This action might not be possible to undo. Are you sure you want to continue?
2.1 Introduction ............................................................................................................................. 38 2.2 Carbon Families...................................................................................................................... 38 2.2.1 Carbon–Carbon Bonds ............................................................................................... 38 2.2.2 Graphite Family .......................................................................................................... 39 2.2.3 Fullerene Family .........................................................................................................44 2.2.4 Diamond Family ......................................................................................................... 45 2.2.5 Carbyne Family ..........................................................................................................46 2.2.6 Modes of Acceptance of Foreign Species...................................................................46 2.3 Formation of Carbon Materials .............................................................................................. 47 2.3.1 Carbonization Process ................................................................................................ 47 2.3.2 Gas-Phase Carbonization............................................................................................ 49 22.214.171.124 Carbon Blacks .............................................................................................. 50 126.96.36.199 Pyrolytic Carbons ........................................................................................ 50 188.8.131.52 Vapor-Grown Carbon Fibers and Carbon Nanofibers ................................. 51 184.108.40.206 Carbon Nanotubes ....................................................................................... 52 220.127.116.11 Fullerenes..................................................................................................... 53 2.3.3 Solid-Phase Carbonization ......................................................................................... 53 18.104.22.168 Activated Carbons ........................................................................................ 53 22.214.171.124 Glass-Like Carbons ..................................................................................... 55 126.96.36.199 Carbon Fibers............................................................................................... 56 188.8.131.52 Carbon Films ............................................................................................... 57 2.3.4 Liquid-Phase Carbonization ....................................................................................... 57 184.108.40.206 Polycrystalline Graphite Blocks................................................................... 58 220.127.116.11 Cokes and Mesocarbon Microbeads ............................................................ 58 2.3.5 Novel Carbonization Processes .................................................................................. 59 18.104.22.168 Template Method.......................................................................................... 59 22.214.171.124 Polymer Blend Method ................................................................................60 126.96.36.199 Defluorination .............................................................................................. 61 188.8.131.52 Carbon Aerogels .......................................................................................... 61 2.4 Nanotexture in the Graphite Family ....................................................................................... 62 2.4.1 Classification of Nanotextures .................................................................................... 62 2.4.2 Planar Orientation ....................................................................................................... 62 2.4.3 Axial Orientation ........................................................................................................64 2.4.4 Point Orientation .........................................................................................................66 2.4.5 Random Orientation ................................................................................................... 68 2.4.6 Importance of Nanotexture ......................................................................................... 68 2.5 Microtextures in Carbon Materials ........................................................................................ 71
© 2010 by Taylor and Francis Group, LLC
Carbons for Electrochemical Energy Storage and Conversion Systems
2.6 Conclusion............................................................................................................................... 73 References ........................................................................................................................................ 73
Carbon materials have always played important roles for human beings, charcoal as heat source and adsorbent since prehistorical era, flaky natural graphite powder as pencil lead, soots in black ink for the development of communication techniques, graphite electrodes for steel production, carbon blacks for reinforcing the tires in order to develop motorization, membrane switches for making computers and control panels thinner and lighter, etc. In electrochemistry, electric conductive carbon rods and carbon blacks support the development of primary batteries; a compound of graphite with fluorine, graphite fluoride, improved the performance of primary batteries; and the reaction of lithium intercalation/deintercalation into the galleries of graphite was greatly promoting the development of lithium-ion rechargeable batteries. Carbon nanotubes and fullerenes developed recently are promoting the development of nanotechnology in various fields of science and engineering. Carbon materials are predominantly composed of carbon atoms, only one kind of element, but they have largely diverse structures and properties. Diamond has a three-dimensional structure and graphite has a two-dimensional nature, whereas carbon nanotubes are one-dimensional and buckminsterfullerene C60 is zero-dimensional. Fullerenes behave as molecules, although other carbon materials do not. Graphite is an electric conductor and its conductivity is strongly enhanced by AsF5 intercalation, becoming almost comparable to metallic copper, whereas diamond is completely insulating. Diamond which is the hardest material is used for cutting tools, and graphite is so soft that it can be used as a lubricant. In this chapter, an overview on structures and textures of carbon materials is presented, through introducing a concept of carbon families, before going into the chapters concerning the detailed applications of carbon materials for electrochemical energy storage.
2.2 CARBON FAMILIES 2.2.1 CARBON–CARBON BONDS
The carbon atom has four electrons in its outermost 2s and 2p orbitals, namely 2s22p2. When it forms a chemical bond with other atoms, it can have three different hybridizations, sp, sp2, and sp3. The hybridized sp orbital is composed of two σ electrons, associated with two π electrons, the sp2 of three σ electrons with one π electron, and the sp3 of four σ electrons. It is well-known that various combinations of these hybrid orbitals produce a variety of organic hydrocarbons, from aliphatic to aromatic ones. This situation is illustrated in Figure 2.1, by showing typical hydrocarbons. The carbon–carbon bonds (C–C bonds) using sp2 hybrid orbitals give a series of aromatic hydrocarbons (benzene, anthracene, phenanthrene, etc.). The C–C bonds using sp3 hybrid orbitals give various aliphatic hydrocarbons, such as methane, ethane, propane, adamantane, etc. Mixing the different types of hybridizations, sp, sp2, and sp3, in a molecule expands the variety of hydrocarbons. Figure 2.1 also shows how the inorganic carbon materials, diamond, graphite, fullerenes, and carbynes, result from the extension of these organic molecules to giant ones [1,2]. A simple repetition of C–C bonds with sp2 hybrid orbital gives planar hexagons of carbon atoms, as benzene, anthracene, ovalene, etc. The extension of this series of aromatic hydrocarbons reaches graphite, in which the σ bonds using the sp2 hybrid orbitals are reinforced by the delocalized π electrons. The giant planes tend to stack on each other due to the interactions between the π-electron clouds of the stacked layers, giving rise to weak van der Waals-like interactions. The somewhat curved corannulene molecule is formed by associating a pentagon of sp2 hybridized carbon atoms with five hexagons. By the polymerization of these corannulene molecules to form a closed shell, various sizes of carbon clusters are formed and the resultant carbon materials are called fullerenes,
© 2010 by Taylor and Francis Group, LLC
Structure and Texture of Carbon Materials
Aromatic hydrocarbons H2 C Fluorene Benzene sp2 Hydrocarbons Carbon H H C C C C H H H H 1,3-Butadiene sp sp3 H H H H C C C H H H H Propane Adamantane Ovalene Anthracene Carbon materials
H C C C C H Butadiyne H H H H C C C C C C C C H H H H Polyacetylene C C C C Polyyne C
C C C Cumulene Carbyne
FIGURE 2.1 Construction of organic hydrocarbons and inorganic carbon families, using the sp, sp2, and sp3 hybrid orbitals.
where carbon hexagons have to be located between the pentagons. The smallest closed shell is the buckminsterfullerene C60, consisting of 12 pentagons and 20 hexagons of carbon atoms. As shown schematically in Figure 2.1, the infinite repetition of C–C bonds using sp3 hybrid orbitals results in a three-dimensional network of carbon atoms, which is known to be diamond. The carbon atoms in the organic compound named as adamantane and in diamond are exactly in the same atomic positions. The infinite repetition of C–C bonds with sp hybrid orbital gives the carbon materials called carbynes, in which the carbon atoms form linear chains either with double bonds (one σ-bond with one π-bond) or with the alternative repetition of single (one σ-bond) and triple bonds (one σ-bond with two π-bonds), the former being called cumulene type and the latter polyyne type. Based on the extension by the repetition of three kinds of C–C bonds to infinite molecules, we may define carbon families, consisting of diamond, graphite, fullerenes, and carbynes . In each family, the structure shows characteristic diversities; representative structures are listed in Figure 2.2. The detailed diversity in structure will be explained in the following sections for each family. Most structures in each family are thermodynamically metastable, and the family is represented by the allotrope name. In Figure 2.2, some possibilities to accept foreign species are also illustrated.
The carbon family having a sp2 bonding type is represented by graphite, in which the layers of carbon hexagons are stacked in parallel. The ABAB… sequence belongs to the hexagonal crystallographic system (hexagonal graphite) . The ABCABC… stacking regularity is also possible,
© 2010 by Taylor and Francis Group, LLC
Carbons for Electrochemical Energy Storage and Conversion Systems
Doping into sphere
Doping in interstices
C60, C70, …C960 Multiwalled Fullerenes Variety in structure Carbyne Cumulene type Polyyne type
Hexagonal graphite Rhombohedral graphite Turbostratic structure Graphite Carbon family Diamond Cubic diamond Hexagonal diamond Diamond-like carbon
Variety in acceptance of foreign species
Substitution Intercalation Doping in interstices
FIGURE 2.2 Structural diversity in the carbon family and possibilities for accepting foreign species.
and belongs to the rhombohedral system (rhombohedral graphite) . The unit cells of these two allotropes are shown in Figure 2.3, together with their crystallographic data, space group, equivalent points, and lattice parameters. The rhombohedral and hexagonal cells are shown together in the figure presenting rhombohedral graphite.
Hexagonal graphite C
Rhombohedral graphite A
000 2 10 3 3
1 00 2 1 00 2
00 2 3
1 21 3 32 000 000 2 10 3 3 000 000
1 2 2 3 3 3 1 2 1 3 3 3
2 11 3 33
2 10 3 3 000
Space group: P63/mmc z number: 4 Equivalent points: 0,0,0; 2/3,1/3,0; 0,0,1/2; 1/3,2/3,1/2 Lattice parameters: a0=0.2462 nm, c0=0.6708 nm
(a) Rhombohedral system (thick lines) Space group: R3m z number: 2 Equivalent points: 1/6,1/6,1/6; 5/6,5/6,5/6 Lattice parameters: a0=0.3635 nm, α=39.49°
(b) Hexagonal system (double lines) z number: 6 Equivalent points: 0,0,0; 2/3,1/3,0; 1/3,2/3,1/3; 2/3,1/3,1/3; 1,0,2/3; 1/3,2/3,2/3 Lattice parameters: a0=0.2462 nm, c0=1.0062 nm
Unit cells of hexagonal and rhombohedral graphite with their crystallographic parameters.
© 2010 by Taylor and Francis Group, LLC
which is exactly the same as for the A layer.6].5). 1/3) is possible.4. for example. their presence was recently shown through a detailed analysis of scanning tunneling microscopy (STM) images . by grinding [5. The diffraction lines of graphite have to be classified into three groups. 1/3) translation (1/3. By repeating the same translation (2/3. where only the l even indices are allowed because of the extinction rule due to the ABAB stacking sequence of the layers. hk0. © 2010 by Taylor and Francis Group. However. and in this case the third layer is not at the same position as either the A layer or the B layer. In hexagonal graphite. 2/3) translation FIGURE 2. where the three-dimensional structure has to be established with graphitic stacking of layers. Although they are difficult to be differentiated in practical carbon materials by conventional techniques. The rhombohedral phase tends to saturate at around 33%. below 1300°C. additional lines indexed as 101 and 102 based on the rhombohedral structure appear around 44° in 2θ in the diffraction pattern of hexagonal graphite (Figure 2. the second layer (B layer) is translated by (2/3. and the lines with hkl indices come from the planes declined to the basal planes. 1/3). Figure 2.5 (top) shows the x-ray powder diffraction pattern of natural graphite with a high crystallinity.4 Translation of adjacent layers in hexagonal graphite to construct a regular stacking sequence. Therefore. 1/3) along the a and b axes from the first layer (A layer). LLC . The lines with hk0 indices are due to the reflection from the crystallographic planes perpendicular to the basal planes. the parallel stacking of the layers without any regularity occurs mostly in the carbon materials prepared at low temperature. This random stacking of layers is called turbostratic structure . mainly because of the strong anisotropy in structure. With increasing grinding time. which seems to be reasonable because the rhombohedral stacking is formed mainly due to the introduction of stacking faults in the crystallites having the hexagonal stacking regularity. In this case. giving the ABCA stacking. The rhombohedral structure of graphite was shown to form by applying shearing forces. with 00l. as shown schematically in Figure 2. The structural relation between hexagonal and rhombohedral graphite is explained in Figure 2.6. The lines with 00l indices are due to the reflection from the basal planes (hexagonal carbon layers and graphite basal planes). With a further translation by (1/3. 2/3) for the third layer. In addition to these regular stacking modes. it is said to be the ABA stacking. the layers of hexagons are usually small in size. the total translation becomes unity in the two directions.Structure and Texture of Carbon Materials b axis b axis A B B C 41 A β α C a axis a axis Second layer First layer A B (2/3. Therefore. In this random stacking. because of the introduction of ABC stacking regularities (stacking faults in the ABA stacking regularity) . and only few layers are stacked in parallel. the hkl lines are called three-dimensional lines. the fourth layer coincides with the A layer. and hkl indices. and is thus denoted as C layer. a second translation again by (2/3. two kinds of displacement are possible. translation and rotation.
42 Carbons for Electrochemical Energy Storage and Conversion Systems As-received natural graphite 002 004 101 103 100 102 006 112 105 110 104 90 20 30 40 50 60 70 80 2θ (CuKα)/degree Hexagonal 101 Hexagonal 100 Rhombohedral 101 Rhombohedral 102 As-received natural graphite Ground for 8h 19 h 35 h 45 h 60 h 42 44 46 2θ (CuKα)/degree FIGURE 2.6 Translation and rotation of neighboring hexagonal carbon layers to construct the turbostratic structure. (a) Translated (b) Rotated FIGURE 2.5 X-ray diffraction pattern of natural graphite and its change with grinding. © 2010 by Taylor and Francis Group. LLC .
Because of the interaction with the lower-lying atoms in the B layer. the spots form a hexagonal arrangement (Figure 2. the hexagonal carbon layer looks like a triangular arrangement of spots (Figure 2.8 STM images for the graphitic and turbostratic stackings.7. the interactions with the lower-lying atoms do not exist.) © 2010 by Taylor and Francis Group. Japan. Nagano National College of Technology. and consequently. The diffraction pattern is characterized by very broad 00l lines due to the small number of stacked layers. they are expressed as 10 and 11 in Figure 2. as shown on a petroleum coke heat-treated up to 1000°C in Figure 2. When graphite is observed by scanning tunneling microscopy (STM). however.7 X-ray powder diffraction pattern of a petroleum coke heat-treated at 1000°C having a typical turbostratic structure. (Courtesy of Prof. including the 100 line for hexagonal graphite and the 101 line for rhombohedral graphite (Figure 2. mainly the carbon atoms designated by α in Figure 2.Structure and Texture of Carbon Materials 43 On the other hand. and by unsymmetrical hk lines and not hkl lines due to the random turbostratic stacking of layers. Oshida.7. because it consists of random stackings of small layers. With permission. K.8a).5). The diffraction lines due to the planes perpendicular to the hexagonal carbon layers have a missing l index because of the absence of regularity in the direction along the normal to the layers. (a) Graphitic stacking (b) Turbostratic stacking 1 nm 1 nm FIGURE 2. Nagano. In the turbostratic structure. therefore. The grinding of natural graphite for a long time results in broadening all the diffraction lines.8b) . the powder pattern that is given by low-temperature-treated carbons is quite different from natural graphite. LLC . because of the irregular stacking. 10 004 002 11 20 30 40 60 70 50 2θ (CuKα) (degree) 80 90 FIGURE 2.4a are detected under STM.
A single-wall carbon nanotube is characterized by its diameter and chiral vector [14. which is a characteristic of the fullerene family. LLC .13]. The closed ends of a nanotube consist of carbon pentagons with hexagons. another way to increase the number of hexagons is to make two groups of six pentagons apart from each other.3 FULLERENE FAMILY Although based on sp2−type hybridization of carbon atoms. from the smallest closed shell of C60 to giant fullerenes [12. the bonding nature in fullerenes is different from graphite in the fact that the molecule is curved by the introduction of pentagons. which is the fundamental structural unit composing the graphite family. 2 θ C60 C70 Single-walled Double-walled C240 Single-layer (hexagonal carbon layer or graphene) Multiwalled C54040 Fullerenes Carbon nanotubes Multilayers with regular stacking Graphite FIGURE 2. 2. a wide range of structural diversity may result in the graphite family [10. The texture at the nanometric scale (nanotexture) will be separately discussed on the carbon materials classified in the graphite family.2.e. most of them can be dissolved into an organic solvent. The illustration on the right-hand side of Figure 2. are highly anisotropic. which results in a single-wall carbon nanotube. In this fullerene family.1). indicating that introducing too many stacking faults leads to a turbostratic structure . The introduction of additional hexagons while keeping a closed shell morphology leads to giant fullerenes. The repetition of this curved molecule can result in various closed shells. T O a1 a1 a2 Ch a2 A 5. giving a characteristic color. the graphite family can have various textures.. Fullerenes behave as molecules . the carbon nanotube seems to locate in between the graphite and fullerene families. In different scales.9.15].. carbon nanotubes.9. as seen in corannulene (Figure 2. Since this turbostratic structure can be partly transformed into a regular stacking of layers with a heat treatment at high temperatures. To some extent. the 100 line becomes broad and unsymmetrical. The graphitization degree is defined as the probability of occurrence of the regular graphitic AB stacking in turbostratic stackings. because it has some of the graphite characteristics together with those of fullerenes. and graphite. As shown in the center of Figure 2. i. as shown on the left-hand side of Figure 2.9 presents an example.11].e. i. and the tube wall consists of carbon hexagons and can be considered to be rolled from an hexagonal carbon layer. the variety of structures is mainly due to the number of carbon atoms building the closed shell. mainly because the basic structural units (BSU).44 Carbons for Electrochemical Energy Storage and Conversion Systems After 60 h of grinding.9 Structural relationships between fullerenes. the stacked hexagonal carbon layers. © 2010 by Taylor and Francis Group. which is exceptional in the carbon families because all other materials are not dissolved in any organic solvent.
and is called diamond-like carbon (DLC) . was found in either thin films or nanoparticles . in the case of a random rotation between the two basement triangles of tetrahedra. and it contains a relatively large amount of hydrogen. a periodic and regular repetition of the C–C bond is required in a long range. If there is no rotation between these two basement triangles (Figure 2. to make a tetrahedron because of directional sp3 bonds. Looking down these two tetrahedra centered on the A and B atoms along their connecting line.10a). including A. an amorphous structure is formed . most of which are supposed to be connected with hydrogen atoms for stabilization. as shown in Figure 2.10c). Figure 2. Diamond is very hard and electrically insulating. Figure 2. consisting of a face-centered cubic unit cell with a parameter of 0. If these two basement triangles are rotated with respect to each other by 60°. LLC . are cubic. Most of the diamond crystals. DLC is as hard as diamond crystal. in other words.Structure and Texture of Carbon Materials 45 2. A A B (b¢) (b) Cubic diamond B A (a) Basic carbon tetrahedra (c) Hexagonal diamond (c¢) B FIGURE 2. because it is also based on sp3-hybridized atoms. In the case where a long-range periodicity is not attained between interconnected tetrahedra (Figure 2. the carbon atom A has to be connected with four carbon atoms.10b. there are two possibilities in mutual relation between the two basement triangles consisting of three carbon atoms. in which the purely covalent chemical bonds extend three-dimensionally. the structure belongs to the hexagonal system (hexagonal diamond.10c') . Construction of the cubic and hexagonal diamond structures based on tetrahedra of © 2010 by Taylor and Francis Group.10b').4 DIAMOND FAMILY Diamond consists of sp3-hybridized carbons. either occurring in nature or synthesized. some carbon atoms cannot form chemical bonds with the neighboring carbon atoms. A metastable crystalline phase of carbon atoms. Because of a random rotation between tetrahedra. the resultant diamond crystal belongs to the cubic system (cubic diamond. including B. and the atom B has also to be surrounded by four carbon atoms.10a. This is usually obtained as a thin film. For a couple of carbon atoms indicated as A and B in Figure 2.3563 nm. which give two crystal structures. mainly because a random repetition of tetrahedra is difficult to keep on a long distance.2.10 carbon atoms. To construct a diamond crystal.
Its effects on accelerating the development of graphitic stacking [25. even though the amount substituted is very limited [23..24].e. Only the intercalation of either iron or potassium is reported to stabilize Chain of carbon atoms Layer formation FIGURE 2. i.26] and on improving the electrode performance in lithium-ion rechargeable batteries have been reported . The detailed structure of carbynes is not yet clarified. A structural model is illustrated in Figure 2. The substitution of either boron or nitrogen atoms for carbon atoms is possible for all carbon families. Boron substitution has extensively been studied to improve the functions of carbon materials in the graphite family. Diversities in foreign atom acceptance are illustrated for each family in Figure 2. Foreign atoms are intercalated between the layers that are supposed to stabilize the carbyne structure. though the state of the nitrogen atoms in the carbon matrix was not yet well understood. the variety of structures seems to be mainly due to the number of carbon atoms forming a linear chain. 2.5 CARBYNE FAMILY Carbynes are supposed to be formed of sp-hybridized carbon atoms bound linearly. in other words. Intercalation between the layers of graphite and carbynes is effective and useful for the modification of their properties. © 2010 by Taylor and Francis Group.2. LLC .2. Nitrogen-substituted diamond crystals occur rarely in nature. was also reported . C59N (heterofullerene). and to the density of chains in a layer. various modifications have been investigated on different types of carbon materials. In the carbyne family.11 Structural model for a carbyne. Nitrogen substitution in buckminsterfullerene. Since this substitution is expected to modify the properties of carbon materials without noticeable structural changes.6 MODES OF ACCEPTANCE OF FOREIGN SPECIES Each carbon family also shows various characteristic possibilities for accepting foreign species. Recently.2. where some numbers of sp-hybridized carbon atoms form chains that associate together by van der Waals interaction between π-electron clouds to make layers.1) .11. to the layer thickness. an alternative repetition of single and triple bonds (polyyne) and a simple repetition of double bonds (cumulene) (Figure 2. but some structural models have been proposed [19–22]. and then the layers are stacked. giving two possibilities. where two π electrons have to be involved. nitrogen-containing carbon materials were reported to have a high capacitance in electrochemical capacitors .46 Carbons for Electrochemical Energy Storage and Conversion Systems 2.
CO2 H2 (CN)2. Associated with this hydrocarbon release. which occupy all the tetrahedral and octahedral interstices between the molecules.g. gas. AsF5 and SbF5 graphite intercalation compounds were reported to have high electrical conductivity [34. but to date experimental results have not been reported. Intercalation/deintercalation of lithium ions is the fundamental electrochemical reaction for the discharge/charge of lithium-ion rechargeable batteries . the insertion into the inner space of the closed clusters  and the covalent bonding of organic radicals . and interesting results have been obtained [30. Rare earth elements can be inserted into fullerene cages (endohedral metallofullerenes).3 FORMATION OF CARBON MATERIALS 2. By contrast.35]. are produced by heat treatment of some organic polymers. The intercalation of sulfuric acid is widely used for the production of exfoliated graphite. cyclization and aromatization proceed in the Temperature (°C) 200 600 1000 1500 2000 Main outgassed components Aromatic Aliphatic CH4 hydrocarbons hydrocarbons CO.) can be intercalated in the galleries between neighboring hexagonal carbon layers.3. Either donors (such as lithium. or liquid Carbonaceous solid Carbon solid FIGURE 2. in which the carbon atom is the principal constituent. a wide variety of foreign species.31].. doping by intercalation into the space between the carbon chains in a layer is theoretically possible.e. although it strongly depends on the carbon precursor used. potassium). bromine. aliphatic and then aromatic molecules with low molecular weight are released as gases. etc. At the beginning of precursor pyrolysis. there are two additional possibilities to accept foreign species.12 for a solid carbon precursor. In the carbyne family. etc. and even molecules. but they were never used in practice mainly because of instability of the compounds in air. The Gd-metallofullerenol Gd@C82(OH)n has been reported to be useful as a contrast agent for magnetic resonance imaging . have been intercalated into the carbon materials belonging to the graphite family. atoms. © 2010 by Taylor and Francis Group. which is converted to a graphite sheet for shielding and packing . potassium. such as phenolic resin or cellulose. the process is called carbonization. giving rise to a superconductive material C60(AM)3 . LLC .1 CARBONIZATION PROCESS When carbon materials. by indicating the main outgassed components and changes in residues. in addition to the substitution of carbon atoms in the shell and doping in the interstices between molecules. carbon precursors. ions.Structure and Texture of Carbon Materials 47 the structure of carbynes .12 Carbonization process of a solid precursor.. In the fullerene family. The general scheme of the carbonization process is shown in Figure 2. up to a temperature around 2000°C in an inert atmosphere. ferric chloride. 2. mainly because some of the C–C bonds are weaker than C–H bonds. N2 Graphitization Growth of layers and improvement of stacking order Pyrolysis Reactions in residue Cyclization aromatization Carbonization First carbonization Second carbonization Polycondensation Formation of carbon layer Growth of layers States of residue Solid Solid.) or acceptors (such as sulfuric acid. The buckminsterfullerene C60 crystal can be doped with alkali metals (AMs) (e. i. higher than metallic copper.
The carbonization process may be divided into two steps.e. the first carbonization being associated with the evolution of hydrocarbon gases and the second carbonization with the evolution of light gases. The carbonization proceeds in three steps: (i) the first step occurs in a rather narrow temperature range of 500°C–600°C. a negligibly small shrinkage. the “carbonization” process is rather simple. a heat treatment up to 2000°C is required.. and a little shrinkage. CO. and amount of evolved gases with carbonization temperature for a polyimide (Kapton) film. LLC Evolved gas (μl/g °C) .13 Changes in weight. To eliminate the latter. the evolution of small amounts of methane and hydrogen. and CH4. From around 600°C. the main gas evolved is H2 because of polycondensation of aromatics. the whole process from the precursor to the carbon material is called “carbonization. mainly foreign atoms such as oxygen and hydrogen are released as CO2. and concentration (particularly in the case of gaseous precursors). strongly depending on the chemical state of these foreign atoms in the carbonaceous solid. heating rate. as shown above. As an example. carbonaceous solids. often overlap with each other. The residual solids carbonized above 800°C are often called carbon materials. pressure. (ii) the second step occurs in the temperature range from 600°C to 1000°C (first carbonization) with a small weight loss. In this stage. © 2010 by Taylor and Francis Group.13 . Usually. and it is known that the starting molecular structure of the polyimide used governs the structure and nanotexture of Molecular structure of starting polyimide (Kapton) O O N (a) O N O O n Changes in weight and size of the film 100 Weight Evolved gas (μl/g °C) Shrinkage (%) 80 Weight (%) 60 40 Shrinkage 20 0 (b) 0 400 600 800 1000 Carbonization temperature (°C) (c) 10 20 1500 Changes in gases evolved from the film CO 1000 100 500 H2 CO2 CH4 N2 50 0 400 0 600 800 1000 Carbonization temperature (°C) FIGURE 2. film size. The release of nitrogen in the third step was found to continue up to temperatures higher than 2000°C. In the case of polyimides. the evolution of gases during the carbonization of a polyimide film (commercially available Kapton film with 25 μm thickness) together with the changes in weight and size of the film up to 1000°C is shown in Figure 2. showing an abrupt weight loss associated with the evolution of a large amount of carbon monoxide and a pronounced shrinkage along the film (pyrolysis). and S. mainly temperature. and a small weight loss (second carbonization).48 Carbons for Electrochemical Energy Storage and Conversion Systems residues and then polycondensation of aromatic molecules occurs. the residues are in either liquid or solid phase depending on the starting precursors. Above 800°C. but still contain hydrogen and a small amount of foreign atoms. N.” This process depends strongly on the carbon precursors and also on the heat treatment conditions. such as O. The pyrolysis of precursors and carbonization of the pyrolysis products. leaving a large number of pores in the film if it was heated continuously up to 2400°C . i. and the residues may be called carbonaceous solids that still contain hydrogen. (iii) the third step is accompanied by the evolution of nitrogen.
without any catalyst Carbon vapor Carbon vapor Plants. In Table 2. carbon fibers (VGCFs) and carbon nanofibers with various nanotextures and morphologies are produced. When a solid substrate is placed in the carbonization system. A large variety of carbon materials over the whole carbon family was produced through gas-phase carbonization (Table 2. various nanotextures Thin film. pitch. are added to the carbonization system. carbonization is the most important process for producing carbon materials. Moreover.1). the nanotexture of carbon materials is principally established during the carbonization process. LLC . Therefore. coal. phenol resin. carbon blacks are obtained. 2. and phenol resin with stabilization Polyimide films Liquid-phase carbonization Pitch.1. decomposition in space Hydrocarbon gases. preferred orientation Fibrous morphology. single-wall. and the representative carbon materials formed are listed with their characteristics. For a high concentration of hydrocarbon gases. the carbonization processes are classified on the basis of the intermediate phases of the precursor used . molecular nature Highly porous adsorptivity Amorphous structure. various degrees of orientation the resultant carbons. pyrolytic carbons are produced. and multiwalled Spherical.2 GAS-PHASE CARBONIZATION When carbon materials are produced through the decomposition of hydrocarbon molecules in gaseous phase. Poly(acrylonitrile).3. cellulose. so-called “structure” Various textures. gas impermeability. © 2010 by Taylor and Francis Group. have a much more complicated molecular composition so that their carbonization processes are much more complicated. carbon nanotubes and fullerenes are formed.Structure and Texture of Carbon Materials 49 TABLE 2. nanotexture has determining effects on the structural changes at high temperatures and also on the properties of carbons.1 Carbonization Processes for the Production of Various Carbon Materials Carbonization Process Gas-phase carbonization Precursors Hydrocarbon gases. However. If some fine metallic particles. deposition on substrate Hydrocarbon gases. sp3 bond. the carbon precursors used for industrial carbonization processes. with metal catalysts Hydrocarbon gases. conchoidal fracture surface Fibrous morphology. etc. various carbon materials. high mechanical properties Film wide range of graphitizability Spherical particles Solid-phase carbonization Carbon fibers Carbon films Cokes Mesocarbon microbeads (MCMB) Polycrystalline graphite blocks Cokes with binder pitches Various densities. carbon nanofibers DLC Carbon nanotubes Fullerenes Activated carbons Glass-like carbon Characteristics Fine particles. From the carbon vapor produced by electric-arc discharge or laser ablation. As it will be explained below. the process is called gas-phase carbonization. such as Fe or Ni. cellulose. and pitches Furfuryl alcohol. amorphous structure Tubular. such as pitches. coal tar Carbon Materials Carbon blacks Pyrolytic carbons Vapor-grown carbon fiber (VGCFs).
which are in different sizes and more or less coalesced into aggregates. They are characterized by spherical primary particles. LLC .14 Transmission electron micrographs of carbon blacks. On the basis of the reaction process and raw materials.2 Pyrolytic Carbons Carbon deposition occurs on the surface of a substrate inserted into the carbonization system using hydrocarbon gases. channel blacks. lamp blacks.50 Carbons for Electrochemical Energy Storage and Conversion Systems 2. small substrate particles are fluidized (a) Thermal black 300 nm (b) Channel black (c) Furnace black (d) Furnace black FIGURE 2. 2. which is produced as a by-product of heavy oil gasification and has a size of primary particles of 30–40 nm and a high surface area (ca. such as methane and propane .3.3. In the former.2. © 2010 by Taylor and Francis Group. 1300 m2/g) . which is heated either by direct passing of electric currents or from the surroundings. This process is a kind of chemical vapor deposition (CVD) and the products are called pyrolytic carbons.1 Carbon Blacks Carbon blacks formed through incomplete combustion of either gaseous or mist-like hydrocarbons are very important industrial products . Ketjenblack. In order to control the structure. have been frequently used as conductive additives in the electrodes of primary and secondary batteries and also for electrochemical capacitors. carbon blacks are classified into furnace blacks. thermal blacks.14). and acetylene blacks.2. the deposition conditions have to be controlled. and also acetylene black. They have been used as colorants in inks since the third century AD and are now applied in large amount for rubber reinforcement. the substrate is placed in a furnace. what is called “structure” in the field of rubber reinforcement (Figure 2. The deposition can occur on either static or dynamic substrates. In the latter.
M. dark-field images with 002 and 10 diffractions. it is necessary to use a low methane pressure as low as 1. With permission. Shinshu University. In order to prepare pyrolytic carbon with high density at 1400°C–2000°C. The factors controlling the structure and properties of pyrolytic carbons are (i) the kind of precursor hydrocarbon gas.48]. and finally (v) the geometrical arrangement of the furnace. Endo. (iii) the deposition temperature. particularly the ratio of the substrate surface area to the volume occupied by the gas .15d) . Nagano. LLC . The long and straight layers of the central hollow tube are aligned exactly Central tube (carbon nanotube) 10 nm (a) 10 lattice fringes 1 nm 002 lattice fringes (b) 1 nm 002 lattice fringes (c) 1 nm (d) FIGURE 2. and 002 and 10 lattice fringes) shows that the resultant VGCFs are constituted of two parts.7 × 10 −2 mbar. which is governed by the gas flow rate and the size of the furnace.15: a hollow tube with few straight layers (carbon nanotube) (Figure 2. The transmission electron microscopy (TEM) analysis using various modes (bright-field images. selected area electron diffraction. which is known to be mainly due to the formation of carbon black particles incorporated into the pyrolytic carbon . High methane pressure of 4 mbar gives low density pyrolytic carbon in this temperature range. 2. as shown in Figure 2. Japan.15b and c) and oriented small layers deposited on the wall of the hollow tube (Figure 2. (ii) the gas concentration.3 Vapor-Grown Carbon Fibers and Carbon Nanofibers VGCFs are formed on a substrate from benzene vapor in a flow of high-purity hydrogen using fine iron particles as catalyst [47.Structure and Texture of Carbon Materials 51 in the furnace. (iv) the contact time between the gas molecule and the substrate heated at a high temperature.) © 2010 by Taylor and Francis Group.3.2. (Courtesy of Prof.15 Transmission electron micrograph and lattice fringe images for VGCF.
) © 2010 by Taylor and Francis Group. The hollow tubes thus obtained show a wide range of diameters from 1 to 50 nm. in which nanometric catalyst metal particles are formed in situ by the decomposition of its precursor. and are differentiated from carbon nanotubes and also from VGCFs . carbon helical microcoils with a controlled pitch were prepared [62–64]. Most of them are closed at the end with the help of pentagons.74]. Fibrous carbons with a stacking of cup-like carbon layers along the fiber axis.2. and the small layers deposited on the wall of the tube are preferentially and concentrically oriented along the fiber axis.60]. Now. which are well aligned perpendicular to the precursor wafer [73. instead of the method where the catalyst is seeded on the surface of a substrate plate (seeding catalyst method).16 Transmission electron micrograph of a carbon nanotube.3. Since most VGCFs can be changed to well-graphitized carbon fibers and can be prepared with high purity. without the coexistence of other carbon forms like carbon blacks. the floating catalyst method was developed . 2. under different conditions [54–58]. By selecting the arc discharge conditions between the graphite electrodes. Similar works reported recently are aiming to prepare highly pure carbon nanotubes with a high yield [59. LLC . Nagano. Figure 2.66].16 shows the TEM image of a carbon nanotube.4 Carbon Nanotubes Carbon nanotubes were found in the carbon deposits on the graphite anode after arc discharge in He atmosphere . Vertically aligned singlewall carbon nanotubes were synthesized from an alcohol with a high formation rate. Endo. The carbon nanotubes consisting of a single carbon layer were also found later [70. several works were performed to prepare fibrous carbons through the decomposition of various gases. were also prepared in a similar process [65. The formation of similar VGCFs was reported by using different precursor hydrocarbon gases. and deposition conditions [50–52]. Shinshu University. these fibrous carbons are called nanofibers (or nanofilaments). their length reaching up to 5 μm . Carbon nanohorns.71]. catalyst metals. were also synthesized by a similar technique . By selecting the decomposition conditions. The decomposition of a SiC single crystal wafer under reduced pressure (1 × 10 −4 mbar) at 1700°C was found to give carbon nanotubes. 10 nm FIGURE 2. Japan.52 Carbons for Electrochemical Energy Storage and Conversion Systems parallel to the fiber axis. cup-stacked nanofibers. relatively high yields of carbon nanotubes were reported. carrier gases. The temperature at the graphite electrode was estimated to reach up to 2500°C. (Courtesy of Prof. To get a high yield of VGCFs. the smallest diameter being the same as the size of the smallest fullerene C60. not only hydrocarbons but also CO. and their walls consist of different numbers of carbon layers. M. showing a high storage capacity for methane. The addition of a small amount of VGCF into the electrode of lead-acid rechargeable batteries was reported to improve the performance .
which contain a large number of closed pores.5 Fullerenes The carbon cluster C60 was first found in the soot formed by laser ablation of graphite in He atmosphere and was named as buckminsterfullerene [12. for example. which is used. For the predominant applications of activated carbons as adsorbents. carbon disulfide. where macropores (>50 nm width) and mesopores (2–50 nm Activated carbon produced from coconut shell Macropore Relative positions of the pores Macropore Micropore Mesopore 10 μm (a) (b) FIGURE 2. and also cellulose can be converted to carbon materials by solid-phase carbonization. which is called “activation. 2. He atmosphere gives relatively high yield of fullerenes in most cases. and are now used widely not only in our daily life but also in various industries for production processes and for the treatment of the waste.Structure and Texture of Carbon Materials 53 2. including pitches and coals.” Various carbon precursors. C60 was also found in the carbon deposits formed by arc discharge between graphite electrodes . 2. such as C70. If the carbonization is performed so slowly that the resultant carbonaceous solids can shrink completely. C960.17 Scanning electron micrograph of an activated carbon and pore structure model. the scanning electron microscopy (SEM) micrograph of a carbon prepared from coconut shell. In order to develop the small pores. which are usually evaluated by surface area and pore size distribution [77–79]. C82. a large number of open pores are formed.13]. The pores observed by SEM are macropores. micropores with a width less than 2 nm. is shown.. which were examined for the formation of fullerenes. which originated from the cell structure of the precursor coconut shell. but their presence before activation is preferable for creating micropores in the walls. but also some thermoplastic resins.3. not only thermosetting resins. Carbon clusters with different sizes. such as phenol-formaldehyde and furfuryl alcohol.17a.2. etc. the pore texture is the most important property to be controlled. were identified and this series of clusters was called fullerenes.1 Activated Carbons In activated carbons.3. most thermosetting resins. © 2010 by Taylor and Francis Group. are used. This carbon cluster C60 could be extracted using solvents. When the carbonization of most of these precursors proceeds rapidly. the resultant carbon materials become porous.3. Among the different gas atmospheres.17b. LLC .3. They have been used as adsorbents since prehistoric age. In Figure 2. such as toluene.3 SOLID-PHASE CARBONIZATION In contrast to gas-phase carbonization. a slight oxidation of carbonized materials is usually carried out. These macropores are not effective for adsorption of various molecules. including natural biomass as plants. The pore texture of most activated carbons is illustrated in Figure 2. and could also be separated from the deposits by vaporization at around 400°C in vacuum . as a filter in cigarettes. …. the so-called glass-like carbons are produced.
the so-called stabilization. During gas activation.. the pores may grow from micropores to mesopores and finally to macropores. steam. Figure 2. KOH.19 Progressive change from ultramicropores through supermicropores to mesopores during air activation of glass-like carbon spheres. etc. SEM image Micropore volume Pore volume (arb) Supermicropore volume Ultramicropore volume Mesopore volume 1 10 Oxidation time (h) 100 FIGURE 2. © 2010 by Taylor and Francis Group. For thermoplastic precursors.54 Carbons for Electrochemical Energy Storage and Conversion Systems width) work as paths for oxidizing agents to create micropores during the activation process and also for adsorbate molecules to reach the micropores during adsorption application. and then the ultramicropores Thermosetting carbon precursor Carbonization in inert atmosphere Activation Gas activation Chemical activation Washing Thermoplastic carbon precursor Stabilization in oxidizing atmosphere Activated carbon or porous carbon FIGURE 2. CO2.19 shows the changes in pore size during air activation of glass-like carbon spheres .7 nm) are formed.18 Preparation process of activated carbon from thermosetting and thermoplastic precursors. [77–79]. etc. Figure 2. which is a slight oxidation. At the very beginning of oxidation. and chemical oxidation using H3PO4. different processes are employed: oxidation using diluted oxygen gas. ultramicropores (<0. LLC .18 shows a conventional process for the production of activated carbon from thermosetting and thermoplastic precursors. air. For activation. is required prior to carbonization. presumably by the opening of closed pores existing in the glass-like carbon matrix. ZnCl2.
20b) . By the control of the micropore size. A proper combination of micropores and mesopores is pointed out to be important for the electrodes of electric double layer capacitors to get a high performance [82. etc.0 1. Figure 2. through an exact control of the heating process [88. Mesopores are effective for the adsorption of gasoline vapor composed from large hydrocarbon molecules (Figure 2. LLC .Structure and Texture of Carbon Materials Activated carbons 10 ΔV/Δ(log d) (mL/g nm) 8 For gas adsorption 6 4 2 0 0.20 Pore size distributions in various porous carbons.20d shows a distribution of cross-sectional area of macropores formed in worm-like particles of exfoliated graphite. Figure 2. the carbonization and activation processes are often combined in one heat treatment.86] and macromolecular biomedical fluids . the activated carbons may be successfully used as molecular sieves for various gases. poly(furfuryl alcohol). cellulose.7–2 nm). They are characterized by an amorphous structure and also by © 2010 by Taylor and Francis Group. grow to supermicropores (0. which play an important role in the recovery of spilled heavy oils [85.89].2 Glass-Like Carbons Glass-like carbons (glassy carbons) are produced by the pyrolysis of different precursors. a great success to get a high surface area reaching 3000 m2/g was obtained using KOH for activation .0 Frequency 0 Frequency 50 100 150 Pore area (μm2) 200 0 5 (c) 10 15 20 Pore width (nm) 25 30 (d) 0 500 1000 1500 2000 Cross-sectional area of pore (μm2) FIGURE 2. The pore size distributions of activated carbons used for the adsorption of small gas molecules and decolorization of water are shown in Figure 2.1 (a) For decolorization ΔV/Δ(log d) (mL/g nm) 20 Activated carbon for vehicle canister 55 15 10 5 1 10 100 1000 Pore width (nm) 0 (b) 1 5 10 Pore width (nm) 50 Carbon with bimodal mesopores Worm-like particle of exfoliated graphite ΔV/Δ(log d) (mL/g nm) 2.3.20c shows a bimodal distribution of mesopores in the carbon prepared from Mg citrate and gluconate mixture..3. such as phenol–formaldehyde resin.5 0.0 0. For chemical activation. which has an excellent rate performance in the electric double layer capacitors .83]. Recently.5 1.20a. 2.
oxygen. so that the heating rate for carbonization is crucial for the production of glass-like carbons. Tokai Carbon Co. for which micropores are known to be responsible..) properties very similar to inorganic glasses. etc. suggesting that most of the pores are closed. The formation of closed pores with a rather homogeneous size of about 3 nm was reported on a glasslike carbon. volume. and gas impermeability. volume. The pores formed initially during the pyrolysis and carbonization of the precursor below 800°C are closed above 800°C.3 Carbon Fibers In order to produce carbon fibers from poly(acrylonitrile) (PAN) and various pitches. 2. almost gas-impermeable. hydrochloric acid vapor. It suggests that a large number of pores exist in glass-like carbons. In Figure 2. Ltd.5 g/cm3. Emmett. and show a very low gas permeability of 10 −12 cm2/s. while the bulk of the product shrinks. but all of them are closed.3–1.3. the volume of which reached around one-third of the bulk .21.56 Carbons for Electrochemical Energy Storage and Conversion Systems Weight and volume changes (%) 90 70 Weight change 50 Water vapor adsorption (mass%) Volume change 40 12 8 4 0 BET surface area (m2/g) BET surface area 20 Water vapor adsorption 0 400 800 1200 1600 2000 Carbonization temperature (°C) FIGURE 2. (Courtesy of Dr. such as high hardness.21 Changes in weight. .3. The rapid decreases in weight and volume up to 700°C–800°C are due to the precursor pyrolysis and correspondingly the Brunauer. The most important parameter for their production is a very slow heating slower than the rate of shrinkage to compensate the formation of open pores due to the evolution of decomposition gases from the precursor block. With permission. Yamada. Japan. stabilization is essential after the spinning. BET specific surface area (surface area determined by the Brunauer. which consists of a chemical reaction using different oxidizing gases. and adsorption of water vapor with carbonization temperature are shown for poly(furfuryl alcohol) condensates . The commercially available glass-like carbons have a bulk density of 1. Above 800°C. The stabilized fibers are then © 2010 by Taylor and Francis Group. the BET surface area and water vapor adsorption decrease quickly. Teller method). S. and water vapor adsorption during the carbonization of poly(furfuryl alcohol) to form glass-like carbon. chlorine. the changes in weight. Shizuoka. LLC . brittle conchoidal fracture. BET surface area. such as air. however. Emmett and Teller (BET) surface area and adsorption of water vapor increase.
the stabilization process is not necessary and the spinned fibers are subjected directly to carbonization (intrinsic solid-state carbonization).13b . Based on their mechanical properties. from highly crystalline graphite to amorphous glass-like carbon films . Even if these changes in weight and size are not so small. When cellulose and phenol fibers are used as precursors. high modulus and high strength types . Polyimide films with different molecular structures have been developed because of their practical and promising applications. isotropic-pitch. the yield after carbonization is relatively high. general-purpose and high-performance grades. i.3.and pitch-based carbon fibers. and their characteristics are summarized. 2. etc.3.4 Carbon Films Polyimides have been developed as thermoresistant polymers and used in different fields. the latter being classified into two series.22 shows a crane made by paper folding. This is a typical case in which the molecular structure of the organic precursors and the texture of the films govern the structure and texture of the resultant carbon films. As shown on a polyimide Kapton film in Figure 2. about 50 wt%. Figure 2.2. such as pitches. crystallinity and preferred orientation of hexagonal carbon layers.2 Classification of Carbon Fibers Based on Their Precursors and Their Characteristics Precursor PAN Isotropic pitch Mesophase pitch Cellulose Phenol Hydrocarbon gases Carbon Fibers PAN-based carbon fibers Isotropic-pitch-based carbon fibers Mesophase-pitch-based carbon fibers Cellulose-based carbon fibers Phenol-based carbon fibers VGCFs Characteristics Different grades and types General-purpose grade Random cross-sectional nanotexture High modulus types Various cross-sectional nanotextures General-purpose grade Random nanotexture General-purpose grade Random nanotexture High graphitizability Ring texture in cross section subjected to solid-state carbonization (extrinsic solid-phase carbonization) in inert atmosphere. depending on the pitch precursors subjected to spinning. which become viscous fluids before carbonization. The latter is further divided into two types.e. This process has been used to produce various polycrystalline graphite blocks for steel refining and electrical discharge machining.3. The heat treatment of these films at high temperatures leads to a wide variety of carbon structures. the form of which is kept after carbonization up to 1300°C and even after graphitization at about 3000°C. structural components of nuclear reactor. The resultant carbon fibers are called PAN.4 LIQUID-PHASE CARBONIZATION Liquid-phase carbonization occurs for some precursors. carbon fibers are classified into two grades. although a little care to avoid mechanical shock is required. carbon fibers are classified on the basis of their precursor. © 2010 by Taylor and Francis Group. jigs for the growth of semiconductor crystals. and the linear shrinkage along the film is slightly larger than 20%. it is noteworthy to mention that the film can keep its original form. 2.. LLC . especially in the field of electronics. In Table 2.Structure and Texture of Carbon Materials 57 TABLE 2.and mesophase-pitch-based.
carbon blacks. or cold isostatic pressing (CIP or rubber pressing). the compressive force is applied hydrostatically. are sometimes employed. In advance. coke is used as a filler and a pitch as a binder . petroleum and coal tar pitches are used in most cases.3 mm are fabricated by this forming process. H. as mentioned above. By isostatic pressing. cokes derived from petroleum and coal tar pitches are usually used. The filler and the binder are mixed at a temperature higher than the softening point of the binder. AIST. but natural graphite. in accordance with the requirements of the applications. the spheres grow and coalesce with © 2010 by Taylor and Francis Group. LLC . The particle size of the filler and the mixing ratio of the filler to the binder have to be controlled. 2. giving the so-called needle-like cokes. the filler particles are statistically aligned perpendicular to the compressing direction. and also recycled graphite particles are sometimes included. For the filler. However. (i) in the process of filler coke preparation and (ii) in the carbonization of the binder pitch. The carbon blocks heattreated at a high temperature are often called “polycrystalline graphite” or “synthetic graphite. which are called mesophase spheres. Forming is an important process for the fabrication of polycrystalline graphite blocks. and also leads for automatic pencil with a diameter as thin as 0.3. With permission.58 Carbons for Electrochemical Energy Storage and Conversion Systems (a) Polyimide film (b) After carbonization (c) After graphitization FIGURE 2. carbon rods with different sizes. For the binder. which is applied for the fabrication of carbon brushes for electric motors and electric contacts. In the course of liquid-phase carbonization of pitches. thermosetting resins.22 A crane made from a polyimide film by the paper folding technique and after its carbonization and graphitization. which is usually called carbon past. because it governs the preferred orientation of the filler particles. the cokes are carbonized to avoid a large number of volatiles that might introduce some shape distortion and cracks in the product and also might reduce the density. By further heating. is formed after warming up at a temperature around 150°C by either extrusion. (Courtesy of Dr.3. The extrusion gives a preferred orientation of either flaky or needle-like filler particles along the direction of extrusion. Japan. molding. Hatori. such as phenol and epoxy resins.1 Polycrystalline Graphite Blocks To produce graphite blocks. The formed blocks are carbonized at a temperature of 700°C–1000°C (sometimes called calcination) and then graphitized at a high temperature above 2500°C.) 2.” For producing graphite blocks. liquid-phase carbonization is involved in two steps. which are now important raw materials in the production of large-sized graphite electrodes for metal refining . because they have relatively high carbon yield as about 60 wt%. optically anisotropic spheres are formed first. which leads to producing isotropic high-density graphite blocks. Tsukuba. in this case. Electrodes for metal processing with large diameter. The mixture thus prepared.4. the filler particles are randomly oriented. In the molding process.4. and also because they give a carbon similar to the filler cokes after carbonization.2 Cokes and Mesocarbon Microbeads Cokes are also the product of liquid-phase carbonization of pitches. The nanotexture of the resultant cokes can be changed by applying a shear stress during liquid-phase carbonization.
20 μm FIGURE 2.24 Scanning electron micrograph of MCMB.1 Template Method The template carbonization technique was first developed for the preparation of thin. A series of polarized-light microscope images (Figure 2. Japan. two-dimensional graphite layers using layered compounds. (b) growth and (c) coalescence of mesophase spheres in a pitch. In relation to electrochemistry. Carbon nanofibers were © 2010 by Taylor and Francis Group.95]. Tokyo. shown in Figure 2.5 NOVEL CARBONIZATION PROCESSES The recent developments in science and technology require a more exact control of structure/ nanotexture and properties of various materials. With permission. Ltd.24. 2.5. A series of works applying this technique reveals a high possibility to control the dimensionality of morphology by selecting suitable template materials: one-dimensional carbon nanofibers were synthesized using anodic aluminum oxide films.3. are called mesocarbon microbeads (MCMB) and have been used as the anode material of lithium-ion rechargeable batteries . The anisotropic mesophase spheres can be separated from the isotropic pitch matrix by using a solvent .101]. and carbonization of organic aerogels . and three-dimensional microporous carbons using zeolite. (Courtesy of Kawasaki Steel Co. called bulk mesophase [94.3. defluorination of fluorinated hydrocarbons. LLC .23 (a) Formation. In order to meet the requirements for carbon materials.. 2.Structure and Texture of Carbon Materials (a) (b) (c) 59 100 μm FIGURE 2. The separated spheres. polymer blend method. including carbon materials. oriented graphite films using two-dimensional spaces in clay minerals with a layered structure [100.23) shows the sequence from the formation of small mesophase spheres to their growth and partial coalescence.) each other to give solids (coke) with different textures composed of optically anisotropic units. various novel carbonization processes have been proposed. the following processes have to be mentioned: template method. Mesophase-pitch-based carbon fibers are produced by spinning from a pitch containing a predominant amount of bulk mesophase .
especially the mesoporous carbons prepared using MgO as the template [105.0 0 20 40 60 80 100 Mixing ratio to PVA (mass%) 0 (b) 5 10 Pore width (nm) 15 20 Vtotal Vmeso. A large number of mesopores with a size of about 5 nm is easily obtained using Mg citrate . prepared by carbon deposition from propylene gas at 800°C on the inner walls of nanosized channels in an anodic aluminum oxide film . a carbon with bimodal mesopore size was obtained (Figure 2. MgO was also used as a template for obtaining mesoporous carbons.0 0.5 Vmicro.20c). Mg acetate. From the mixture of Mg citrate and gluconate. Aluminum oxide is subsequently dissolved either by HF at room temperature or NaOH aqueous solution at 150°C in an autoclave.0 Pore size distribution 2. The size and shape of the pores in the resultant carbon depend strongly on the template used. Then.0 2.60 Carbons for Electrochemical Energy Storage and Conversion Systems Pore volume 3. the one giving a relatively high carbonization yield and the other having a very low yield. poly(ethylene terephthalate). MgO formed through the pyrolysis of the precursor is dissolved by a diluted acid solution. 0 (a) 0.25 shows the pore volume and pore size distribution as functions of the mixing ratio between Mg citrate and poly(vinyl alcohol) (PVA). A thermoplastic carbon precursor [such as poly(vinyl alcohol). were prepared using the three-dimensional channels of zeolite  and mesoporous silica . 5. was proposed and called polymer blend method . and Mg gluconate) and heat-treated at 900°C in inert atmosphere. This idea gave certain success to prepare macroporous carbons from poly(urethane–imide) films prepared by blending poly(amide acid) and phenol-terminated polyurethane prepolymers . liberating the mesoporous carbon [105–107].2 Polymer Blend Method In order to control the pore texture in carbon materials.0 MgO/PVA=5/5 MgO/PVA=3/7 3.0 MgO/PVA=1/9 1.0 MgO/PVA=10/0 Adsorption ΔV (log d) (mL/g) 4. Figure 2. higher than 2000 m2/g. 2. blending of two kinds of carbon precursors.0 1. Since the mesopore size of the resultant carbon is governed by the size of MgO thus formed. Mg citrate.0 FIGURE 2. By coupling this polymer blend method with © 2010 by Taylor and Francis Group.5 1.5. and pitch] is mixed with a MgO precursor (MgO.3. The materials obtained by this technique are extensively presented in Chapter 3.5 Pore volumes (mL/g) 2. the process may be classified as an autogenous template method. LLC .110].25 Pore volume and pore size distribution of mesoporous carbons obtained from the mixture of Mg citrate with poly(vinyl alcohol). Porous carbons with a high BET surface area. The template carbons demonstrate interesting performance in electric double layer capacitors . Asymmetric electric double layer capacitors constructed from these mesoporous carbons coupled with a microporous activated carbon display high capacitance and high rate performance .
and a TEM image of the resultant carbon nanofibers is shown in Figure 2.3. LLC . The preparation procedure is schematically shown in Figure 2.Structure and Texture of Carbon Materials Pore forming polymer 61 Polymer blend Blending Microcapsule Kneading Carbon precursor polymer Pore forming polymer (a) Scheme of the preparation procedure Carbon nanotube Spinning Stabilizing Infusible fiber Carbonization 200 nm (b) TEM image FIGURE 2.119]. on the pore texture of carbon aerogels have been extensively studied [120–122]. such as the drying process.3. © 2010 by Taylor and Francis Group.5. Japan. Gunma University.117]. Also. Oya. A.26a.5.26 Scheme of the polymer blend method to prepare carbon nanotubes and their TEM image. 2. The effects of the type of organic precursor aerogel and of the preparation conditions. Kiryu. (Courtesy of Prof. 2.26b. The carbons derived from PTFE were found to have a large number of mesopores and to give a high electric double layer capacitance [116.3 Defluorination Porous carbons with a high surface area are obtained through the defluorination of poly (tetrafluoroethylene) (PTFE) with alkali metals (AMs) . carbon nanofibers were successfully prepared . the doping by some metals into the organic aerogels was reported to be effective for the development of micropores .) spinning. With permission.4 Carbon Aerogels Mesoporous carbon aerogels are prepared by the pyrolysis of resorcinol–formaldehyde organic aerogels [118.
1 CLASSIFICATION OF NANOTEXTURES In the graphite family. the latter is divided according to the scheme of orientation. The plates of the so-called highly oriented pyrolytic graphite (HOPG)  have a very high degree of planar orientation of the hexagonal carbon layers. finding large-sized crystals (more than 10 mm) is extremely difficult.124]. they are called nanotextures. LLC .2 PLANAR ORIENTATION The extreme case of planar orientation is a single graphite crystal. and around a reference point (point orientation). but the size of the layers is not so large. in parallel to a reference plane (planar orientation).4. 2. the fundamental structural unit is a stack of layers of carbon hexagons. but it is polycrystalline in the parallel direction .4.. Since these are textures constructed by fundamental structural units at a nanosized scale. and results in a variety of textures in carbon materials. Single crystals can be found in either naturally occurring graphite (natural graphite) or in precipitated graphite flakes from molten iron (kish graphite). The way the structural units tend to agglomerate is determined by the schemes and degrees of preferred orientation. a perfect orientation with large-sized hexagonal carbon layers.27 Classification of nanotexture for carbon materials in graphite family. random and oriented nanotextures are differentiated and. A classification has been proposed on the basis of the scheme of preferred orientation of the anisotropic structural units (Figure 2.62 Carbons for Electrochemical Energy Storage and Conversion Systems 2.27) [1. which govern the graphitization behavior at high temperatures. © 2010 by Taylor and Francis Group.e. the structure is close to a perfect orientation in the direction perpendicular to the plates. A SEM image on a fractured cross section of an Planar orientation Reference plane Oriented nanotexture Random nanotexture Point orientation Reference point Radial Random orientation Axial orientation Coaxial Reference axis Concentric Radial Reference axis Reference point FIGURE 2. However. secondly. Firstly. which has a strong anisotropy because the bonds in the layers are covalent and those between the layers are of van der Waals type. In other words. i. along a reference axis (axial orientation).4 NANOTEXTURE IN THE GRAPHITE FAMILY 2.
A. With permission.28a and b. (Courtesy of Prof. whereas Figure 2. the size of the 002 lattice fringes increases and their parallel stacking is improved with increasing HTT. the planar orientation of the layers is improved with increasing heat-treatment temperature (HTT). Japan. In pitch-derived cokes. Tokyo. Tokai Science University.Structure and Texture of Carbon Materials 63 HOPG and a channeling contrast image of an HOPG plate surface are shown in Figure 2. Oberlin. The changes in transverse magnetoresistance (Δρ/ρ0) with the rotation angles ϕ and θ of the magnetic field along and perpendicular to the axis of a needle-like particle (TL and T 1 μm (a) SEM image of the edge surface 100 μm (b) Electron channeling image of the basal surface FIGURE 2.28a.29. (Courtesy of Mme. Japan. Various intermediate nanotextures between the perfectly planar and random orientations are found in pyrolytic carbons and coke particles. depending on the preparation and heat treatment conditions. consisting of small grains of graphite basal planes in different orientations.28 Scanning electron micrograph of a cross section of an HOPG and electron channeling image of an HOPG plate basal surface.) (a) 1100°C-treated (b) 1300°C-treated 1 nm (c) 1800°C-treated (d) 2200°C-treated 1 nm 1 nm 1 nm FIGURE 2. A well-ordered stacking of the hexagonal carbon layers is seen in Figure 2. Musashi Institute of Technology.) © 2010 by Taylor and Francis Group. Yoshida.29 002 lattice fringe images of a needle-like coke heat-treated at different temperatures. Needle-like coke has been widely used for the industrial production of graphite electrodes for steel refining. With permission. LLC .28b demonstrates the polycrystalline nature. Tokyo. respectively. as demonstrated through HRTEM . A. As shown on a coke particle in Figure 2.
θ/° 180 0 90 . VGCFs have a coaxial alignment of small carbon layers on a carbon nanotube at the center (Figure 2. After the 3000°C treatment.0 1770°C TL Δρ/ρ0 (%) 30 –0. the Δρ/ρ0 value at ϕ = θ = 90° is negative and decreases with increasing HTT.30 for different HTTs .31) . from parallel (tubular type) through perpendicular (platelet type) to herringbone type (Figure 2.64 Carbons for Electrochemical Energy Storage and Conversion Systems 50 40 T 3000°C TL 0. different orientation schemes can be found along their axes.e.) rotation). fiber axis) are possible (Figure 2. from radial and concentric to random are possible (Figure 2.4.32a) . indicating the growth of carbon hexagonal layers and the improvement in stacking order (graphitization). Japan.34 for both as-prepared © 2010 by Taylor and Francis Group. Y. the variety in the nanotexture of different carbon fibers is illustrated  and examples are shown in Figure 2. The degree of concentric alignment is greatly improved and the cross section of the fibers is polygonized. For mesophasepitch-based carbon fibers. (Courtesy of Prof.27). a fibrous morphology is possible because of this axial orientation scheme.. The difference in the cross-sectional nanotexture becomes more pronounced after high-temperature treatment (Figure 2.30 Dependence of the magnetoresistance (Δρ/ρ0) with the rotation angles ϕ and θ for a needlelike coke particle.33) or cup-stacked type. Tokyo. the small layers coalesce with each other forming long and smooth layers. Musashi Institute of Technology. different nanotextures of the cross section. in other words.6 0 (b) 0 (a) Needlelike coke 90 . which suggests that this needle-like coke particle has an intermediate nanotexture between planar and axial orientations. However.31. Below 2200°C. With permission.3 AXIAL ORIENTATION An axial orientation of the layers is found in various fibrous carbon materials. it turns to a positive value and increases to very large values above 2400°C. Above 2200°C.15). In carbon fibers. A concentric alignment of the layers is realized in multiwalled carbon nanotubes and various carbon nanofibers.4 TL 2200°C T 10 T 2600°C TL T 2400°C –0. The Δρ/ρ0 value at ϕ = 0° and 180° does not coincide with that at θ = 0° and 180°. the coaxial and radial alignments of the layers along the reference axis (i. LLC . respectively. most of which are grown through CVD using fine catalyst particles. Hishiyama. 2. In Figure 2. Examples of herringbone type and tubular type nanotextures are shown in Figure 2.32b and c).2 Δρ/ρ0 (%) T TL 1980°C T 2800°C 20 T TL –0. mainly due to crystallite growth (Figure 2.32. are shown in Figure 2. θ/° 180 FIGURE 2.
© 2010 by Taylor and Francis Group. 1800°C-treated 1200°C-treated 1600°C-treated 1 μm 3000°C-treated 3000°C-treated 3000°C-treated (a) Coaxial (vapor-grown) (b) Radial (mesophase-pitch-based) (c) Random (isotropic-pitch-based) FIGURE 2. Impregnation of molten poly(vinyl alcohol) into the channels of anodic aluminum oxide films gives nanofibers with a platelet nanotexture . mainly because of the layer growth. After the high-temperature treatment. the nanotexture is recognized more clearly.31 Nanotextures in the sections along and perpendicular to the fibre axis of various carbon fibers. LLC .Structure and Texture of Carbon Materials 65 Vapor-grown Mesophase-pitch-based Fiber axis High degree of orientation Vapor-grown Mesophase-pitch-based Low degree of orientation PAN-based PAN-based Isotropic-pitch-based Phenol-based Cellulose-based (b) Perpendicular to the fiber axis Random orientation (a) Along the fiber axis Isotropic-pitch-based Phenol-based Cellulose-based FIGURE 2. Cross section of as-prepared and high-temperature-treated carbon fibers showing different and high-temperature-treated carbon nanofibers .32 nanotextures.
In single-wall carbon nanotubes. The concentric orientation of the carbon layers is more © 2010 by Taylor and Francis Group.36a and 2. LLC .34 Two different nanotextures in carbon nanofibers. the diameter of which is from few tens to few hundreds of nanometers. minute hexagonal carbon layers being preferentially oriented along the surface (Figures 2. As-prepared As-prepared 5 nm 2900°C-treated 2800°C-treated (a) Herringbone nanotexture (b) Tubular nanotexture FIGURE 2.4 POINT ORIENTATION In the point orientation.27).37a) .4. various chiralities are realized from arm-chair type through zigzag type to chiral type (Figure 2. The extreme case of concentric point orientation is found in the fullerene family. 2. which are known to govern their properties .33 Schematic illustration of nanotextures in carbon nanofibers.66 Carbons for Electrochemical Energy Storage and Conversion Systems (a) Platelet (b) Herringbone (c) Tubular FIGURE 2. This orientation is also found in the spherical particles of carbon blacks.35). concentric and radial alignments also have to be differentiated (Figure 2.
Ltd. and carbon spherule. (Courtesy of Tokai Carbon Co. 10 nm 5 nm (a) As-received (b) 3000°C-treated FIGURE 2. LLC . With permission.Structure and Texture of Carbon Materials 67 θ=30° θ=0° θ (a) Arm-chair type (b) Chiral type (c) Zigzag type FIGURE 2. Shizuoka. mesophase sphere..36 002 lattice fringe image showing the nanotexture of a furnace black (a) as-prepared and (b) high-temperature-treated.37 Models of nanotexture for small-sized carbon black.) (a) Carbon black (b) Mesophase sphere (c) Carbon spherule FIGURE 2. Japan. © 2010 by Taylor and Francis Group.35 Schematic illustration of the various structures of single-wall carbon nanotube.
In this model. the increase in the graphitization degree.36b). the particles are polygonized and a hollow core appears (Figure 2. A 002 lattice fringe image of sugar coke heat-treated at a high temperature is shown in Figure 2. where the layers become somewhat larger. are frequently applied to carbons in order to modify and improve their nanotexture and properties. but at their center the orientation of the layers is not radial (Figure 2. this model is believed to be realistic. These cracks might explain the good performance of MCMB as anode materials for lithium-ion rechargeable batteries... they are supposed to accommodate the expansion due to lithium intercalation.g. 2.e.136]. Heat treatment at high temperatures. in inert atmosphere is an essential process for the production of graphite blocks.38 Scanning electron micrograph of MCMB after heat treatment at 2800°C. such as phenolic resin. and doping by boron and nitrogen. The fundamental structural units comprising most glass-like carbons are so small that they are difficult to be observed by TEM. in most cases up to 3000°C.5 RANDOM ORIENTATION A randomly oriented nanotexture occurs in glass-like carbons and in carbon materials obtained by carbonization of polymer precursors (e.. marked near the surface. which are formed by pressure carbonization of a mixture of polyethylene and poly(vinyl chloride) (Figure 2. i. LLC . their nanotexture was often discussed on the basis of TEM observations on high-temperature-treated materials. including glass-like carbons (Figure 2. and a model of nanotexture is proposed for the carbons derived from various precursors.6 IMPORTANCE OF NANOTEXTURE Various treatments. 2. whereas the layers are randomly oriented at the center. such as high-temperature treatment. The development of the © 2010 by Taylor and Francis Group. When large-sized carbon black particles are heat-treated at high temperatures. sugar.68 Carbons for Electrochemical Energy Storage and Conversion Systems 10 μm FIGURE 2.4. because of the crystallite growth.39b) . A radial alignment of the layers to form a sphere is found in the carbon spherules. tangential cracks are formed after heat treatment at high temperatures (Figure 2. The principal purpose of this treatment is the improvement in structure. phenol resin and sugar). etc.38) . As a consequence of the radial orientation near the surface.37b) [95. By taking into consideration the large number of closed micropores in most glass-like carbons and their gas impermeability.4.39a . closed pores are formed by concentric hexagonal layers. intercalation of different foreign species. Therefore. The radial point orientation scheme appears near the surface of most mesophase spheres (MCMB).37c) [133–135].
L a. Conventionally. are often used as parameters to estimate the graphitization degree.) Interlayer spacing (d002) 0. which is the probability to have the AB stacking sequence for neighboring hexagonal carbon layers.3354 nm and more than 0.344 0.340 0. d002 approaching 0.336 0.3354 nm and L a being more than 100 nm.339–0.341 nm and small L a of 20–50 nm.40 Influence of HTT on the interlayer spacing d 002 and crystallite size L a of carbon materials with different nanotextures. respectively. With permission. give relatively high d 002 values of 0. d 002. It is exactly evaluated by the graphitization degree P1. the average interlayer spacing between neighboring layers.Structure and Texture of Carbon Materials 69 (a) 002 lattice fringe image of sugar coke (b) Model proposed FIGURE 2.350 0. The d002 values of highly crystallized graphite and amorphous carbon are 0. Oberlin and Prof. The needle-like coke mainly with a planar-orientation nanotexture and VGCFs with a coaxial orientation scheme show a rapid decrease in d 002 and a rapid increase in L a with increasing HTT. Tokai Science University. however. (Courtesy of Mme A.348 0.338 0. even after heat treatment up to 3400°C. which are determined by x-ray diffraction analysis. Carbon blacks. M. which have a coaxial point orientation. Shiraishi.344 nm.346 d002 (nm) Glass-like carbon 120 100 80 La (nm) Crystallite size (La) Needlelike coke VGCFs Regular coke Thermal black Furnace black 0. Tokyo. thermal and furnace blacks. Glass-like carbon with a random orientation gives much larger d002 and very small L a even after 3000°C treatment.334 1500 VGCFs Thermal black Regular coke Furnace black 60 40 20 Needlelike coke Glass-like carbon 2000 (a) 2500 HTT (°C) 3000 3500 (b) 0 1500 2000 2500 HTT (°C) 3000 3500 FIGURE 2. Japan.39 (a) 002 lattice fringe image of sugar coke and (b) nanotexture model for glass-like carbon.40a and b show the variation of d002 and L a versus HTT for various carbon materials with different nanotextures . and the layer size. Figure 2. © 2010 by Taylor and Francis Group. LLC . graphite structure is evaluated by different parameters.342 0.
3379 nm La: 56 nm FIGURE 2. can be easily intercalated in various carbon materials. accompanied by the disruption of the original nanotexture . as clearly seen in Figure 2.g. expressed by low d002 and high L a values. The difference in graphitization behavior is now known to be mainly due to the nanotexture. The intercalation of sulfuric acid into natural graphite can proceed at room temperature in concentrated sulfuric acid with a small amount of oxidant.146]. In the case of intercalation reactions. because intermediate behaviors are very often found. in order to intercalate sulfuric acid into carbon fibers.41 shows that the cross-sectional nanotexture also governs the graphitization behavior of the fibers . Potassium as a vapor.3385 nm La: 40 nm 1 μm (c) Concentric d002 = 0. but those presenting a zigzag radial nanotexture have a poor graphitization degree. Figure 2. Fibers with a straight radial nanotexture in their cross section have a relatively high graphitization degree. and the latter either nongraphitizing. graphitizable. on the other hand. In order to change glass-like carbon with random nanotexture to graphite.40. or hard carbon [141–143]. LLC . The resulting intercalation compound is commonly used in industry for the preparation of exfoliated graphite . even in low-temperature-treated carbon fibers .41 Scanning electron micrographs and structural parameters of mesophase-pitch-based carbon fibers with different cross-sectional nanotextures. However.. it was proposed to classify the carbon materials into two classes before this treatment. However. (a) Straight radial d002 = 0. or soft carbon. heat treatment under high pressure is required. © 2010 by Taylor and Francis Group. The former was called either graphitizing. As already illustrated in Figure 2. mesophase-pitch-based carbon fibers can have different cross-sectional nanotextures. the nanotexture of the host carbon materials has a strong effect. the one that can change to graphite and the other that cannot.3367 nm La: 81 nm (b) Zigzag radial d002 = 0. nongraphitizable. such as nitric acid. e. electrolysis is needed [145.31.70 Carbons for Electrochemical Energy Storage and Conversion Systems Since the behavior with the treatment at high temperatures is quite different from carbon to carbon. such a classification is not used now.
Optical microscopy images on polished sections of isotropic high-density graphite blocks having different bulk densities from 1. a marked difference is easily seen in the micrographs. such as cokes. have been applied to get high strength and high modulus of the composites. Although the difference in bulk density looks rather small. showing different shapes. i.44 shows the plots of mechanical properties (elastic modulus. the particles of needle-like coke tend to be oriented along the rod axis during their forming process through extrusion with pitch binder. for example.5 MICROTEXTURES IN CARBON MATERIALS Most particles with planar and axial orientation. In large-sized graphite electrodes for metal refining. where small-sized coke particles are formed using isostatic pressing . the microtexture. LLC . The presence of pores in the formed carbons influences the properties of the material. fractal dimension. In such a case. roundness.. etc.43 . and distributions of the pores in the cross section.848 g/cm3 are shown in Figure 2. it is necessary to take into consideration the texture formed by the preferred orientation of these anisotropic particles in order to understand the properties of different carbon materials. has to be taken into account in addition to that due to the orientation of anisotropic particles. and carbon nanotubes.Structure and Texture of Carbon Materials 71 2. The texture due to the preferred orientation of anisotropic particles may be called microtexture. average cross-sectional area. The latter. and as a consequence their agglomeration can create a further variety in texture. The former is realized in the so-called isotropic high-density graphite blocks. were determined with the help of image analysis . was realized in glass-like carbons. Two methods have been employed for realizing the isotropy of carbon materials that fundamentally consist of anisotropic structural units or crystallites: (i) the random aggregation of micrometeror millimeter-sized particles. Figure 2.42. Different pore parameters of these carbon materials. for example. because the particles are often of micrometer or millimeter size. including the shape and size of the pores. The microtexture is usually formed during the forming process of bulky carbon materials. even though these particles are anisotropic and (ii) the random agglomeration of nanometer-sized crystallites in the bulk.42 Different arrangements of carbon fibers for the preparation of reinforced composites. such as density. Chopped fibers Random M R L K N M R L N R M S M P M K One-directional Long fibers U L S L M N S M R L N Three-dimensional Two-directional U T V W U U V W U V Y W T U W U X V X T U N W U N T V Y W T V Y Three-directional FIGURE 2. in addition to the nanotexture and also graphitization degree of each particle.. which are isotropic and have a nongraphitizing nature .e. To prepare carbon-fiber-reinforced plastics (composites). some examples of which are shown in Figure 2. different microtextures based on the carbon fibers’ orientation. are also anisotropic. © 2010 by Taylor and Francis Group. sizes. Therefore.735 to 1. aggregation of nanosized carbon layers. carbon fibers.
4 (c) 0 200 400 Average pore area (μm2) 600 FIGURE 2.848 g/cm3 (f ) 1.8 0.72 (a) 1. Nagano.44 Relationship between the mechanical properties and average pore area of high-density isotropic carbons. Japan.788 g/cm3 (c) 1.) Elastic modulus 1400 Bending strength (kg/cm2) Elastic modulus (kg/mm2) Bending strength 1000 800 600 400 200 0 (b) Fracture toughness KIc 1200 1000 800 0 200 400 600 0 200 400 600 (a) Average pore area (μm2) Average pore area (μm2) 1. Oshida. LLC .802 g/cm3 100 μm FIGURE 2.735 g/cm3 Carbons for Electrochemical Energy Storage and Conversion Systems (b) 1. (Courtesy of Prof. Nagano National College of Technology. K. With permission.6 0.842 g/cm3 (d) 1.2 1.43 Optical micrographs of polished cross section of high-density isotropic carbons. © 2010 by Taylor and Francis Group.0 KIc (MPa m1/2) 0.842 g/cm3 (e) 1.
Jarkov. Tctarenko. and Dresselhaus. Electrochemical carbonization of fluoropolymers. A. Nature 1942. 2: 551. M. Curl.E. 2000. M. 106: 749.C.N. Warren. L. and carbyne on the basis of hybridized sp3. M.M. and Khvostov. Bernal. Endo.. 17. 278: 58. 9. and primary batteries. M. J Chem Phys 1934. When they are applied for electrochemistry. and Eklund. planar. 1973(74): 76. 23.P. Vol. Inagaki. and sp orbitals used. and Hofman.. their detailed structure and texture must be exactly understood.. 2006. Macropores in exfoliated graphite. i. R. Y. 69. Beijing. Dresselhaus. Mugishima. Structure and texture of carbon materials. M.S. 15. 1998. Kudryavtsev.. Acta Crystallogr 1950. G. mainly due to the preferred orientation of the anisotropic BSU in the graphite family. 11. In Chemistry and Physics of Carbon.F. New Carbons—Control of Structure and Functions. 4. LLC . Dresselhaus. © 2010 by Taylor and Francis Group.. and Kintner.O.C. Inagaki. which strongly depend on the preparation conditions. S. flat sp2. Takeuchi. J. F. Takahashi. M. Vol. J Appl Phys 1971. and liquid). fullerene. K. The importance of nanotexture. London. P. 16. 36: 595. Nature 1985. 10. 8. and Stokes. electric double layer capacitors.E. 149: 328. R. Evsyukov.E.. V. Z Anorg Chem 1955.. F. fuel cells. The formation of these carbon materials from organic precursors (carbonization) is shortly described by dividing the process into three phases (gas. Kavan.G. R.. Y. 18.. Babaev.R.N. S.E. 19. P. China: Tsinghua University Press..L. New York: Marcel Dekker. F. 20.R. Curl. Hearth. K. Beijing. R. Guseva.. S. and Smalley. 3: 137. 2.. and Kang. 2006. In Chemistry and Physics of Carbon. point. H. Carbyne—A linear chainlike carbon allotrope.. 5.. London: Elsevier. M. Before closing this chapter. Carbon 1998..S..F. Kobori. Inagaki. Oshida. Lipson. A. H. G. diamond. Aisenberg.. Inagaki. 1–69. New York: Marcel Dekker. is particularly emphasized. 10: 1461. 46: 3437. J Mater Res 1995. axial. Franklin. respectively. 1996. G. REFERENCES 1. K.. Carbon families. G. K. based on the intermediate phases formed during carbonization.F. A dependence of the mechanical properties of these carbons on pore size is clearly shown. Science of Fullerenes and Carbon Nanotubes. 4: 253. and fracture toughness KIc) versus the average cross-sectional area of the pores. solid. Bundy.D. and Kasper. 7. R. 42: 2953. which can sorb up to 80 g of heavy oil per 1 g of exfoliated graphite . 6.P. U. H. Acta Crystallogr 1951. 12. M. 2. the structures and textures of carbons at different scales are explained. 3. UK: Imperial College Press. China: Tsinghua University Press. R. K. Proc R Soc A 1924. Each family has its own characteristic diversity in structure and also in the possibility of accepting foreign species. and Chabot.S. Sci Am 1991. In Carbon Materials Science and Engineering.6 CONCLUSION In this chapter. Dresselhaus. B.e. graphite. Science 1978. S. The carbon materials are classified into four families. Bacon.20d.P. 32.E.. curved sp2. 318: 162. An example of a histogram for the cross-sectional area of macropores formed in worm-like particles is shown in Figure 2. and Dresselhaus. O’Brien. 14. V. 25. J Chem Phys 1967.Structure and Texture of Carbon Materials 73 bending strength. J. Physical Properties of Carbon Nanotubes. 200: 763.. TANSO 1973. The following chapters will present the practical applications of various carbons in various electrochemical devices. 1991(October): 32. 1991. such as lithium-ion rechargeable batteries. and Hosokawa. 1996. and Kang. it has to be emphasized that carbon materials have a wide range of structures and textures.S.. J. Whittaker. 21. 23. Boehm. R. and random orientation schemes. M. Kroto.. 13. and Churilov. were analyzed with the aid of image analysis . In Carbon Materials Science and Engineering. and Smalley. Saito. San Diego: Academic Press.Z. R.
Y. B. New York: Marcel Dekker. and Tiedje. J. Inagaki.. 36.. M. Y.. 54: 1645.. I. Y. 39. M. J Phys Chem Solids 1993. Graphite Intercalation Compounds and Applications. T. 33: 1167. Bonnamy. T. Fibrous carbon materials. Diefendorf...G. Enoki.. Nakahashi. H.E. B. and Iwanaga. K. Inagaki. Iwanaga. Okada. A.. Bokros. 269: 1554. Matsubara. Nagahama. and Kang. Sleigh. Nishimura. U. J. 2004. Maeno. Way. 1. J. H.. S.. Phys Rev B 1998.. Motojima. Higaki. and Kaburagi. 59... Hamwi.. T. Shimada. Harada. Hummelen.. 50. Endo. Hasegawa. Y. M. B. 8: 3233... S. 27. H. K. Zhou. Ishioka.. In Lithium Batteries.. S. 80: 1267. Hatori. A. 48. Shi. and Oberlin. 46. 28.. 64. 1972. Vogel. Nanotexture development in carbon materials.. H. Beijing.R. Jpn J Appl Phys 1974.. J Chim Phys 1960. Motojima. 32.A. M.M.J. Ouyou Butsuri 1985.R. Shioya..S... C. M. J.. M. 51. Oberlin. Hayashi..S. J. Konno. Kim. S. Zhong.P. Fryer. M. Brown. S. and Inagaki.. H. 63: 843. Phys Rev B 1992. 17: 127.. Yanagisawa. Lowell. M. S. Matthewa. Tanigaki. 2002.. 24. and Murakami. J Am Ceram Soc 1967. M. U. M... J Mater Res 1993. A. New York: Marcel Dekker. 18: 73. 1. K. J Mater Res 1989. Mater Sci Eng B 2004.D. 43.. and Grant. F. Science 2001.. and Kang.K. Hishiyama.. 35. © 2010 by Taylor and Francis Group. T. Rodriguez. and Merino. 63. M.. Appl Phys Lett 1990. and Morita. J. Appl Phys Lett. In Carbon Materials Science and Engineering. Reimers. C. TANSO 1997.K. Tamaki. Carbon 1995. Fukai. Nishimura. 35: 723.. M. 38..R. 45. 40. Alvergnat. Soneda. Y.... Yoshida. 26.. F. H.. M.. J. 37. and Inagaki. Industrial Chemistry Library. M.. S. Toganoh.... S. Endo. 32: 335. X. T. M.. 58. London. Carbons and graphites as substitutes for the lithium anode. 65. Pavlovich. 11: 583. Yamaguchi.: Oxford University Press. Taninaka. Koyama.. Carbon 2000. Conesa. and Hishiyama. 359. F. 13: 1933... J.E. H. 54: 507. Fujii.. W.. Soneda. 49. T.. T.. In Chemistry and Physics of Carbon. M. Sato. M. Audier.. A. H. Y. B. M. and Schoen. 58: 8991. 30: 517... J. 31.. 2003. Kawaguchi. 5. and Kamegawa. 44.. Coulon.. T.. J. Carbon 1997. and Voet. 11: 674. and Inagaki. S. 63: 245406.C..N. M. H. Carbon 1973.. Phys Rev B 2001. S.B. 34. Endo. 23.... and Koyama. and Endo. F. Dahn. Asakura. Kim. T. E. Gonzalez.L.. T.. TANSO 2006. C. K. 54. R. 30. 29. R.J. Kodama. 57. Carbon 2006. Rep Prog Phys 2000. Gonzalez.D. M.M. 56: 321. and Toyoda. Chen. 62. C. Carbon Black. J Mater Sci 1977. New York: Marcel Dekker. N. Donnet. Koyama.C. Nozaki.74 22. Matsubara. W.. 9. 55. 73: 431. 125: 4391.. and Dresselhaus. Kaburagi. Vol.. Y. Carbon 1997. and Béguin. H. Y. T.. China: Tsinghua University Press. Reimers. K. Vol. A. Carbon 1992. Y.. Sleigh. J Am Chem Soc 2003.. M. S. Y. S. M.. Vol. and Endo. M. Exfoliation of graphite via intercalation. 12: 591. Hakler.. Martin-Gullon. In Chemistry and Physics of Carbon. Kanazawa. 33. K. M. Y.. Isobe. M.. J..A. Science 1995. K. Carbon 1981. 2006. M. Endo. In Carbon Materials Science and Engineering. Egashira. 27: 253. 1976. N. Carbon 1992. 1997 (178): 122. F.. T. 53. F. Ando. J Cryst Growth 1976. A. Oxford U. I. M. Shinohara. 15: 808. Endo. F..K. Carbons for Electrochemical Energy Storage and Conversion Systems Yamada.. Irumano. H. Y. Weydanz. M. and Nakamura. Beijing. Endo. Y. 61. Baird. Y. M. 14: 133.. Inagaki. and Shinohara. A. 222: 140. Horino. Hishiyama. LaGrange. Matsunaga. T. Yamashita. Nakajima. LLC . 47. Suzuki..L. G.J. T. Inagaki. 18: 503. Katsuki. Karaki.... China: Tsinghua University Press. L. 108: 156. T. J. H. and Wudl. Okumura. Knight.M. A. 38: 478. 52. S. Inagaki. 291: 1944. J. M. Burger. Q.. 25. and Shikata. Carbon 1976. and Motojima. Kato.. Oshida. and Hishiyama.K.. U. 44: 1572. 29. 103. S. 45: 3773. 56.. and Kawasumi. Synth Met 1987. 12: 982. 60. and von Sacken..: Elsevier. 35: 669. J Cryst Growth 1985. Carbon 1974..N. 42. Sawamura.. M. Tibbetts. Vera.. K.. H. Boehm. M. T. 41. 9: 148. Carbon 1980. H. J. and Makino.... 4: 1560.. 47. and Iwanaga. Control of structure of carbon for use in bioengineering. 1994. 50: 241. H. J Mater Res 2000. 2006. Chu. Dahn. Kang. and Dresselhaus. S. Carbon 1989. In-Hwang. Yokawa.
.. Y. Carbon 2001... Miyauchi. In Chemistry and Physics of Carbon. Noda.S. Oi. Chem Phys Lett 2002. Hishiyama. Activated carbon for automotive application. Nature 1988.. T..S..K. Zhao.. Y. and Yamada.. M. J. T. Inagaki. Rokkaku. Takeichi. Ceramics 1976. T. Wang. TANSO 1983.. and Nishikawa. Kang. H.. and Inagaki. K. and Ryoo. and Dresselhaus. and Suzuki.. S. and Kohno. Derbyshire. M.. Y. Iwashita... and Beyers. Toyoda.K. 73. Sakamoto. M.. Matusita. Marsh..Y. Microporous structure of activated carbons as revealed by adsorption methods. 96. New York: Marcel Dekker.. K. A. S. 39: 937. 4. Carbon 2007. and Wennerberg. 1968. U.. Jagtoyen. 42: 1401. M. Nature 2000. Muramatsu. W. Activated carbons—production and applications. Vol. F.J. S... K. Beijing.. 2006. Donnet. Higuchi.. 89. T. and Nishizawa. 7: 1427.J.S. D. 92: 7029. 39: 1287. Nagai. 41: 1941. K. Kim. and Taylor.. Mabuchi. Ishihara. Appl Phys Lett 1997. Imamura. Hayashi... M. S. K. Morishita. S. S. New York: Marcel Dekker.. H. 37: 6486. Kyotani. F. Boca Raton. Toyoda. M. 91. M.M.C. Bethune. Inagaki. New Carbon Mater 2003.. Chiashi. and Rodriguez-Reinoso. Brooks. S.. K.. Yudasaka.. Yanagisawa.. Carbon 2003. F.. S. 22: 603. and Béguin. 70. Nature 1993. Carbon 1969. 102... K. 67.. Honda. H. Schaffer. Morishita. 26.H. 72. 93. Inoue. Soneda. LLC . S. Stucky. 75.. Sonobe. M. Zheng. Kakiyama. Shioyama. T. Ads Sci Tech 2006.M. H. © 2010 by Taylor and Francis Group. 142: 716. R..M. In Carbon Materials for Advanced Technologies. 354: 56.. Shiraishi. and Fujimoto. Carbon 1974. M. Terasaki. Carbon Fibers. M. T. China: Tsinghua University Press. O.. Y. 9: 609... Iijima. Inagaki. R.A... H. 1999. M.: Elsevier. Carbon 2001. Amsterdam.. Kato. K. M. Wang. N.. 269. S... 82.R. 1.. Nature 1993. Activated Carbon..Structure and Texture of Carbon Materials 75 66.. M. D. 24: 55. Krätschmer.S. Nishikawa. In Chemistry and Physics of Carbon. Lowell. K. 71.. K. Setsuda. S. 12: 307.. H. Carbon 1984. In Chemistry and Physics of Carbon. J. M.. Marsh. 3rd edn.. W. and Inagaki. Bandow. Y.D. Vol. Oshida. Terrones. Shin..R. 97. K. H.. 18: 161. Endo. M. T.. and Williams. A. 98. T. and Fukuda. Johnson... T. Polycrystalline graphite blocks. K. Inagaki. M. H. Y. 83. FL: Taylor & Francis... S. and Thwaites. T. In Porosity in Carbons. G. R. F. 363: 603. 79. Tsai.. 309: 165. M. M... 101. Sonobe. M. T. Kyotani. Terrones. 92.. and Oberlin. G. O’Grady. E.. Wang. 77. Fostiropoulos... 37: 1605. Fukuyama. Kiang... and Nishizawa. H. Savoy. Y.. and Peng. 331: 331. Y. 170: 167. 74. 45: 209... D. Vol.. Desalination 1998... M. Tatsumi. Krätschmer. Lamb. Vazquez. and Yamada. 88. and Tomita.: Edward Arnold.K. Ezaka. London. Chem Mater 1995. F. The Netherlands: Pergamon.. 363: 605. J Non-Cryst Solids 1969. deVries.B. Sorption of heavy oils into carbon materials. Hishiyama.J. and Tomita. 1: 285. Hayashi. London. 85. T. and Inagaki. 11: 612. K. Fukuyama. Rebouillat. 245. Iijima. Shibata. In Carbon Materials Science and Engineering. Nishimura. T. 78. and Ichihashi. D. 115: 199. T. and Kang. 68. E. 105. Rokkaku.. N. J. Carbon 2004. New York: Marcel Dekker... 104.. T.. J. 1983 (113): 60. Kojima. and Hirayama. K. T. 90. and Inagaki. S.. U. M. W. Kaneko. and Dresselhaus. Fitzer. Iijima. and Hoffman. Rodriguez-Reinoso. 21..... Carbon 2006. H. Kyotani. Murayama.. 227. T. 2006.. P. 1998. 235. Yamada. Yan. H. Kameda. and Otani. 18: 2620. R. and Linares-Solano. M. Iwashita. W. M. Kim.. L. 243. F. J Phys Chem 1988. C. and Inagaki. New York: Marcel Dekker. Jpn J Appl Phys 1998. Nature 1990.. 86. Tsumura. Zhao. 94. M.. 360: 229. D. Kim. Hatakeyama. Frackowiak.. H. 100. In Chemistry and Physics of Carbon. R. D. G. 103.. M.. A. Honda. 44: 2360.. T. J.. Fujimaki. Y.S.. A. and Tomita.. T. Chem Phys Lett 1999. Endo. M. J. Kyotani. 30: 177. 69. Nishikawa. Kokai... A. Yamada... Gorman.. Chem Mater 1997.. Kusunoki.. M. T. 84. and Takahashi. 80..A. Jpn J Appl Phys 1998. A. K.H. 347: 354. and Huffman. Fostiropoulos.S. D. 76. Miyashita. 408: 44953. R. 95. 2007. M. N. Y. H.. Inagaki. A. 81. 7: 643. T. Kusunoki. Nature 1991. J Electrochem Soc 1995. L. Chem Phys Lett 1990. Shen... High quality graphite films from aromatic polyimides. Suenaga. 1999. M. The formation of some graphitizing carbons. Sakaebe. H. A. M. K. Aizawa. 99. N.. F. 1995. 1995. K. J.. and Tomita. 87. T.
113. T. Oya.. T. 209: 196. Hayashi. V.. T. 125. F. Yoshida. 130.. 149.. Hulicova. Washiyama. New Carbon Mater 2003. 53: 882. N. Ishioka. W.. M.. Carbon 2004. 105: 329. N. F... and Kang. Carbon 1975. Carbon 1983.. TANSO 1996.. Tamon.... Franklin.. Jansta. Ohizumi. Shiraishi. T. TANSO 1995.. Carbon 1999. D. F.. and Centeno. K. Carbon 1997. and Yamada. Ishizaki. and Inagaki.. 26: 303. Nishikawa.. University of Buffalo.. M. and Shen. 115.. Habazaki. Suzuki. Toyoda. H. 12: 1625. F. 18: 241. Kato. M.. 129. Toyoda. Endo.. M... S. TANSO 2006. Yamamoto. Vol.. M. and Meyer. M. Konno. Kato. Koishi. Bonnamy. and properties of pyrolytic carbon. 123. T. K. 144. 42: 2756.. 39: 1438. Morita..P. N. H.. Stress graphitization. In Chemistry and Physics of Carbon. Fibrous carbons.A. Beijing. 2007 (226): 19.. M. Inagaki. Yoshida. A. and Oya. Electrochim Acta 2007. 116.. Iwata. Proc R Soc A 1951.. Y. N. Tsumura. TANSO 1985. High-resolution TEM studies of carbonization and graphitization. T.. and Patzelova..E. S... Fernández. and Inagaki. Ekinaga. 1. Morishita. Beijing. Sato. 29. and Okazaki.. 1. S. 137. 127. 1956.. Yoshida. Inagaki. J Mater Res 1992. TANSO 2007. In Carbon Materials Science and Engineering.. Trans Inst Elect Eng Jpn 1985. Tokyo. Adsorption 1998. and Tamon. 110. Kurihara. A. Introduction to Carbon Materials. 134. Kaburagi. A. and Kaburagi. Hatori. A. Inagaki. M. Oberlin.. 42: 2567. Inagaki. Y. W... 52: 3207. M. Y. Inagaki. 35: 791. M.A. 343. M. M. M. Pekala. R. Polym Properties 1989... New York: Marcel Dekker. H. 119. 14: 1. M. Inagaki. M. M. 1969. T. China: Tsinghua University Press. 1999. Y. M. 114. Hishiyama. 111. 149. 11: 1. M.. 1984. A. S. Inagaki. F. E. T. 21: 231. Alvarez. Inagaki. Inagaki. 135. 40: 457. Soneda. Sato. Oberlin. A. 8: 270. structure. Morishita.. Tsumura. Carbon 1988. Yamamoto.B.S.. Yoshida. 145.. Yoshizawa.. and Sakai. Ishihara. 136. 139. F.. and Stoeckli. Oberlin. A... Japan: Carbon Society of Japan. 122. S. Bekyarova. T. K. K. T. 4: A5. Nakahara. 118. Carbons for Electrochemical Energy Storage and Conversion Systems Morishita. A. Okabe.. 39: 2374. Adv Mater 2000.. Beijing. 1996 (173): 142. and Kang. M. T. China: Tsinghua University Press. and Naka. 141.... M. Morishita. Kaneko. Y. Zuo.. Tamon. 131. M. In Carbon Materials Science and Engineering. and Inagaki. Y. and Hishiyama. 128. Oya.W. Oberlin. Carbon 1980.. and Inagaki. 2006. H. 126. Hanzawa. 22.. S. Oshida. Inagaki. Lafdi.. O.. S. Carbon 2007.P. M. H. Mrozowski. and Oya. 1979 (98): 89. Y. K. Hishiyama. M. and Dresselhaus.76 106. 107. In Proceedings of the Conference on Carbon. T. China: Tsinghua University Press. J. 1989.M. Igarashi. J.. H. Y. 133. M.. Fuertes. Carbon 2001.. and Kang.W. Hishiyama. Carbon 2002. and Ito. H.. Electrochim Acta 2007. Yoshida. and Inagaki. F. Tsubota. New York. F. Y. and Yamada... 30: 221.. 26.. H.A.. 146. 148. 45: 1121. M. H. A. 359. A. Centeno. and Inagaki. 7: 1400. International Committee for Characterization and Terminology of Carbon. Kamiya. M... 112. D. H. Shiraishi. 1991 (147): 57. Carbon 2001. M.. K.. Oberlin. 121. 117. 20: 445. Pekala. Takeichi. Zheng. Mechanical strength. Iwashita. P.. M. M. J. Bokros. and Inagaki. Inagaki. Yoshizawa. LLC . Sakai. T. F. Carbon 2001. Structural development in carbon materials (graphitization). 39: 1697. 120. A. M. Non-graphitizing and glass-like carbons. Augie. and Inagaki.. Morishita. M.. M. M.C.. Kaburagi. M. TANSO 1991. 1985 (122): 114. M.. Carbon 1982. Toyoda. High Perform Polym 1999.. A. M. 18: 337. T. K. In Chemistry and Physics of Carbon. Ishizaki. Y. 132. Y.. Kang. 31.. New York: Marcel Dekker. R. J Power Sources 2008. 37: 2049. M. Ueno.. Wang. S. In Chemistry and Physics of Carbon. H. 108. L. Shimizu. R. Nishimura. S. A.A. Electrochem Solid State Lett 2001. 223: 220. 138.. and Suzuki. Deposition. Endo. and Inagaki. High Temp High Press 1976. Inagaki. G.. Dousek. K.. thermal expansion and structure of cokes and carbons. Sevilla... 112. 140. N. T. and Kaneko. 2006.. In Carbon Materials Science and Engineering. H. Ishihara.. Vol. Carbon 2004. K. M. 2006. M. R. and Terriere. S. A... © 2010 by Taylor and Francis Group.. and Kong.. A.. Endo.. Yamada. T. Vol. M. High Temp High Press 1971. Kuroda.. 143. J Microsc 1972. 124. T. Mikami. 175: 675. and Hyvernat. Toyoda. 150. and Iizuka. Ozaki. 5. M. M.. T. K. and Inagaki.. 147. 35: 1031. and Mizuuchi. J. Suzuki... Stoeckli. Y. 13: 377. Shiraishi... and Naka. 4: 187. 1995 (168): 169. Carbon 1997. New York: Marcel Dekker. 142. 109. TANSO 1979. M. Tanaike.. K. M. M. Y. 3: 355. Toyoda..
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.