OH] + H+ + e(1) The process of anodic oxidation of an organic
Step II: The adsorbed OH in an ‘active state’ participate in O-transfer reaction to the organic molecule R.1. peroxodisulphate). 2. S[OH] + R = S[ ] + RO + H+ + e(2)
Step III: Oxygen evolution as side parallel process by oxidation of water.
is oxidized anodically and this approach is economically feasible at higher concentrations of cyanide (>1 g dm-3). PbO2 and SnO215 and Bi as well as Fe doped PbO212 were also employed. These radicals are adsorbed on the electrode surface and react on SnO2 anode with phenol to Aromatic intermediates were formed in small The rate of phenol
CO2 or react with oxygen in a side reaction.
It is known that in electroplating and surface finishing industry one still use large amount of cyanide to obtain very finely grained metal deposits. Ni.
removal is almost the same for both anodes.
Comninellis and Pulgarin15a studied oxidation of phenol using Pt and SnO2 anodes and proposed a reaction scheme that involves the initial formation of hydroxyl radicals by the electrooxidation of water. while they were formed in large concentrations on Pt. graphite or stainless steel) is:
CN. while Ti/SnO2 anode showed higher rate of total organic carbon (TOC) removal.+ 2 OH-
CNO. Therefore.+ H2O + 2e-
. The main products were CO2 and the side products were benzoquinone and maleic acid. glassy carbon and titanium supported oxide electrodes such as IrO2. RuO2. most of the metal ions may simultaneously deposit with hydrogen The overall reaction at the anode (generally used anodic materials are
evolution as side reaction. a complete oxidation of phenol was achieved. the wastewater must be treated with
In conventional chemical method.17. At the cathode. By using a packed cell a high rate was achieved with PbO2 anodes16. For phenol
concentrations >>1 mM fouling of the noble metal anode was observed by films of polymeric material. respect to its cyanide content. At optimum pH
and temperature conditions. hypochlorite is used as an In electrochemical process. cyanide
oxidizing agent to oxidize the cyanide to less harmful cyanate.
concentrations on SnO2.materials like Pt14 as reference.
chlorine is substituted by this hydroxyl radical. chlorinated phenols from bleaching in the pulp and paper industry.
is an alternative. using specific microorganisms or enzymes are under development. In the first step.
process economy NaCl was added to the electrolyte so that chlorine is formed at the anode. Other
treatment options include membrane separation. showing the similarity in the mechanism in both cases involving hydroxyl radical formed from water. the energy demand is 10 – 40 kWh kg-1 cyanide at the The remaining cyanide at low concentrations at the outlet To achieve lower residual concentrations and a better The
reaction temperature 232 – 363 K.
They may also appear as products
in chemical reactions between chlorine and dissolved hydrocarbons in various waste streams. because of high cost of transportation.
Chlorinated hydrocarbons are used as solvents and disinfectants. e. Chemical reduction methods such as catalytic Biological techniques
dehalogenation with hydrogen or other reducing agents are also employed.Cyanate further reacts in alkaline solution to form Na2CO3. the high consumption of fuel and in some cases. The decomposition of p-chlorophenol follow concentration – time curves that are
similar to those of phenol. chemical oxidation with air. which could be employed either anodically or cathodically. adsorption on activated carbon and stripping. In
subsequent steps.17b showed that p-chlorophenol and pentachlorophenol could be destroyed anodically on PbO2 anodes. Combustion is a frequently used
destruction method but is not suitable for the treatment of dilute wastewaters. N2 and NH3. oxalic acid and CO2.
efficiency of the direct electrooxidation process can be improved by using three-dimensional electrodes. further oxidation yields quinone.
Wabner et al. corrosion problems.g. There is a risk that the chlorine
. which decomposes into maleic acid. reaction. The side products formed at the anode are O2 and O3.
O2 evolution is a side
The current density 500 A/m2.
stream has to be oxidized by hypochlorite. which will be discussed subsequently. ozone or other oxidants..
thiocyanate20 and sodium dithionate24. phenols. Ir. cyanide23. was examined. Pd. studied on several electrodes22. the products were sulphate and dithionate. In the presence of chloride.
Ammon21 have carried out kinetic study for the direct oxidation of SO2 in solution using Pt. dyes and aromatics19. The suitability of various anodic materials for the oxidation of phenols
For the intermediates (especially aliphatic species) the anodes are however. Rh. Direct oxidation of SO2 as a tool for flue gas treatment was At graphite electrodes. Numerous
A continuous neutralization of generated acid is a necessity in these processes. The oxidation of azodyes leads to the formation of CO2.
fundamental investigations have been carried out for the anodic treatment of aqueous effluents containing inorganic pollutants. Re and Au.g.
Other substrates that have been researched for direct anodic oxidation includes: sugars. A major
. aliphatic carboxylic acids. Reasonable current efficiencies were achieved using Pt/Ir coated Ti electrode for sulphite to sulphate oxidation in an undivided cell20. alcohols distillery effluents. effective. e.
the anodic oxidation of aromatic and aliphatic compounds using batch and flow electrolysis in divided and undivided cells.ions formed may be oxidized to hypochlorite. whilst RuOX – TiO2 / Ti and IrOX – TiO2 / Ti were inactive. the oxidation Scott20 investigated
of azodyes takes place primarily through the formation of “active chlorine”19. The electrochemical treatment may also be extended for dechlorination of other chlorinated aromatic compounds in aqueous solutions such as hexachlorobenzene. An interesting alternative is to
use the dechlorination step only and decompose the less toxic phenolic substances biologically. It was found from using DSA that PdOX/Ti showed the highest catalytic
activity in these experiments. less Lu and
Graphite and SnO2 anodes are suitable for the oxidation of formic acid. which can then form chlorinated organic compounds with low molecular mass species formed in the reaction sequence. Ru. parachlorobenzene (PCB)18 and tetrachlorodibenzodioxin. cyclic and aliphatic hydrocarbons and aromatic amines.
N2 and Na2SO4 apart from the formation of aromatic esters.
converted to CO2 and H2O by oxidation with air.
which is separated from the anodic chamber by means of a cationic selective membrane. peroxidisulphate and ozone. Some AgII might oxidize the organic compounds directly in the anolyte. which is reoxidized to nitric acid by air in a separate reactor.1.
It is known that dilute alkaline cyanide solutions can be oxidized homogeneously by anodically formed ClO-.842 and 0. Comninellis studied the electrochemically generated Mn
(III) in sulphuric acid28. Water is recycled to the anodic chamber to replace the water The net effect is that dissolved organics are This technique is employed successfully to
loss by electro-osmosis through the membrane. phenols. For example. including benzene.987. AgNO3+. nitric acid is reduced to nitrous acid. ClO. The reduction of nitric acid followed Vetter mechanism26 to form NO.problem for the oxidation of SO2 is to avoid the formation of elemental sulfur at the cathode. Scotland19 developed a process using AgII. 2.2.
destroy a variety of organic compounds. which then react with organics. higher is the columbic efficiency. Ebonex® was tested as cathode material for these experiments20. Indirect / Mediated Electrochemical Oxidation In this process.77 V respectively. but it has the disadvantage that it forms toxic chlorinated Other examples include peroxide. AgII is probably stabilized in the solution as a nitrate complex. which can be regenerated back to nitric acid by the oxidative absorption in columns27.
AgI is anodically
oxidized to AgII on platinized titanium in concentrated nitric acid in a membrane divided cell. chlorine or hypochlorite. In cathodic chamber. Fenton’s reagent25. compounds. CoIII and FeIII were also used and the The higher the redox
standard potentials vs. 1.is an efficient oxidant. which leads to the formation of aldehydes in counter current columns and complete oxidation of NO to HNO3.
AEA technology in Dounreay. Mediators of types AgII. the oxidant is electrochemically generated. SHE are 1. potential. cylindrical fluoro-carbon-impregnated carbon anodes were used for ozone generation in a solid polymer electrolyte cell19. oils and chlorinated organic
The use of metal ions with high oxidation potential like Ag (II) and Co (III) can This technique was originally employed in Ag (II) was found to be
completely oxidize the organic compounds to CO2.1. under favorable flow conditions high current densities of more than 5 kA m-2 could be obtained. and this experience initiated the treatment of mixed radioactive wastes (e. For total oxidation. Ag (II) / Ag (I) and Fe (III) / Fe (II)]. This is enriched in the anolyte and can be
separated from time to time by cooling as potassium perchlorate35. where for the first time intermediates and mechanism for the oxidation of phenol and chlorinated phenols were examined.488 cm2 sec–1 (β = Diffusion coefficient).
the most efficient oxidant for this purpose. Removal of Heavy Metal Ions
nuclear industry to dissolve refractory plutonium dioxide in nitric acid30.
(II) system.compounds. at AEA Dounreay32 and at Forscungszentrum Karlsruhe33.
2. The kinetics of the oxidation of water by the Degradation of chlorinated organic
mediator as a function of temperature was carried out34.g.
Reports on the studies on Co (III) generation showed that anodic oxidation of water and Co (III) formation are probably simultaneous reactions. The formation kinetics of the oxidizing state of the mediators was investigated by the The formation of Ag (II) is mainly diffusion For the Ag
rotating disk electrode (RDE) experiments34. solvent of the purex process) at Savanah River Laboratory31.2.2. only redox
couples with a high oxidation potential are suitable [Co (III) / Co (II). which are redissolved in excess of Ag (II) by oxidation of chloride to perchlorate. and this method was applied for a plurality of hazardous wastes.
controlled with an average value for β of 0. tributyl phosphate.
compounds leads to the intermediate precipitations of silver chloride.
Cathodic removal of heavy metal ions from different wastewater is an attractive alternative process. graphite felt. 1.
Most three-dimensional electrodes used for metal removal are of fixed bed type. printed circuit board production or battery technology. graphite fibers and reticulated vitreous carbon. which gives a voluminous metal hydroxide sludge that has to be disposed off in an environmentally acceptable way. operation at the
limiting current density across the whole depth of the electrode would give a high hydrogen
. The efficient electrochemical engineering
approach is to employ the packed bed electrode or more generally. expanded metal. extent of the side reactions such as hydrogen evolution36. unless the mass transfer rate could be substantially improved.
If the bed is too thick. metal wool. hydroxide precipitation is not a viable method. complexed metal ions in alkaline solutions. since the potential drop in the dilute This determines the
electrolyte is along the depth of the electrode in the direction of current flow. photo development processes. electroplating. The engineering aspect is of importance. A possible
solution to this problem is to use a rotating cylinder cathode or use expanded metal mesh electrodes immersed in a fludized bed of small glass beads. also be a three-dimensional electrode or just a planar electrode.Waste water containing heavy metal ions generated in metallurgical.
The anode may
The cathodic materials employed
are graphite particle. The conventional
purification of these streams uses hydroxide precipitation. three-dimensional electrodes as shown in Fig. The
basic problem is that the mass transport controlled limiting current density for cathodic metal deposition from dilute solution is so low that the conventional use of planar electrodes would require too large a surface. since the metal can be recovered in the pure metallic form or as a concentrated solution that can be recycled or the extraction of the pure metal in an electrowinning process may be possible. requires special treatment to remove toxic metal ions or recycling of valuable materials.
In electrodes of this type.
not possible to decrease the concentration of these species below 1 ppm in an acceptable overall current efficiency. the metal deposited during the preceding cathodic phase is dissolved
into a concentrated solution. particularly at lower concentrations. concentrator. Three-dimensional electrodes are effective in the treatment of dilute solutions since they offer both a high specific surface area and high mass transport rate conditions. This method requires robust anion – selective membranes to prevent leakage of metal ions from the concentrated anolyte solution to the dilute catholyte solution. the side reaction of hydrogen evolution Therefore it is
predominates and the current efficiency is low. For less noble metals such as Zn and Cd. and the space required by the process is
The deposited metal in the cathode may be recovered as a concentrated solution by chemical dissolution or by switching the polarity of the cell.evolution rate in the part of the bed facing the membrane or diaphragm. which has generated the waste solution. Outlet concentrations of less than 1 ppm can be achieved. Operational costs are favorable compared with the classical wastewater treatment In some cases. The energy consumption is of the order of 1 kWh-1. the cell will function as a
At the anode. 100 to 0. also low. An alternative regeneration procedure is to use three-dimensional electrodes made of foamed graphite or carbon felt to recover the deposited metal in an external procedure according to the principles of electro-refining. the metal concentration can be reduced from say. so that the metal precipitates as hydroxide. Processes utilizing packed–bed electrodes have been employed in the chemical industry mainly for waste solutions containing Cu and Hg38. A further complication is that excessive cathodic hydrogen evolution may This phenomenon can be used to
increase the pH.
. the removal efficiency is higher. A
better approach would be the concentrated metal ion solution could be recycled to the process. systems. In the latter case. remove Cr (VI) as Cr (OH)3. which separates the cathode from the anode.1 ppm at a residence time of few minutes37.
2. The electrode materials employed were graphite/carbon fiber
A reasonably a high over potential for competing hydrogen evolution
reaction was achieved and there was a complete removal of chlorine from organic molecules in aqueous solution. with high surface area. Electrochemical Dechlorination Schmal et al. The dehalogenation results in a decreased toxicity and an increased The energy consumption and The dechlorination of
biodegradability.2.⇔ Me (6) The removal of metal ions Mez+from wastewater is based on the cathodic metal
From a thermodynamic point of view.
organic toxicants can occur not only anodically but also cathodically according to the overall reaction: RCl + H+ + 2e↔ RH + Cl(5)
Electrochemical reduction can be used with polar compounds and does not give a concentrated toxic waste that has to be treated further or dumped in special depots.2. some of which are already commercialized and being used now in the industry41-44.2. deposition: Mez+sol + ze. thus enabling further biological treatment. trichloroethane.2. Cathodic destruction of
monochloroethane. the Nernst equation predicts that it should be possible to decrease the Mez+ concentration in solution to an arbitrarily low level. if the
. Optimization of cell design
Most of the metal ions were removed by cathodic deposition.
conversion rates of this process are technically and economically viable. epichlorohydrin and of aromatic halides40 has also been demonstrated.3. Electrochemical processes have been developed.39 studied the feasibility of electrochemical reduction of wastewaters containing halogenated organic compounds.
05 ppm is no
longer economical due to increasing electrolysis time and unacceptable space-time yield. the specific energy demand for an electrochemical wastewater purification process is generally quite low. the rate of the mass transport controlled process strongly decreases. electrolysis at concentrations below 0. typically in the order of 0. A the actual electrode area. Another important point for consideration is that the specific For
the cathodic metal deposition in an electrochemical reactor of volume V. In practice. I = il:
. the space-time yield is defined as the amount of metal dm (in grams of current units) deposited in a time interval dt: l dm ρ = __ __ V dt According to Faraday's law. at extremely low concentrations. and M the molecular weight of the metal deposited.05 M. The optimal process conditions are met when the rate of the (9) (8)
heterogeneous reaction attains its maximum at the limiting diffusion current density. Since the current densities at low metal ion concentrations are small.potential E of the Me/Mez+ electrode is maintained sufficiently negative with respect to the standard potential E°Me/Mez+: cMez+ = c+exp [zF/ RT] (E .E°Me/Mez+) (7)
However. Aφci dt: M dm = Aφci dt __ zF Where φc is the current efficiency. dm is proportional to the electrolysis charge. which are inversely proportional to the space-time yield of the reactor.
high specific electrode area ae and/or large mass transport coefficient km.cMez+ il = .e.zFDMez+ ____ δ Where DMez+ is the diffusion coefficient. Therefore.time yields.
designs have been directed towards optimizing of the space-time yield ρ according to the key formula (Eq.
.1 ci) within 1 s in a reactor volume of 1 cm3. Kreysa46.time yield can be expressed as: ρ = φcMackmcMez+ (11) On replacing the current density i in Eq. i.47 introduced the definition of a normalized space velocity ρsn for the characterization of the reactor performance for a given degree of conversion: Iφc ci (12)
ρsn = ____________ log __ (ci . and km = D/δ is the mass transport coefficient. δ the Nernst diffusion layer thickness.ce)VzF ce
This figure gives the volume of wastewater in cm3 treated by reducing the inlet concentration ci by a factor of 10 (ce = 0. The reactor performance is not independent of the properties of wastewater. (9) by il the = . space . For a given metal ion concentration cMez+ a high
mass transfer coefficient km and a large specific electrode area ac = A/V are essential to obtain high space .zFkmcMez+ (10)
This is the key formula for the design and construction of an electrochemical reactor for wastewater treatment and metal recovery.
Different types of cell constructions have been designed in the recent years. 11).
the RETEC cell61. the packed-bed cell62-64 the fluidized bed cell65-69 and the rolling tube cell70. Examples are the Porous flow-through cell60.
Anion selective membranes.
. can be used in cells with threedimensional electrodes for metal deposition.With respect to these criteria. The design of the three-dimensional electrodes originates from the fact that in contrast to the planner configuration the electrode area is distributed throughout all three dimensions. but with a relatively small electrode area in a given cell volume. This has resulted in
the developments such as the Multiple-cathode cell57. the electrochemical cells may be classified in the following three groups. Examples are the Pump cell48. 2. • Cells to accommodate large electrode area in a small cell volume. the ECO cell51-55. which allow only anions to pass. Acid can be recovered from spent pickling In
baths by using anion-selective membranes with oxygen evolution at a suitable anode. • Cells with improved mass transfer coefficients and enlarged specific electrode area by the use of three-dimensional electrodes.55 and cells with vibrating electrodes or electrolytes56. the Beat rod cell54. this arrangement provides not only a large specific electrode area but also large values for the mass transport coefficient.71. The pictorial representations and discussions on the diagram and
operation of various types of cells are presented elsewhere9. • Cells with improved mass transport and thus increased current density by setting the electrodes in motion or by applying turbulence promoters. Due to
the specific fluid dynamic conditions inside such a three-dimensional bed electrode. the Chemelec
cell50. the Swiss-role58 or the ESE (extended surface electrolysis) cells59.3.
(2) to form tight surface layers on the anion exchange membranes. the membranes carryout the main part of the work by splitting the inlet flow into one more concentrated and no more dilute stream. (4) to impregnate hydrophilic compounds in the anion exchange membranes to increase hydrophilicity of the membranes.
Cation exchange membranes introduced commercially in the membrane cells for chlor-alkali production can also be used in electrochemical processes for environmental protection. fermentation and rayon manufacture. (3) to decrease hydrophilicity of the anion exchange membranes or their surfaces by introducing specific anion exchange groups in the membranes. metal pickling. Electrodialysis has since been used for salt or brine production and in desalination processes for obtaining fresh water. Permselectivity
of specific anions through the anion exchange membranes is governed mainly by the balance of hydration energy of anions with hydrophilicity of the membranes. It can be combined with the process of electrolysis for
Aqueous streams containing NaCl and Na2SO4 are generated in many chemical-processing operations such as flue gas scrubbing. desalinating water streams. except the membranes having an oppositely charged layer on the membrane surface. Large volumes of highly concentrated sodium salts resulting from neutralization of acidic or
. The studies are classified as: (1) to increase cross-
linkage of the anion exchange membranes. (5) to control permselectivity of anions by photoirradiation using membranes with a photoresponsive group and (6) to control permselectivity of anions through thermally responsive anion exchange membranes with temperature. partially by hydrated ionic size of the anions. Recent studies on anion
exchange membranes and electrodialysis methods to permeate specific anions through the membranes are reviewed by Sata72.electrodialytic processes.
reaction is accompanied by a positive change of the enthalpy.alkaline solutions are economic motivations to reinforce the demand for zero effluent technology3. Such a membrane can
. such a process can only be realized by an electrochemical route. in this case a pure sulfuric acid solution is not obtained as in the threecompartment cell. In such a cell. An example is the electrolytic splitting of sodium
sulfate solutions into sodium hydroxide and sulfuric acid solutions in a three-compartment cell with cation or anion exchange membranes. which are obtained from the dissociation of water. Protons H+ and hydroxyl ions are produced during oxygen and hydrogen evolution at the anode and cathode of the cell as shown in Fig. This concept can also be used in a
exchange membranes. as shown in Fig. a hydrogen gas diffusion electrode of the type used in fuel cells on the anode side and utilizing the hydrogen evolved at the cathode.ions. hydroxyl concentrations of ~ 10 mass% can be achieved. there is an increasing interest in technologies to recover the Since the reversal of the neutralization
sodium salts back to sodium hydroxide and acid. an anion selective region and the interface between the two regions. and a very thin interface between anion and cation regions to allow efficient transport of H+ and OH-. When a direct current is passed through the
bipolar membrane with the cation selective side toward the cathode. As a result. The energy requirement can be reduced by using instead of the oxygen-
evolving anode. which consist of three parts: a cation selective region. electrical conduction is achieved by the transport of H+ and OH. 2. two-chamber process73. 3. The energy consumption is 1600 – 1800 kWh tonne-1 caustic at a Energy savings may also be achieved by using bipolar ion
concentration of 13-18%. A high efficiency requires that the membrane have a high water permeability to
provide water from the external solutions to the interface. The cell
voltage and thus the energy demand are to a great extent determined by the anode and cathode potentials.
The ion exchanger materials are continuously regenerated electrochemically by The
H+ and OH. protons and hydroxyl ions are generated by electrolysis and pass the ion exchanger membranes for continuous regeneration of the resin beds. 4. concentration and recovery
of metal ions from solutions.
major application of this technology is the production of ultra-pure water and the removal and recovery of heavy metals and precious metal ions from industrial effluents. which are released into the central chamber of the concentrate.g: CuCl2 recovery (See Fig.ions that are produced by water splitting in an applied electrical DC field. The process
. which can be constructed as a compact stack.
The feed solution was passed through separate beds of cation and an anion exchanger. works with a current efficiency of 30%.b.
power consumption and increases the available surface area of conventional electrodialysis processes. This approach significantly reduces stack resistance.
This technique may be used to produce sodium hydroxide without the simultaneous generation of chlorine. The energy requirement for producing sodium
hydroxide is in the range 1300 . This energy demand is lower than that of the conventional chlor-alkali processes.
The ion pure
(Millipore) and the electrodiaresis (Euva) concept are employed for de-ionisation of pure water76a. replacing the Cu2+ and Cl.be combined with anion and cation selective membranes into three-compartment units. e. for typical representation).
Ganzi et al75 employed three different concepts in their technology. Gutbealet et al74 described the combinations of ion exchange membranes and conventional ion exchanger resins for the treatment of water and processed solutions with continuous regeneration of the ion exchanger.ions. The third concept was directed towards the separation.2000 KWh tonne-1 at 1000 m-2 and a current efficiency of 80%. Under applied electrical field.
technology is associated with the emission of mercury into the air and mercury . The low height of the electrolyzer avoids The progress in decreasing the
gas accumulation and contributes to further energy savings.
specific energy consumption for chloralkali electrolysis by the invention of this new process is depicted in Fig. diffusion and convection. If heavy metal ions are present in the ground water they will move to the cathode This method is not restricted to ionic
and become electrodeposited on its surface. Such membrane cell
technology has been commercialized by AZEC in Japan.The conventional process for chlor alkali electrolysis is the amalgam process77. The main electrode reactions are generally oxygen evolution at the anode and
hydrogen evolution at the cathode as shown below.→ H2 + 2OH-
As in ordinary electrolysis.
. which is a plate and frame cell block only 40 cm in height and up to 2 m wide. which is characterized by electrodes pressed directly onto the diaphragm in order to minimize the IR drop caused by the gas evolution. H2O → ½ O2 + 2H+ + 2e(13) (14)
2H2O + 2e. The ground water or an externally supplied fluid is
used as electrolyte. as shown in Fig 6.
2. 5. Another interesting improvement to the process has been achieved by ICI with the FM21 electrolyzer.4
Electrochemical Remediation of Soils
There is a great need for cost-effective methods for restoration of contaminated soils.
zero gap cell concept.
of electrochemistry for this purpose simply means putting electrodes in the soil and applying a voltage over them.containing wastewaters. movement of ions will due to migration. With the development of fluorinated ion exchanger membranes a new process This new technology employ the
became available which represents a cleaner technology. Acar and Alshawabkeh79a and Probstein and Hicks79b reviewed this technique.
acid front will thus move from the anode towards the cathode. mass transfer by migration will generally be higher
This technique can be employed in situ. the cations migrating towards the cathode. while an alkali front moves in the opposite direction. e. Without
external control of the chemistry of the system. The alkaline front causes precipitation of most heavy metals and radionuclides. For example.osmosis. according to equations (13) and (14). Thus. which
will make the pore liquid flow preferentially through the larger pores. when they meet the acid front. in contrast to forced convection by means of pumping.
unless they form negatively charged complexes. These problems may be solved by means of pumping solutions. These complexes migrate towards the anode and will form free metal ions again. For ions. This also allows for a control of the chemical conditions. These reactions will make the anode region acidic and the cathode region basic. species
are concentrated in the region where the two pH-fronts meet and pH changes abruptly. than that by electro.g. The penetrating acid solution will release heavy metals and other
cations that are sorbed on negatively charged clay surfaces.contaminants but can also be used to extract organic compounds by means of the electro osmotic flow that is generated by the electric field in fine-grained soils with pores that are of micro-size or smaller.: by ion exchange or chemical precipitation.
. the electrode reactions are generally oxygen evolution at the anode and hydrogen evolution at the cathode. In this fashion. the hydroxide
precipitation at some distance from the cathode may be avoided by adding an acid solution to the cathode region. on-site and off-site the flow around the electrodes and through the soils can be controlled so that the contaminating species in the fluid may be removed either at the electrode or in an external extraction system. electro-osmotic flow will be effective in smaller pores.
+ 2H+ + 3eSO42.7.142 V E°= 0.+ 4H+ + 3eNO3. Many gaseous
pollutants such as chlorine.775 V E°= 0.138 V (15) (16) (17) (18) (19)
NO + 2H2O ⇔ NO2 + H2O ⇔ SO2 + 2H2O ⇔
Different concepts of electrochemical gas purification have been well discussed in literatures80. provided that they are first dissolved into an electrolyte.360 V E° = 0.+ 4H+ +2eE° = 1. heating combustion units or chemical plants requires the development of new concepts of electrochemical gas purification techniques. The overall process will then generally consist of two steps: absorption of the
gaseous species in a liquid and the subsequent electrochemical conversion of them to less harmful products.
. since the physical absorption process will not be limited by the equilibrium solubility of the absorbed gaseous pollutant.
may also be removed electrochemically.957 V E°= 0. especially
for smaller scale power plants. An increasing demand for off-gas purification. since the standard potential of the corresponding reactions are all within the stability range of aqueous electrolytes: 2Cl H2S ⇔ ⇔ Cl2 + 2eS + 2H+ + 2eNO3. hydrogen sulfide. nitrous oxides or sulfur dioxide permit electrochemical conversion in an aqueous environment.5
Electrochemical Gas Purification
The processes discussed deal with pollutants present in aqueous solutions. Estimated costs for the technique79b indicate that they may be several times lower than that involved in conventional methods.Electro kinetic remediation has been tested successfully in field studies in Netherlands and in USA.
2. The two steps can be integrated into one device or are separated in two The rate and capacity of absorption will be
different devices80 as represented in Fig.
advantage of heterogeneous mediators.
Indirect. step is absorption of the pollutant species into a liquid phase.
The schematic design of such a device. is directly converted at the surface of the packed bed electrode. electrochemical processes with homogeneous redox mediator are the so-called `peracidox' process developed by Furgi 83 using peroxodisulphate as the redox mediator for SO2
. In any case. 8. The dissolved pollutant
Such a construction exhibits
high a space-time yield end has been successfully employed for electrochemical absorption of sulfur dioxide and chlorine81b. such as oxides.
Direct electrochemical conversion of gases by an inner cell process can be carried out in a specially designed electrochemical absorption column. the transfer from the gas phase into the solution phase must be supported by a reaction. the mediator has to be generated electrochemically. which consists of a three-dimensional packed bed electrode of conducting particles in contact with a cylindrical feeder electrode and a counter electrode separated by a porous diaphragm or ion exchanger membrane81. Both the electrochemical conversion of the
pollutant and the electrochemical regeneration of the redox mediator can be achieved either by inner cell or an outer cell processes as illustrated in Fig. Homogeneous and heterogeneous catalysts were employed as redox mediators.The reduction or oxidation may occur directly at the electrode or indirectly through a redox mediator. which usually operates under counter current flow conditions of the gas and the liquid phases is shown in Fig. the initial
Since the solubility of several
gases in aqueous-solutions is small. is that a separation of the reaction products from the mediator is not necessary. which converts the primarily dissolved species permanently to a more soluble one.
(in both cases. which migrates
to the anode. and the modified `Mark 13 A' process developed at the joint European Research Center Ispra.86a employed a copper catalyzed (Cu2O / Cu42+) process for Iliev et al.84 using bromine as a mediator for the indirect oxidation of SO2.
gas diffusion electrodes for the conversion of SO2 using pyrolized phthalocyanines as electrocatalyst. reactions are depicted in Fig 9. the electrochemical regeneration of the redox mediator is performed by an outer cell process in a separate electrochemical cell. The process scheme and the
porous electrodes and a molten Na2S-Li2S electrolyte at 623 K has been examined for removal of SO2 and H2S87. Since flue gases not only contain SO2 but also NOx the simultaneous removal of both components is the subject of recent investigations89. At the cathode SO2 is reacted with oxygen to sulfate ion. where it is oxidized to SO3 and O2. In an indirect outer cell process that
employs Ce4+as homogeneous redox mediator the simultaneous oxidation of SO2 and NOx to sulphuric acid and nitric acid respectively has been released. NO is reduced to N2 and CH4 is oxidized to COx. SO2 + O2 + 2e→ SO42(22)
High temperature solid state electrochemical cells based on yettria stabilized zirconium dioxide YSZ and porous palladium electrodes have been studied by Hibino88 for the electrochemical removal of both NO and CH4 at 923-1023 K in an oxidizing atmosphere. Electrode technology borrowed from the fuel cell technology has also been used for A cell construction similar to that of a molten carbonate fuel cell with
effluent gas treatment.oxidation. Kreysa et al.86b employed porous
the combined electrochemical and catalytic removal of SO2. SO2 + Br2 + 2H2O 2HBr → → H2SO4 + 2HBr Br2 + H2 (20) (21)
Strafelda and Krofta85 suggested PbO2 as a heterogeneous redox mediator to catalyze the oxidation of SO2.
amidosulphonic acid and SO32-. addition of Fe (II) EDTA at the partial pressure NO at the outlet is drastically decreased and remains at lower level as long as dithionate is present in solution. The products were
The formation of N2 was negligibly small. first enters an absorption column.
Non-faradaic electrochemical modification of catalytic activity (NEMCA) was described for over 60 catalytic systems92. where it oxidized directly to sulphuric acid at the anode. SO2.
the solution reaches a critical concentration of 30 – 40% HNO3 and H2SO4. where NO is absorbed
by the complex forming agent Fe (II) EDTA and simultaneously reduced with dithionite.b.in an electrochemical cell. It includes the significant increase in the catalytic activity and
selectivity of metal and metal oxide catalyst deposited on solid electrolytes such as Y2O3 -
. The second compound. separation of the nitrate effluent from the sulfate solution and recycling of Ce3+ are performed in a separate unit.
Lead dioxide dithionate process. Micro-kinetic studies of NOx absorption revealed that the degree
of NO conversion can be improved at the low content of Fe (II) EDTA in absorption solution. where Ce4+ is regenerated. in which HNO3 is first separated by distillation and the excess H2SO4 is then continuously removed by liquid / liquid extraction technique90.d which combines direct and indirect conversion of SO2 and NOx respectively in two steps with dithionate as homogeneous redox mediator for the indirect reduction of NOx and lead dioxide as heterogeneous catalyst and mediator for the direct oxidation of SO2.
optimization of this process requires further investigations on the complex chemistry of NOx74. The gas mixture.91a.The acidic. passes through the NO absorption
column without reaction and enters an electrochemical cell. The redox mediator dithionate is continuously regenerated by cathodic reduction of SO32. Since. NH4+.89c. solution is continuously fed down to the anode. S2O42.
World energy consumption is increasing enormously as
3. the use of
coal may be secure and relatively inexpensive but is not environmentally acceptable.stabilized ZrO2 (YSZ) or β" . namely security of supply as well as minimal environmental effects. mainly because of the growing demand for energy in developing countries as they attempt to improve their living standards. period are given in Table 2
The data on world energy consumption for this
.thermal generators does satisfy two of the It is
requirements. It is hard to meet all these requirements at the same time. A positive
influence of NEMCA on the catalytic reduction of NO by C3H6 in the presence of O2 leading to the formation of CO2 and N2 has been recently reported93. For instance. Electricity from non.Al2O3 by electrochemical polarization of the catalyst electrode. If the growth of world population continuous at
ELECTROCHEMICAL POWER SOURCES
The development that has been made on energy sector during the last two decades indicates that it is actually a transition time for improving strategies regarding energy production. coal and natural gas are limited has led to a growth of scientific efforts to find alternative energy sources which have one following basic attributes: (1) The energy should be inexpensive as possible. storage and conversion. The rate of the catalytic reaction is typically increased by a factor of 5-100. it will be difficult to deliver energy equitably at the present consumption levels of the developed nations as well as to satisfy the needs of the developing countries.
. The demand for the usage of fossil fuels like coal. (2) a secured supply should be ensured. (3) its use should lead to minimum environmental pollution.
The fact that the resources such as oil. and (4) it should be socially acceptable. The population figures for the period between 1989 and 1998 are given in Table 1. Synthetic fuels produced from coal may also prove to be environmentally incompatible and at the same time expensive. oil and natural gas is
increasing day by day due to the increase in population.
Adopting electrochemical methods is one of the ways of ensuring pollution free operation94b.1
An electrochemical capacitor stores the electrical energy electrostatically by charging of the electrochemical double layer at the electrode/electrolyte interface. transport. The effects of various pollutants on human health are outlined in Table 4. fusion. which multiply health hazards. chemical engineers have a key role to
power losses in transmission. met at least partially through electricity. which are most harmful to health. In some systems
intermediates are absorbed on the electrode surface or intercalated into the electrode material. ocean thermal gradients and wave power can be used to produce electricity. to find.
play in the energy conversion processes. 10). like non-renewability.
Today we are using fossil fuels as energy sources. refine and consume.
more of any of these pollutants gives rise to secondary pollutants (Fig. The principal pollutants derived from fossil-fuel consumption.known that all other energy sources like fission.
3. are listed in Table 3. uneven distribution around the globe and problems of environmental pollution. one has to incur transmission expenses and the concurrent Storage of electricity as chemical energy is more convenient This is why chemists. But they have
should be pointed out that storage of electricity is expensive and it has to be produced when and where it is required. photovoltaic. Otherwise. because these are readily available and relatively convenient to use i. Air quality has been deteriorating rapidly over the years resulting in health hazards. and comparatively inexpensive. Similarly. all energy requirements can be
In spite of these advantages of electrical energy. This table also shows the sources and types of The combination of two or
pollutants including the extent of emissions in a particular year.
5 W h kg-1 and deliver 1kW kg-1. and metal oxides as electrode materials.
50% of the total emissions of nitrogen oxides. Ultra capacitors in aqueous
electrolyte can store 1.4 kW kg-1 in the near future96. organic or a solid polymer. carbon monoxide and hydrocarbons. are electrochemical energy systems / devices in which chemical energy is directly converted to electrical energy. The electrolyte may be aqueous. Approximately 20% of the primary energy Road traffic alone generates more than The
used in the European Union goes to transportation.
3. With increasing energy density the possibility
increases of using only electrochemical capacitors as storage device for electrical energy in hybrid electric vehicles. or complement to batteries is electrochemical capacitor (also known as ultra capacitors or super capacitors).
An interesting alternative.2
Batteries for Electric Vehicles
Batteries or galvanic cells.
Research and development is going on since the early 1990s to develop ultra capacitors using various types of carbon doped conducting polymers.which gives an additional so called pseudo-capacitance that may be 10 to 100 times higher than the double layer capacitance95. have enacted a law that requires that 10% of all new
authorities in California. while the best values reported for devices using an organic electrolyte are 5-7 Wh kg-1 and 2 kWkg-1. where the transportation fleet is responsible for more than 75% of the air pollution in the Los Angels basin.
fairly high amounts of electrical energy may be stored per unit volume or mass. In a finely porous electrode with a high specific surface area. Further development is
expected to result in ultra capacitors with an energy density of 10-15 W h kg-1 and a power density of 3 . which can give peak power densities greater than 1 K W Kg-1 while the energy density is only 2-10% of that stored in a battery to deliver the same power96.
Some of the systems that have been proposed to meet the mid-term goals include batteries like sodium-sulfur. collected and later reassembled into fresh cassettes. lithium . The desiring range is claimed to be
The overall advantages of electric vehicles with respect to the environment must be
considered with respect to the total system design. sodium . These
performance requirements are compared in the same table with some battery systems of special interest for electric vehicles and load leveling. zinc . The United States Advanced Battery Consortium (US ABC) for The joint research is also
cooperation towards improved power sources for electric vehicles.OpelCorsa Comb Vans. lithium . metal hydride .metal sulfide. which is then fed into an electro-winning bath where zinc is deposited.
funded by the Department of Energy and EPRI. The electric vehicle itself emits no pollutants.vehicles sold in the state must be so called zero emission vehicles by the year 2003. meet the long-term goals. 300 km. Zinc oxide is dissolved in a KOH
solution.nickel chloride. On the other hand. Ford and Chrysler in the USA decided during Jan 1991 to form a consortium. In order to recharge the zinc anode rapidly and their system solution
includes a refueling system for mechanically exchanging zinc anode cassettes and a regeneration system for recycling depleted cassettes.nickel oxide. None of these yet
Electric Fuel Limited in Israel has developed a refuelable zinc-air energy system for powering electric vehicles97.nickel oxide. This system is being tested by Deutsche post with Mercedes Benz vans and GN . the electricity generating plants delivering electric energy to
. The total budget is $1260 million for five years. The goals that have been set by the US ABC are shown in Table 5.polymer and lithium ion batteries. In order to meet these new regulations ‘the Big Three’ General Motors.air and Zn .
vehicles that are likely to meet these demands are electric vehicles.
nine years ago marked the beginning of the era of the treatment of health disorders by battery powered implantable devices. Neurostimulators. are in routine use. Holter devices for cardiac monitoring rely on
Ambulatory external drug delivery systems are powered by batteries. the
use of batteries in the treatment of disease will continue to be an important feature of medical care. The efficiency of fuel utilization is also higher. batteries for energy. Drug delivery
systems provide carefully controlled administration of medication inside the patient.
The list goes on and
Motorized wheel chairs. At both battery technology and device development progress. The development of the devices mentioned above has been made possible in part by the
.3. ranging from surgical tools to motorized wheel chairs. For example. Left ventricular devices provide life-saving `bridge' for patients awaiting heart
transplants. but the intensive research that is going on world wide will hopefully lead to a break through for the electric vehicle in the future. Portable external defibrillators powered by rechargeable batteries are present in most emergency response vehicles. In addition to these internal devices. implantable defibrillators save thousands of lives annually. increasingly rely on secondary batteries for their power. which relieve severe pain and treat conditions such as epilepsy.
Batteries for Modern Health Care
The invention of the cardiac pacemaker thirty .recharge the vehicles give additional pollution if they are based on fossil fuel combustion. Since that time
several different battery powered implantable devices have been developed and are in use.
3. Batteries play an important role in external medical devices as well. Batteries are still to expensive and do not
meet the requirements with regard to energy and power densities for electric vehicles. batteries have played an important role in powering external medical devices. tools without cords enable surgeons to operate with less inconvenience.
particularly for implantable devices. The cell generated hydrogen gas as a by . smaller and longer lasting power sources for external medical devices.
advances currently under way in the field of secondary batteries provide the promise of lighter.advances in battery technology in the last 40 years. (A) The Cardiac Pacemaker * Greatbatch and Chardack. Above all. Longevity is a crucial factor.
The evolution of implantable biomedical The
devices proceeds as the development of advanced primary lithium batteries has evolved. Early
pacemakers used as many as ten of these batteries in series/parallel combinations. devices show many important features. Life-saving devices simply must work Methods of
The end of the life time of the cell Later
was rather abrupt.product of the cell The cell showed
reaction and this prevented hermetic sealing of the pacemaker. significant self-discharge at body temperature. invented by Puben99 was used for first 10 years. Power sources for medical
Size and weight are always important considerations.
assessing quality and reliability of medical batteries have been developed and are used to ensure that power sources meet the requirements. Especially batteries
using unique materials will allow the development of medical devices for demanding environments such as the magnetic resonance treatment arena. the requirement is for the highest standards of quality and reliability. with little indication that cell depletion was imminent. between 1958-60 made the first successful cardiac pacemaker. but significant drawbacks were present. This cell. Mallory. Zinc/mercuric oxide batteries was the power source98. and General Electric showed some improvement in longevity and self-discharge100.
versions of the cell developed by companies such as Leclanche'. and the battery is a crucial component in ensuring reliable performance.
But patient compliance was a problem. which offers 3. the lithium/cupric sulfide system106 and the lithium/thionyl chloride system107. These cells used plutonium to generate heat. rechargeable pacemaker was developed using a specially designed nickel/Cd battery101. self-healing electrolyte/separator provides inherent reliability and the system exhibited excellent record of reliability and safety108. invented by Schneider and Moser103 and developed by Greatbatch. * Nuclear batteries were developed for pacemakers. This system was reliable and successful but it associated with regulatory burden. The cell was recharged through the skin by an alternating
field. which was converted into electrical energy by thermopiles102. providing greater longevity in a much smaller package and self-forming. Gradually the other systems gave way to the
lithium/iodine-PVP system. and today all cardiac pacemakers use this system.0 W h cm-3.86 ampere hours of capacity per
gram made possible the development of pacemakers with years of longevity which could be hermetically sealed and the cell depletion could be detected easily by the circuitry of the device. the energy density approached 1. Lithium metal.* In 1970s. The first lithium battery to be used in a cardiac pacemaker
was the lithium / iodine .polyvinyl pyridine (PVP) system. The limitations are: (1) The system contains solid electrolytes which
grow thicker as the cell is discharged the resistance of the cell is rather high and
. * The real progress in achieving a truly long-lived pacemaker came with the development and commercialization of lithium primary batteries in the late 1960s and early 1970s. so the cell and the pacemaker can be hermetically crated. The advantages of lithium/iodine-PVP system include: There is no gas generation unlike Zn/Hg oxide battery. Several other
lithium-based systems found significant use in pacemakers. Mead and Rudolph104. especially the lithium / silver chromate system105.
which exhibits a resistance of thousands of ohms in the final stage of discharge. could be treated by an implantable device.PVP system. It has been proposed that using a solid cathode. This device places a challenging demand on the battery. (B) Implantable Defibrillator/Cardioveter It was
Implantable defibrillator/cardioveter was developed by Morowski et al. resulting in a cell which
retains the volumetric energy density of the lithium / iodine-PVP system while doubling the gravimetric energy density. The resistance of the cell remains under 50 ohms throughout
discharge. stopping the fibrillation and restoring normal cardiac rhythm. a working model was
implanted in a human. The power source must operate efficiently at low current drains necessary to power the monitoring circuitry and. because iodine itself is rather dense and the cell is encased in stainless steel. must provide a very high energy power (~ 35 joules) to change the capacitors and provide the shock to the heart.increases with discharge. when ventricular fibrillation is lined.110 in 1970s. The solid cathode liquid electrolyte systems. the gravimetric energy density is not as advantageous. pacemakers.
lithium / carbon monofluoride and lithium/manganese dioxide are likely to find their application in pacemakers in the near future109. By 1980.delivery limitations. unlike the lithium/iodine . liquid electrolyte system could help to alleviate these drawbacks. a major cause of death.
believed that ventricular fibrillation. (2) The cell shows
excellent volumetric energy density. The lithium / carbon monofluoride system has been proposed for future
This system can be encased in a titanium enclosure. which increases as the cell is depleted and results in current . leading to a voltage drop under load. which could detect the onset of the condition and provide a shock to the heart.
The device provided a constant flow of a drug through the
expansion of the bellows and so control of the drug administration other than that provided by the mechanical pump.
electrical signals showed in clinical trials to be effective in reducing the frequency and severity and epileptic seizures117.000 implantable defibrillators.The first power source used in this application was Li/V2O5 cell developed by Horning and Viswanathan at Honeywell Corporation171.level current drains necessary for effective stimulation118.
effectiveness of the device in prevention of sudden cardiac death. (D) Implantable Drug Delivery Systems
Implantable drug delivery systems began in 1970s and first such units employed bellows pump activated by liquefied freon119. which can provide the milliampere .
and this source was soon replaced by batteries using silver vanadium oxide as cathode material based on original technology developed by Liang et al. Later.. These devices currently are powered by lithium/thionyl chloride
batteries. liquid electrolyte
batteries in these devices. Further development have shown that direct stimulation of the brain
may be effective in controlling the tremors associated with Parkinson’s disease116.b. The Li/Silver vanadium oxide energy source Recent clinical studies established the
was used in over 75. A multi-programmable implantable These
pulse generator delivers electrical signals to the left vagus nerve via bipolar electrodes. They exhibited shorter longevities than needed. (C) Implantable Neurostimulators Few types of chronic intractable pain can be effectively managed by electrical stimulation of the spinal cord115. It is anticipated that the future will employ solid cathode.112 and adapted for the implantable defibrillator application by Keister et al113a. electrically powered pumps and advanced electronics were
models of these devices permit the patient to control the level of stimulation in response to the level of pain involved. Neurostimulation has been developed to treat epilepsy. Implantable neurostimulator has been used for this purpose.
65 V) needed by the electronics. resulting the possibility of stroke. Cd batteries are employed. (G) External medical devices
. evaluation123. energy levels of about three joules or less are necessary to achieve This energy is adequately provided by implantable batteries capable Solid cathode.
The use of implantable
pumps administer several drugs for therapies such as cancer. (F) Left ventricular assist devices (LVAD) / total artificial heart (TAH) For more than 10 years the development of LVAD & TAH has been under way124.
of delivering milliampere . Nickel /
Current progress in lithium-ion secondary battery technology
offers the promise of lighter. cerebral palsy and injuries 120. and implanted pectorally.
by electrical stimulation. The device
detects the onset of atrial fibrillation. blood can pool and A device has been developed to treat atrial fibrillation
clot. The classic example is insulin121.
deliver the milliampere-level current drains required by the device and the higher voltage (3.
lithium/vanadium oxide systems are employed in these devices. Drug pumps of the future may employ solid cathode liquid
electrolyte systems such as lithium/manganese oxide or lithium/carbon monofluoride.level pulses. Units are currently in clinical
Typically. applies electrical pulses to the heart. and after careful diagnosis of the appropriate electrophysiological signals. liquid-electrolyte cells such as the
reversal of the condition. Because all the blood is not pumped out of the atrium.employed to provide a more controlled administration of drugs. irregular atrial impulses and in effective atrial contractions occur.122 which resembles cardiac pacemaker. (E) Implantable Atrial Defibrillators Atrial fibrillation is an arrhythmia in which rapid. The defection and stimulating leads are placed transvenously into the heart. The most commonly used battery system This system offers the ability to
for these devices is the lithium/thionyl chloride system. smaller battery packs in future versions of this type of device. multiple sclerosis.
Batteries allow patients to be equipped with portable monitoring or therapeutic devices while remaining ambulatory. They allow surgeons to use electrical tools and visualization devices without the encumbrance of power cords attached to house power. They make it possible for
the wheel chair users to travel about without providing manual propulsion of their devices. On interruptible power sources prevent the loss of line power from causing severe problems in hospitals. The specific examples of the many types of external devices are given elsewhere125.
Batteries indeed contribute in an important way to the maintenance of health and saving of lives. We can look forward with confidence to more exciting applications of battery-powered
devices as scientists, engineers and physicians continue to make progress. 3.4
From today's perspective, the present status of our industrialized world requires new approaches to solve energy and environmental problems. Fuel cells are becoming widely
accepted as a preferred means of generating electricity for distributed electrical power generation because of their high fuel conversion efficiency, environmental compatibility and reliable and quiet operation. Fuel cells differ from conventional internal combustion engines It differs from the secondary battery in that It differs from primary batteries in that
in that they do not suffer from Carnot's limitation.
they are not chargeable in the conventional manner.
the reductant (fuel) and the oxidant (typically air or oxygen) are continuously supplied and not prepacked. The challenges this approach is supposed to meet could dominate energy
conversion systems introduced in the energy market in the foreseeable future. Possible advantages of such a scenario are: • Providing power for both stationary and mobile applications. • Preserving material and energy resources. • Minimizing environmental problems on a local basis (i.e., emission, noise and summer smog).
• Reducing emissions (greenhouse effect) on a global basis and considering new fuel concepts. On the other hand, the economic and technological challenges include: • Competing with established low-cost technologies showing considerable development promise (efficiency improvement, reduction of pollutant emissions). • Solving specific problems associated with new technology • Providing acceptance of the new technology and • Discussing the application prospects of new fuels. Steady progress has been made in various aspects such as catalysis, electrolytes, electrode structure design, theoretical understanding of gas diffusion and fuel cell engineering. Possible configurations of fuel cells and their relative merits are given in Table 6126. The schematic
representations of various types of fuel cells such as alkaline fuel cell (AFC), polymer electrolyte membrane fuel cells (PEMFC), direct methanol fuel cell (DMFC), molten carbonate fuel cell (MCFC) and solid oxide fuel cells (SOFC) are given in Fig. 11, along with their respective reaction at the electrodes. Excellent reviews and books are available on various
aspects of different types of fuel cells127-141. Fuel Cells for Electric Vehicles New drive systems with fuel cells and the energy carriers required could play a major part in improving the overall environment. • • • Within the past 2 years 18 prototype fuel cell vehicles have been produced142. Most of the major OEM's are gearing up for a year 2004 launch of fuel cell cars. Ford's P2000 and Daimler Chrysler's NECAR 5 are currently undergoing real world test in California partnership driving for the future. • Jürgen E. Schrempp of Daimler Chrysler, at the launch of the NECAR 5 was quoted saying, "Today we declare the race to demonstrate the technical viability of fuel cell vehicles over. Now, we begin the race to make them affordable"143.
All these points can be seen as evidence that fuel cell cars are on their way soon.
technical systems under discussion will have to be evaluated on the basis of three reference criteria namely: performance, lifecycle and cost. drive systems will have to compete with • Combustion engines (on the basis of clean primary energy carriers), • Hybrid drive systems (with higher drive weight and higher cost and • Electric drive systems with batteries (with higher cost, shorter range and higher drive weight). One question that still seems to be unanswered though is whether the customer will be refueling their vehicle directly with hydrogen or via the hydrogen-rich carrier, methanol. This is an In particular, electrically powered fuel cell
important issue not just from a refueling infrastructure perspective but also from the public perception and from the gearing up of production, retraining of staff and mechanics, developing guidelines and dealing with safety issues that will need to put in place for the new fuel.
As compared with conventional cars, fuel cell cars would be equipped with novel drive units, that is, the fuel-cell unit (PEFC) and, in addition, fuel processing or gas production unit in the case of methanol or hydrocarbons (clean gasoline or clean diesel), when used instead of hydrogen. These new fuel-cell systems for road traffic are confronted with the following key
requirements: • • • • • • • Low manufacturing costs (< 70 DM/k Wel), Light and compact construction (< 6 kg/k Wel, < 61/k Wel), Efficient energy management, Efficient water management, Efficient gas processing, Quick start-up and systems dynamics, Compliance with environmental standards,
• • • •
Adequate life cycle (>10 years), Mass production, Driving comfort and Safety considerations.
The efficiency rates achieved in various units of gas producing systems, including gas after treatment and fuel-cell systems with net power generation for the electrically powered drive systems, are interrelated process parameters which determine the energy management in the New European Driving Cycle (NEDC) in terms of both the drive system and the overall energy requirements at the wheel basis.
In fuel cell systems, that is PEFC systems that are ready for operation at ambient temperature with optimum operational temperatures between 60 and 80°C are integrated in electrically powered drive systems, the overall energy management depends on various performance parameters that determine not only the energy and emission balances but also the material balances. Major variable performance parameters showing particular impact on the power
yield in the fuel-cell system are: • • • • • • • • Temperature Pressure at the anode and cathode unit Excess air in the cathode unit Fuel - gas processing in anode unit Fuel - gas rarefaction or pollution (e.g. CO) Design of membrane and electrode Quality and quantity of electrode / catalyst, and Energy and water management
directly. which drives one to reflect on an alternative fuel. transmission mechanism. stability. oxidizing ability and electrical yield per gram of fuel144. The main problem is that the electrochemical reaction of In addition. existence in liquid state. A direct methanol fuelcell system offers higher system efficiencies because there is no energy consumption for fuel processing. there are two concepts for using methanol The actual
power densities may be achievable. current transformer and electrically powered drive with electric motor and. Next to hydrogen. oxidizes at the cathode. As a consequence.
is seen from the table that hydrogen is the most promising fuel because of its maximum energy density and the maximum voltage that can be derived which is close to the theoretical value. availability. thus defining the energy efficiency rate of power generation as a function of the drive load. the use of hydrogen is always associated with the complexity in storing and handling. uses methanol directly for electric power generation and promises technical advantages for power trains. The fuel can be delivered to the fuel cell in a gaseous or liquid form. methanol is kinetically hindered. At the same time. efficiency. based on a PEFC. it appropriate.
. methanol permeates through the electrolyte and Furthermore.
The various fuels that can be employed as the reductant in fuel cells are listed in Table 7.All these parameters influence the current/potential characteristics of the cells.
they determine the overall energy management for fuel gas supply.
power densities of a DMFC are clearly lower than those of a conventional hydrogen-fed polymer electrolyte fuel cell. part
This results in a mixed potential at the cathode. net electricity generation of the fuel-cell system.
The direct methanol fuel cell (DMFC). However.
of the fuel cannot be used for power generation and the efficiency of the system decreases. a significantly smaller size and lower costs at comparable In addition. methanol is the favored
fuel from the aspects of cost.
. fuel-cell developments for mobile applications are focusing on the following trends and options: Choosing the "right" fuel Proving the feasibility of the new technology. As for electronic
chemical quantities measured are directly transduced in electrical signals. Numerous investigations have addressed the problem of methanol permeation to find ways to reduce it145. fuel molarity and operating current. Electrochemical sensors are attractive due to their detection ability. and Implementing the steps necessary to gain access to the market.
4. components. For fuel-cell cars operating on hydrocarbons. environmental control (water. two types can be distinguished:
active sensors. for which an electrical source is necessary to apply a signal followed by the analysis of the response (amperometric. coulometric and conductometric sensors). In summary. air. combustion monitoring etc. this is
only partially the case. NOx and NMVOC emissions in the American driving cycle and the EURO4 standard in the European driving cycle. industrial wastes. fuel-cell cars operating on methanol offer emission levels considerably lower than the SULEV standard required for CO. especially in long-time operation Achieving the cost reductions necessary from today's point of view Contributing to minimizing energy demand and emissions. food industry. In general. fuel-cell cars operating on hydrogen prove to be zero-emission vehicles. and biomedical applications (analysis and monitoring) as well as in integrated home systems.
Chemical sensors are used in a variety of applications such as chemical processes. which give a voltage
(potentiometric sensors).Methanol crossover is controlled by cell temperature.). that is. and passive sensors. analysis setups.
spate of investigations have been carried out in this area.analysis in molten salts in
recent158a.bsulfur oxides156 and hydrogen157 were developed.
introduced in 1937. but the first sensors were developed at the end of the century. The first oxygen gauges were tested in 1961154a.1
Principles of potentiometric sensors using solid electrolytes are extensively dealt with in literature162i.147-159 The key finding were: After a first approach made by Nikolskii in 1937.155a.b.Basic electrochemical concepts were established in the 19th century by volta (classification of redox couples). Faraday (relation between electricity and quantity of matter).150 other ISE's based on silver salt or on a LaF3 monocrystalline membrane were developed in 1960s151.b.163a-h.
Severinghaus and Bradley in 1957149.ion. been proposed. New systems coupling amperometric and potentiometric measurements have Excellent reviews are available in this field162a-m and the goal of this
presentation is to explain using electrochemical concepts. The pH electrode using a glass membrane was
discovered by Cremer in 1906146 and then on. Potentiometric sensors are based on the existence of equilibrium at the
. Kohlrausch (conductivity measurements). and Nernst (thermodynamic approach). the working principle of electrochemical sensors and to show their limits of utilization. Kiukkola and Wagner153 employed solid oxide cells for thermodynamic measurements. Amperometric and coulometric oxygen sensors are more Ceramics were first used for O2.160 or crystalline materials are used to improve the selectivity161. ionic materials. amorphous. Nowadays. The first conductometric sensors using a TiOx-based material were developed in 1970s159. pH electrode were employed for pCO2 measurement by After the ion-selective electrode (ISE) for Cl. Similar sensors for halogens.147 a theoretical model was established by Eisenman148 to explain interfering phenomena in sensory using a glass membrane.
) x B (Sol) yzF
RT __ In a (X2+) zF
RT . stabilized
zirconia/O2-.__ In a (By-)Sol YF (33)
.Zμ° y. by exchange of electrochemical species. the mobile ion of the SIC reacts with the analyzed ion to give a complex or an insoluble chemical product at the interface. The Galvanic potential is given by 1 φSIC . • Ionic junction of the second kind: In this case. • Ionic junction of the first kind: In this case. Typical examples are: LaF3/F-. its chemical potential is equal to the standard potential μ°.yμ° Z+(SIC) .
z+ yX SIC
y+ zB sol
The thermodynamic relation is. Yμ°xZ+(SIC) + yRT In a (X2+)SIC +YzFφSIC + zμ°By-(Sol) = RT In a (By-)Sol . mobile ion) is exchanged between the SIC and the analyzed solution (sol). AgCl/Ag+ or Na+-based glass/Na+ interfaces in ISE.YZFφSol = μXyBz (32)
If XyBz forms a separate phase.interface between a solid ionic conductor (SIC) and the analyzed medium. only a single electrochemical species (X2+.φSol = ___ (μ°XuBz .
A pH electrode can be used for CO2. sensors in this field are summarized in Table 8.
Other factors such as electrode reactions.Cl mixtures to If AgCl is a separate phase equation (33) can be applied
determine the activity of Cl. Severinghaus and Bradley employed ISE to measure an active gas pressure. 4. solubility of the membrane in solution is another limiting factor. the voltage is proportional to the logarithm of the activity of the analyzed ion. and the Nernst equation is obeyed. Ag+-ISE for HCN.As in (31). The barrier usually consists of a hole or a porous
. through a material permeable to the gas (TEFLON®). neutral layer. F--ISE for HF and Cl--ISE for Cl2170. NH3. ionic exchange at the interface and interfering phenomena are dealt in detail elsewhere164. which is in contact with the external medium. The gas is supposed to be in equilibrium
with an ion (typically proton) in an intermediate solution (carbonate solution for CO2 measurement).2
Amperometric sensors are based on electrochemical reactions. The characteristics of common ISEs and new
Limit of Detection: Interferences can restrict the measurement of ion concentrations.ions. The
The various gas potentiometric sensors are summarized in Table 9. numerical value of y. governed by the difussion of the electro active species through a barrier171. Of course. S2--ISE for
H2S. if the concentration of X2+ in SIC is high. if the interfering ions are highly concentrated or if their selectivity co-efficient is high. SO3 and NO2. the variation is a function of the
Typical examples are AgCl membranes and Ag2S .
An example of an amperometric
A working temperature of about 400°C is often employed. When this condition is not satisfied.+ ½ Cl2 → AgCl (37)
. candidates for low-temperature sensors176. The conductivity must be as high as possible to avoid an
Another problem is that the diffusion is slow at low temperatures173. conductivity. either n or p type will appear. excessive ohmic drop. with an electronic transport number of
a few percent. Chlorine
sensor proposed by Liu and Weppner179 is based on β"-alumina as SIC with an AgCl layer. the Faradic efficiency is close to one and the error is less disastrous than for potentiometric devices. The electrode reaction is given by Ag+ + e.→ H2 + O2(34) (35) (36)
To apply Faraday's law. an electronic Generally.→ CO + O2H2O + 2e.
Liaw and Weppner175 have proposed Bi2O3-Eu2O3 solid solutions are good
Amperometric oxygen sensors based on PbSnF4
Similar SICs can be used to analyze species such as CO2 or H2O by electrochemical reduction. as for potentiometric sensors172.12. The SICs used for oxygen sensors are generally based on stabilized zirconium (e. YSZ). only gas sensors are based on amperometric principles. the voltage at which the above reactions occur must be compatible with the electrolytic domain of the SIC.Up to now. already operate at room temperature177. The various electrode reactions are: O2 + 4e. oxygen sensor with an air reference is shown in Fig. tetragonal zirconia for measurements down to 250°C. A protonic conductor was employed for a H2 amperometric sensor by Miura et al178. essentially oxygen sensors.g.→ 2O2CO2 + 2e.
but. Vo the volume of our chamber. which is used for measuring the resulting voltage. (a) Direct current mode
Pump-guage devices are derived from amperometric and coulometric devices. 4. with an The O2 excess is then measured by an
excess of oxygen produced by an oxygen pump.The lifetime of this sensor could be limited by the formation of a covering AgCl layer at the electrode. and a gauge part.3
The gas species is dosed by the
Coulometric sensors are similar to the amperometric devices. the diffusion flux between the chamber and the analyzed atmosphere is negligible during the measurement. ideal gas and so its partial pressure is equal to The electro active gas is supposed to be an
t+Δt Pin = ∫ t
R T I (t) dt __________ ZFVo (38)
Where. to which a variable current can be applied. z is the charge number to reduce (or to oxidize) one molecule of the electro active gas. the above equation simplifies to RTIΔt Pin = _________ zFVo (39)
4. and I (t) the dc current during Δt (time delay to obtain Pin → 0 or reverse). in this case. for instance. A reducing gas can be analyzed indirectly by first oxidizing it. amperometric oxygen sensor180. If the current is kept constant during Δt. Only oxygen sensors are based on this principle.
of a pumping part.
the internal pressure Pin can be calculated from the gauge voltage E by using the Nernst equation.
The corresponding voltage may be given as. The current is related to the pressure difference between the analyzed gas and the
internal chamber. I = 4FA (Pout . A sinusoidal current I = Io sin ωt is applied to the pumping part and the voltage is measured on the potentiometric part.Pin) (40)
Where. lead to I = 4FA Pout (1 – exp( 4 FE / R T) ) (42) (41)
The current can be modified by an external source and a plot of I as a function of 1 – exp (4 FE / RT) allows Pout to be measured. The
amplitude of ac voltage is then proportional to Pout-1. A low frequency (lower than 10 Hz) is required to achieve equilibrium in the chamber.183 ES = . The above equation can be simplified if R T Io/4FV ω Pout is small.
. the diffusion coefficient and Vo. the volume of the chamber. Pin = Pout exp (4 FE / R T) The above two equations. A is a coefficient.RT/ nF In [In – (RTIo / 4F Vo ω Pout) cos2Ψ (43)
Where Pout is the oxygen partial pressure in the analyzed gas and Ψ is a parameter depending on the geometric factor of the pore.In the model proposed by the Hetrick et al.b have proposed an AC mode for amperometric devices.182a.181 a pumping gauge system works in steady-state condition. (b) Alternating current mode Maskell et al.
oxygen pressure. E = RT/4F [ln (Pout / Pin) – ln (1 + RTIo / 4FVoω Pin) cosωt (44)
Where. or Ba oxides. Edc = [R2T2Io / 8 π F2 Vo ω] [1/ Pout] The measured dc voltage is then proportional to Pout-1. In these devices. The potentiometric voltage is equal to. which The higher the temperature. an approximate equation is obtained. Mn. the faster The working temperature is generally
should remain constant as a function of time. with a low
frequency (<10 Hz) to obtain equilibrium in the chamber. Here.
At the present time materials such TiOx doped with Fe.4 (45)
In this section. plays an important role. and various electrochemical parameters employed for analysis is given elsewhere164.
. or alkaline earth ferrates are used essentially for oxygen sensors185. Pin and Pout are the internal and external oxygen partial pressures respectively. By employing an electronic system to maintain the mean value of E
equal to zero and to transform the emf into a dc voltage Edc.b. conductometric sensors in which the ionic conductivity of the material plays a role are considered. For example: TiOx. the area/volume ratio
The grain size and the grain boundaries are two parameters. exhibits a variable stoichiometry as a function of the
Semiconductor materials like SnO2 are used in Figaro sensors for analyzing The working
the reducing species. 4. an ac current I = Io sin ωt is applied to the pumping part. work on principles of heterogeneous catalysis185a.
principle of TiOx. Cr. morphological changes of the ceramics will occur.Benammar and Masskell184 have proposed a more sophisticated sensor to limit the parasitic phenomena. Vo is the internal volume.
b. Thin-layer technologies for fabrication of conductometric sensors are being developed186a. Recent developments in photo
electrochemistry have led to new. interesting possibilities. An array of such selective sensors can be built into one device for monitoring the
flue gases and other gas streams containing several toxic components. one in contact with the analyzed atmosphere.
It is known that. the other insulated from it. Such devices have two advantages: the response time is improved and mass production is less expensive. which can destroy pollutants by means of reduction and oxidation. respectively. This photo catalytic methods have been reviewed sometime ago187.
It was also
proposed to use two sensors in a differential mode at the same temperature. thus diminishing electricity consumption.higher than 600°C (at low temperature it becomes a semiconductor sensor). In this way. Table 10 provides an outline of some semiconductor conversion devices. air or water containing organic. Only
semi-conducting materials can store the energy obtained from incident light and allow the stored energy to be converted to other forms.
. In the first case.
5. both for treatment of pollutants and for conversion of solar energy from light to electricity. metals are unsuitable for light energy conversion because their excited electronic states have extremely short lifetimes and energy is rapidly dissipated as heat. inorganic or microbiological pollutants can be effectively treated. A sensor can be made selective by a suitable choice of electrode potential and electrode material.
PHOTO ELECTROCHEMICAL METHODS
This approach is especially appealing since an important energy input contribution from light might be expected. suspensions of
semiconductor particles can be used to harness the light with production of electrons and holes in the solid.
A historical perspective was presented to frame the recent scientific and The exploitation of a deliberately
technological progress that has been made in this field.
properties of nanocrystalline electrodes are reviewed with particular emphasis on electron transport in dye-sensitized nanocrystalline photovoltaic cells by Peter et al190. for several excellent reviews on these topics are already available in literature197-203. we are not
addressing the underlying theory or physics of photoelectrochemistry. Lewis188 recently covered the frontiers of research in photoelectrochemical solar energy conversion.
nanostructured interface which could provide useful enhancements to the kinetics of interfacial charge transfer events and that allow the use of catalysts without suffering concomitant efficiency losses was discussed.as a method for converting solar energy into hydrogen. However. which can be used as a storable fuel. Tryk et al189 discussed the recent The
topics in photoelectrochemistry in terms of its achievements and future prospects. and electrochemical behavior of photoelectrode surfaces.
The considerable amount of research that has been carried out in the two closely related fields of semiconductor photoelectrochemistry and photocatalysis during the past three decades continues to provide fundamental insights and practical applications. Photo electrochemical
reduction of CO2 on semiconductor electrodes. electrical properties.The photo-electrolysis of water to hydrogen and oxygen using semi-conductors as photo electrodes has been studied extensively during last few decades .
. which is regarded as a kind of artificial photosynthesis has recently received attention from the viewpoint of the global environmental problem. A model system was provided for the
elucidation of the interconnections between the chemical modification.
of the driving forces behind the photoelectrochemical approach is the perceived ability to form rectifying junctions in simpler ways compared to the relatively sophisticated techniques required in solid state processing. Another is that barrier height can in principle be varied
easily by choosing appropriate match-ups between semiconductors and redox couples. The latter has
enjoyed continuous development. in the late 1960s204.
. photogeneration of electricity) and electrolytic cells (i. both for regenerative cells (i.205. there has been much work carried out primarily aimed at solar energy conversion as an alternative approach to that of the solid state junction photovoltaic cell.Beginning with work on photoelectrochemical water electrolysis or `splitting'. although practical wafer-based cells give efficiencies in the range 12¯16% 207.e. with the efficiency now reaching over ~24% in laboratory cells206. photogeneration of useful products such as hydrogen). These ideas and interesting results continue to drive research in this area.e. Efforts have been
made to improve the performance of conventional semiconductor electrodes for solar energy conversion.
have recently prepared porous n-Si
porous n-Si electrodes with Pt coating in aqueous HBr/Br2 are improved by thinning the nanoporous layer. 0. jsc. leading to efficient electron-hole separation.5 μm thick nanoporous layers.
Surface modification and thin film electrodes:
Nakato et al.. fill factor. with macroporous layers at the surface. The walls and tops of the Si pillars are further The solar cell characteristics for the
covered with 0. by photoetching in HF. Torimoto
.7 mA / cm2. depending upon the The large specific surface area and high crystallinity of the
etched TiO2 make it an attractive material for photoelectrochemical applications.Nanostructured surfaces : Nanometer-scale control of the solid semiconductor electrode is sensitively related to the photoelectrode behavior and hence to the energy conversion efficiency.701) was obtained. modulated the band energies of an n-type Si chip by the formation of siliconhalogen termination on one side of the chip211.210 fabricated TiO2 nanostructure by photoelectrochemical etching with nanohoneycomb pattern made up of rectangular cells. Sugiura et al. of few hundred nanometers wide and several micrometers deep. A maximum solar energy conversion efficiency of 14% (Voc. crystallographic orientation.573 V. which is one of the top records for n-Si photoelectrochemical solar cells.2¯0. 0. For example. consisting of micrometer-sized pores and Si pillars208. equaling that of Gibbons et al. in contrast to the case in which both sides of the semiconductor have the same type of termination. These cells are regularly ordered. working in nonaqueous electrolyte209. including photocatalysts and dye-sensitized solar cells. Kawakami et al.
34. This surface asymmetry produces an
efficient solar-to-chemical conversion owing to the presence of band bending within the n-Si chip in a photostationary state.
et al.g. Licht et al. Only recently.
size effects of the immobilized nanoparticles on the metal electrode were retained in the photoelectrochemical behavior of the electrode.g. These workers have achieved a solar¯¯
to-electrical efficiency of 19. have adapted a multiple-band-gap approach to photoelectrochemically split water218. which has motivated work in the area of photovoltaic solar cells..
Multiple-band-gap photoelectrochemical cells:
The aim of using multiple-band-gap cells is to capture a greater fraction of the solar spectrum.
thermal treatment. an overall efficiency of 18% was achieved in the charging of a Ni-metal hydride battery with the application as constant voltage power source217. have developed a series of such cells
. pnnp) fashion216. pnpn) or inverted (e. this film electrode exhibited photoelectrochemical current-potential curves similar to those for single crystal n-TiO2 electrodes.
this idea has been applied in the photoelectrochemical area.
Si (narrow band-gap)
Most of their work thus far has involved ohmic rather than Schottky-type
semiconductor-electrolyte junctions.2% using an AlGaAs (wide band-gap) bilayer214. It was suggested that a Bardeen-type
junction is plausible for the electric contact at the TiO2 particle/substrate interface. which unfortunately negates one of the inherent advantages of the photoelectrochemical approach. prepared a TiO2 film electrode After the
by coating a TiO2 colloidal solution on a F-doped SnO2-glass substrate213.S.
Khaselev and Turner at the National Renewable Energy Laboratory (NREL) in U. modified size-quantized CdS nanoparticles with 2-aminoethanethiol and immobilized them on an electrode with the use of glutaraldehyde as a cross linking agent
. Shiga et al. In the most recent example of this
They have provided systematization for multiple-band-gap
photoelectrochemical cells based on whether the solid-state p-n junctions are arranged in a bipolar (e. The solid-
40 V positive of open circuit. p-GaP223. to reduce CO2 in aqueous solution. and p-SiC have been examined.
The reduction of
It is desirable to carry out this reaction with a very low The
consumption of energy and/or with the use of a renewable energy source222. or Au) were used by Hinogami et al. which is different from the case for the solid-state p/n/p/n device.
. Ag.83 eV. eV. photoelectrochemical reduction of CO2 is hence an attractive pathway. which is the ideal fuel cell limit at 298 K (lower heating value of H2). p-Si electrodes modified with metal
particles (Cu. p-InP.
production photocurrent of 120 mA/ cm2 is multiplied by 1. Semiconductor electrodes whose surfaces are modified with metal particles are often known to exhibit improved photoelectrochemical behavior. there is an advantage
efficiency for an incident light intensity of 1190 mW cm-2.42
The theoretical maximum efficiency for a dual band-gap is ca. 41% but the maximum The difference between this type of
efficiency for this combination of band-gaps is 34%.23 V. The GaInP2 band-gap is 1. H2 is produced at the semiconductor electrode.
In the course of the development of photoelectrochemistry. This system yields 12. which is thus cathodically protected. The GaAs band-gap is 1. The authors state that one key aspect appears to
be that the bottom cell current is limiting.221. a variety of p-type semiconductor electrodes such as p-CdTe. but theoretically this effect is relatively small
.state tandem cell consists of a GaAs bottom cell connected to a GaInP2 top cell through a tunnel diode interconnect. H2 evolution starts 0.
cell and the fully photovoltaic tandem cell is that the top junction is p/Schottky rather than p/n.
to using concentrated sunlight. CO2 is an uphill process.4% conversion Of course. in which current matching is desirable. p-GaAs.
Photoelectrochemical reduction of CO2: The fixation of carbon dioxide is one of the most important area220. p-Si.
With p-InP photocathodes. with current efficiencies of over 90% for CO production. In addition. including the concentrations of added water and strong acid. At high current densities and CO2 pressures. this adsorbed complex is responsible for
stabilizing all the three semiconductor electrode materials at high CO2 pressures. the CO2 pressure was the most critical factor. They find their utility in
. as each particle is made up essentially of a short-circuited photo anode and photo cathode. and p-Si. the CO2 reduction Of the various factors that were found to
current was limited principally by light intensity. as well as other reactions. including CO2 reduction.224b. It was proposed that the adsorbed
(CO2)2-. while hydrogen gas evolution was suppressed to low levels. Aulice Scibioh and Viswanathan225 have recently
reviewed the various aspects of photo/ photoelectrochemical reduction of CO2. C2H2.
A high-pressure CO2-methanol system has been found to offer a number of advantages for the photoelectrochemical reduction of CO2 by Hirota et al. This reaction was examined
in a 40-atm CO2-methanol medium using the p-type semiconductor electrodes p-InP. even at current densities as high as100 mA/ cm2. current densities up to 200 mA/ cm2 were achieved.
The reduction process was shifted in
potential approximately 0.resulting in the formation of CH4. p-GaAs.5 V positive compared to that obtained with the corresponding metal electrodes. CO.224a. etc.
Dispersed semiconductor particle suspensions are attractive.
influence the product distribution. radical anion complex reaches high coverages at high CO2 pressures and is responsible for both the high current efficiencies observed for CO production and the low values observed for H2 evolution. water splitting.
respectively.e. Materials with rectangular229 or pentagonal prism230 tunnel structures are capable of carrying out complete water splitting with UV illumination by Ogura et al.
candidates. a sacrificial donor is used as a source of electrons for hydrogen evolution. i. The complete water splitting reaction. by semiconductor particles without the benefit of sacrificial agents has been an elusive goal. both H2 and O2 generation. modified with Ni
Since the early 1980s.Water splitting:
It is well known that the distribution of energies in the solar spectrum does not allow most semiconductor materials to decompose water completely into hydrogen and oxygen. NaTaO3 loaded with NiO showed the highest quantum efficiency (28%) for water splitting for UV light with wavelengths of 270 nm or less
. Cs). For
materials whose valence band energy is not sufficiently positive. Rb.
photocatalytic activities for water splitting for a series of 25 tantalate compounds in powder form were thoroughly examined and compared by Kato and Kudo
. Sayama et al. where A is an interlayer cation (K. found that the
addition of sodium carbonate or other sodium salts to the aqueous suspension remarkably improved the efficiency of complete water splitting in the case of TiO2231.. water splitting under visible light illumination was achieved by
Takata et al. with hydrated layered perovskites such as RbPb2Nb3O10 (>420 nm) and A2La2Ti3O10. and Kohno et al.
Doping with excess Na
(donor doping) was found to be highly beneficial. ion-exchangeable layered oxide compounds such as K4Nb6O17 loaded with Ni have been reported to be capable of generating both H2 and O2 under UV illumination. while for those whose conduction band energy is not sufficiently negative. Recently. Ta2O5 and ZrO2
. a sacrificial acceptor is used as a sink for electrons in order to facilitate oxygen evolution.
Where as Ishihara et al234 employed different types of acceptor-doped KaTO3 materials.
TiO2 anchored in zeolite cavities by ion-exchange method exhibited high photocatalytic reactivity for the direct decomposition of NO to N2. Also by the same group.e. it was supposed that the loaded Pt is
covered with titanium hydroxide. resulted in a shift of the action spectra towards longer wavelengths
These were highly donor-doped and loaded with Ni. including water splitting as well as others.
instance.235. For example. resulting in the suppression of the back reaction. immobilization of semiconductor particles in zeolite cavities was found to improve the photocatalytic activity.
For Pt-TiO2. O2.
implantation of transition metal ions in TiO2 by Anpo et al.
. the highest activities were found for Zr4+ and Hf 4+ doping.236.
Cu2O is a promising candidate for the complete photocatalytic water splitting reaction under visible light illumination.loaded with Pt. particularly in view of the long-term stability exhibited over a period of 1900 h by Hara et al.
It is known that doping can improve the photocatalytic activity for water splitting. i. NiOx or RuO2
. the improvement of Ion
the visible light absorption characteristics could have far-reaching consequences. this material displayed a so-called
mechanocatalytic water splitting reaction.
In the case of Cr-implanted TiO2. and N2O238. One possible explanation of this
There are a number of efforts to develop novel types of photocatalysts for various applications. but the reaction was enhanced under illumination. the solar-based
efficiency was improved by 20%. Surprisingly. doped perovskites such as niobates and titanates layered in the (110) direction were employed by Kim et al. as found by Ikeda et al. without illumination. For example. phenomenon might involve a piezoelectric effect.
overall quantum yield of 23% was reported for UV light of wavelengths of 300 nm or below.
4'. Br-.2'-bipyridyl-4.2¯2 ps241.2'-bipyridyl-4. for this type of dye in conjunction with a TiO2 film electrode240. with relatively high
. where X=Cl-.4''-positions achieved very efficient panchromatic sensitization of nanocrystalline TiO2 solar cells over the whole visible range. There has been recent progress reported in this area. the solar conversion efficiency exceeds 10%. The
electron injection of RuII (2. efficiency and long-term stability are the most essential points for practical use.
The high efficiencies of dye sensitization are attributed to the high rate of transfer of electrons from the excited dye molecule to the conduction band of the semiconductor. There are several advantages that such cells would
have compared to those with liquid electrolytes.191 A typical one is cis-X2bis (2. I-.A variety of sensitizing dyes have been examined to improve the characteristics of both semiconductor photoelectrodes and dispersed semiconductor particle systems.4'-dicarboxylate)2(NCS)2 to a TiO2 film electrode was found to be biphasic. with a photocurrent density of 20 mA / cm2 was obtained.4'-dicarboxylato) Ru(II). and SCN-. CN-. with 50% occurring in <150 fs and 50% in 1. including ease of manufacturing and robustness. extending into the near-IR region to ~920 nm. A
particularly challenging problem is the development of all-solid-state versions of dyesensitized photoelectrochemical cells. The efficiency of photocurrent generation was practically 100% over a wavelength range from 400¯700 nm.. which have been intensively studied by Grätzel et al. and the quantum current efficiency can reach to practically unity239. Quantum The most
successful dyes so far reported are the Ru-bipy complexes.
trithiocyanato-ruthenium (II) terpyridyl complex in which the terpyridyl ligand is substituted with three carboxyl groups in the 4. In the case of X=SCN.and the dye-modified TiO2 film electrode. Further improvements were reported by A black
Nazeeruddin et al.
With semiconductor electrodes using dye sensitized Compared to
nanocrystalline TiO2 films an efficiency of 12% has been reported244. it is
important for research efforts to continue in these areas. It should also be stated that there is an important role
to be played by the more innovative approaches. The situation with the photocatalytic water splitting approach deserves
to be monitored carefully.
pulsed modes and hence increased the levels of sensibilities for analysis.incident photon-to-current efficiencies242.
. attempt to mimic natural photosynthesis245. the overall efficiency is still slightly
Photo electrochemical cells for electricity production offer a sustainable way to for charging batteries in electric vehicles. because of the potential window that could be handled
by increasing the possibilities with respect to electrodes as well as the media to disperse the depolarizer. this type of photoelectro-chemical cell is less expensive. This has become possible.
conventional photovoltaic cells. However. is easily fabricated and does not require expensive crystal purification processes. the prospects for widespread application of solar photoelectrochemical devices appear to be somewhat dim for several reasons. for example. that they are able to sense very low concentrations of hazardous species and converting them to non-hazardous or even useful materials. as already discussed. less than 1% due to other types of losses.
However. Electrochemistry being amenable to the modern electronic resolution by the In fact. because the time may surely come when this technology will be needed. CONCLUSION AND OUTLOOK
Electrochemical methods have reached a mature status.
6. This area has not received as much attention worldwide as that of the photoelectrochemical cell.243.
At present. since it uses inexpensive raw materials.
. In fact. in the compact for the environmental pollution and the analysis and control. The developments in
electrochemistry in the last two or three decades very stimulating and hence can be expected to handle the environmental problems posed by the modern developments in process and manufacturing industries. at the same time converting the pollutants into useful products. for the award of Senior Research Associateship to one of us (MAS).electrochemical means are exactly identical with the natural processes taking place in living or non-living cells and membranes and hence. appear to offer the best way to succeed to keep our environment cleaner as well as suitable for living beings. in future. New Delhi.
is possible that electrochemical methods will occupy prominent position.
Acknowledgement We gratefully acknowledge the Council of Scientific and Industrial Research (CSIR). this is one of the options available to mankind to combat It
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Effects of pollutants on human beings Table 5. Sources and types of major air – pollutants Table 4. Cerium (IV) – assisted process Figure 10. which is pressed against a cation exchange membrane on the electrolyte side and a porous current collector on the gas side. Electrochemical absorption column with 3D particle bed electrode Figure 9. Specific energy of different processes for alkali chloride electrolysis Figure 6. The generation and the consequences of pollutants from fossil fuels Figure 11. Features of semiconductor conversion devices AM = anion selective membrane. Population figures for the period between 1989. CuCl2 recovery from splint solution using electro dialysis combined with continuous electrochemical regeneration of cation and anion exchanger beads Figure 5. The electrochemical reaction occurs at the membrane/catalytic layer interface. where hydrogen gas. US ABC criteria and performance of selected battery systems Table 6. Examples of electrochemical gauges (gas potentiometric sensors) Table 10. Configurations of fuel cells Table 7. Example of an amperometric device Table 1. Schematic representation of various types of fuel cells Figure 12.1998 Table 2. Schematic representation of electrochemical soil remediation Figure 7. The world energy production and energy consumption for the period between 1989 and 1998 Table 3. Chemical and electrochemical data on various fuels Table 8. The gas diffusion anode consists of a porous sheet containing a catalytic layer. Three – compartment cell for splitting of sodium sulfate into sodium hydroxide and sulfuric acid solutions.LIST OF FIGURES AND TABLES Figure 1. Summary of ion selective electrodes Table 9. CM = cation selective
. Two chamber cell with gas diffusion anode in which the hydrogen gas evolved at the cathode is oxidized. Electrochemical gas purification by inner cell and outer cell processes Figure 8. electrolyte and active electrode material form a three – phase contact zones Figure 4. Cell with three – dimensional cathode for heavy metal removal Figure 2. membrane Figure 3.
1995 1996 387.79 3.91
1997 1998 396.916.168.342.23 5.53
1994 382.28 400.60
468.10 707.836.70 2.677.51 347.40 690.20
Country North America Central South America Western Europe Eastern Europe & former USSR Middle East Africa Far east & Occeania World
1989 358.8 5.086.944.69 391.78 373.39
617.Table 1.98 391. Population figures (in millions) for the period between 1989.53
1990 363.12 360.66 390.34
1993 377.23 404.323.7 3.28 3.19
148.39 390.508.99 473.277.6 5.47 379.39 470.46
126.79 5.99 3.992.05 764.92 385.48 5.93
137.97 398.94 392.424.26 151.38 159.588.75 5.040.8 3.86
458.46 2.255.57 385.05
5.87 3.33 391.22 2.21 3.55 389.37 601.37 391.1998.34 5.756.64
653.90 390.896.87 5.09 391.56
155.16 391.42 354.23 746.
90 9.15 71.95 19.57 18.51 11.03
64.13 9.07 99.51 11.44 357.51
63.95 14.19 10.01 69.87
11.33 10.77 101.56 15.16 1991 99.39 52.51 91.31 52.53
14.43 14.19 99.01 80.46
13.11 1990 100.35 347.45
64.63 353.27 378.05 1993 103.25
.88 10.02 14.24 18.70 1994 106.17 9.07 112.99 74.24 65.34 74.50 1995 1996 108.83
11.15 1997 1998 112.53
68.74 77.90 15.60 50.18 85.21
13.72 376.09 346.67 74.72 10.34
69.52 48.58 54.54 60.04 377.Table 2.57 348.96
10.31 16.74 17.72
365.12 111.83 1992 101.58
66. The world primary energy consumption for the period between 1989 and 1998 (Quadrillion (1015) Btu)
Country North America Central South America Western Europe Eastern Europe & former USSR Middle East Africa Far east & Occeania World 1989 100.
Sources and types of major air – pollutants Sources Transportation (motor vehicles) Stationary fuel (Electric power & Heating) Industrial process Solid waste Disposal and Miscellaneous Total CO 75.4
.5 4.5 1.0
SP 1.7 Types – quantity (millions of tons per year) NOX SOX HC 11.0 0.4
30.0 13.0 10.6
5.5 12.0 25.0 2.0 0.4
pulmonary tuberculosis. Nitrosomines. irritation of mucous membrane. US ABC criteria and performance of selected battery systems Couple US ABC criteria US ABC long terms Pb/PbO2 Cd / NiOOH MH / NiOOH Zn/air Na/S Na/NiCl2 Li / Polymer (Projected) LiAl / FeS2(cells) Li . congesti Brain and lungs Acute respiratory infection (chronic pulmonary or cardiac disorders) Chronic respiratory infection Lung and stomach cancer Tissue destruction of the respiratory epithelium Brain damage. PAH etc.ion Specific energy (W h kg-1) 80-100 200 35-40 50 60-80 100-120 100 80 150 180-200 80-90 Peak specific power (W kg-1) 150-200 400 150-300 80-150 200 150 230 130 400 >200 200-300 Deep – discharge cycles 600 1000 100-1000 1000 750 <300 760 1200 <100 100 400-1200 (cells)
. cumulative poisoning (adsorbed in RBC & bone marr
SOx NOx HC SP Pb & PbOx Secondary pollutants Attacks of acute asthma and allergic respiratory infections PAN & NO2 Chest constriction. Respiratory tract carcinoma Olefens.Table 4. Irritation to the eyes Acrolein
Table 5. Effects of pollutants on human beings Types Primary pollutants CO Effects Heart disease. O3 cough and exhaustion 2Asthma. infant mortality and acute respiratory infections SO4 and NO3 Aldehydes. head ache. strokes. pneumonia.
limitati operating temp Higher catalyst than PAFC bot anode&cathode
Noble metals are not required Rapid O2 reduction kinetics
High operating tem
Water managem critical.Table:6 Configuration of Fuel Cells
Fuel Cell System Alkaline Fuel Cell (AFC) Polymer Electrolyte Fuel Cell (PEFC) Temperature Range 60-90° C Efficiency (Cell) 50-60% Electrolyte 35-50% KOH 1. 1. 3. 2.
Molten Carbonate Fuel Cell (MCFC) Solid Oxide Fuel Cell (SOFC)
Molten carbonate melts (Li2CO3/Na2CO3) Yttrium-stabilized zirnondioxide (ZrO2/Y2O3)
Noble metals are not required
Phosphoric acid ionic conductor temperature 2. 3. Phosphoric Acid Fuel Cell (PAFC) 160-220°C 55% Concentrated phosphoric acid 1. CO poisoning a catalyst High operating tem
1. 4. 2. 1. 2. 2. Advantages Low temperature operation Rapid O2 reduction kinetics Non-noble electrocatalysts Electrolyte-good proton conductor Minimum corrosion problem Long life period Able to withstand large pressure differentials Operate at high acid temperature range Water management is easy 1.
Do not reject C Pure H2 & O2 a
Polymer membrane (Nafion/Dow)
56 1.21 1.67 6.33 1.52 5.90 -124.60 -68-20 -195.82 2.17 1.50 -503.98 0.65
Energy density (kWh/kg) 32.14 0.22 4.15 1.04 1.62 1.80 -80.80 -143.72 -
.13 5.70 -61.58 0.69 -166.15 0. Chemical and Electrochemical Data on Various Fuels
Fuel Hydrogen Methanol Ammonia Hydrazine Formaldehyde Carbon monoxide Formic Acid Methane Propane
ΔG0 (kcal/mol) -56.06 1.Table 7.28 1.22 1.20
E0theor (V) 1.35 1.48 1.08
E0max (V) 1.23 1.
d 165a. CN-. Br-. Hg2+ I-. 165a 165a-c 165a. CNAg+. Ag+ Ag+. S2-. Br-. CNAg+. S2-.b 165a. Hg2+.Table 8. Hg2+. Cu2+. Br-. SCN-.c.y ≥ 10-2 Cl . Cl-. Cd2+.d 165c. SCN-. Cl-.f 165f 165a-c 165a. CN-
Ref. Br-. Ag+ CN-. I-. OH-. K+. SCNI-. Br-. SCN-.b 165a. SCN-.g
1-5 x 10-7 1-10-4 1-10-7 1-10-7 1-5 x 10-6
. CNOHAg+.d 165e 165a-c 165a. Summary of ion selective electrodes Ion (x) Membrane Ag+ Br Cd2+ ClCNCu2+ FH30+ Hg2+ INa+ Pb+ S2SCNAg2S Ag2S + AgBr AgBr Ag2S + CdS Ag2S + AgCl Ag2S + AgI Ag2S + CuS LaF3 Glass Ag2S + AgI Ag2S + AgI AgI Glass NASICON Ag2S + PbS Ag2S Ag2S + AgSCN Concentration range 10-1-10-7 1-10-5 10-1-10-7 10-1-5 x 10-5 10-2-10-6 10-1-10-8 1-10-6 1-10-14 1-5 x 10
Main interfering ions Kx. S2-. Cl-. Br . Cl-. S2-. Ag+. S2-. SCN-. S2-.b 165d. Hg2+ I-.b 165a. Pb2+. Li+ H3 O + Ag+. CNH3O+. CNS2-.
Al2O3 300 NASICON BaCeO3-based ceramic 770-1100 Na2CO3 / NASICON 570-1000 Li2CO3/LiTi2 (PO4) 620-1000 K2SO4 Ag2SO4+Li2SO4 500-1200 Na2SO4/β’.h 168i
0.Al2O3 SrCeO3-based ceramic 870-1270 Ag+ .f.84 Table 9.1-106 0.1-106 103-106 10-106 0. Examples of electrochemical gauges (gas potentiometric sensors)
Analyzed species O2
Cl2 I2 H2
NO2 (NOx) AsH3 As4O8 H 2O
Operating Temp.Glass 300
Concentration Range (ppm) 0. 166.Al2O3 Na2SO4/ZrO2based ceramic 400 NaNO3/β’.e 168e.c 168d 155b 167b 155a 167c 168a 167d 167d. Range (K) 750-1100 ZrO2-based ceramic 370-520 PbSnF4 300-373 LaF3 SrCl2-KCl 350-500 BaCl2-KCl 350-500 KAg4I5 313 H.U.167a 168b.β’’.1 x 103in air 50-2 x 103 1-190
169b 169c 169d
.1-106 103-106 >104 >104 >104 103-106 >10 in dry air 80-104 >10 in air
Ref. g 168g.P 300 300 β’.Al2O3 NaNO3/NASICON 1000 Na+β’.
85 Table 10.Fe3+ & Th+/Th/ Pt *PEC(liquid-junction) n-CdS/ Fe(CN)3-/4Cells pH=13/ Pt
Photoelectrolysis (H2O) C/VCl4.high cost. well established All other PG systems have low efficiency Higher efficiencies (10%) for semiconductor coated with sensitizer dye Lab device working for several weeks Bias voltage required No bias voltage Low stability
Pt/Fe2+.% 12-22 9-12 <0. VCl3/p-InP 10-14 n-TiO2/NaOH/Pt n-SrTiO3/NaOH/Pt Pt/ HCl/ p-InP(Ru) * One of the many systems studied. GaAs. 1 1 12
. n-CdS/p-CdS Au/n-GaAs Efficiency. 94b. Features of semiconductor conversion devices Devices Solid state p-n junction Schottky barrier M/SC or MO/SC Photogalvanic cells Materials Used Si.2 5-6 Remarks Single-crystal. This table is taken from Ref.