Edited by -I - Timothy D. Burchell * Carbon Materials for Advanced Technologies Carbon Materials for Advanced Technologies Edited by Timothy D. Burchell Oak Ridge, National Laboratory Oak Ridge, TN 37831 -6088 U.S.A. 1999 PERGAMON An Imprint of Elsevier Science Amsterdam - Lausanne - New York - Oxford - Shannon - Singapore - Tokyo ELSEVIER SCIENCE Ltd The Boulevard, Langford Lane Kidlington, Oxford 0x5 IGB, UK @ 1999 Elsevier Science Ltd. All rights reserved. This work is protected under copyright by Elsevier science, and the following terms and conditions apply to its use: Photocopying Slngle photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery. 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Contents Gon~ibutors xi Acknowledgments xiii pref~ce xv 1 Structure and Bonding in Carbon Materials P Brian Me E naney 1 Introduction 1 2 Crystalline Forms of Carbon 3 3 The Phase and Transition Diagram for Carbon 12 4 CarbonFilms 14 5 Carbon Nanoparticles 18 6 Engineering Carbons 20 7 ConcludingRemarks 28 8 Acknowledgments 29 9 References 29 2 Fullerenes and Nanotubes 39 Mildred S . Dresselhaus . Peter C . Eklund and Gene Dresselhaus 1 Introduction 35 2 4 Applications 84 5 Acknowledgments 87 6 References 87 Fullerenes and Fullerene-based Solids 37 3 Carbon Nanotubes 61 3 Active Carbon Fibers 95 Timothy J. Mays 1 Introduction 95 2 Background 96 3 5 Acknowledgments 111 6 References 111 Applications of Active Carbon Fibers 101 4 ConcludingRemarks 110 vi 4 High Performance Carbon Fibers 119 Dan D . Edie and John J . McHugh Introduction 119 Processing Carbon Fibers from Polyacrylonitrile 119 High Performance Carbon Fibers from Novel Precursors 133 Carbon Fiber Property Comparison 133 Current Areas for High Performance Carbon Fiber Research 134 Summary and Conclusions 135 References 135 Carbon Fibers from Mesophase Pitch 123 5 Vapor Grown Carbon Fiber Composites 139 Max L . Lake and Jyh-Ming Ting Introduction 139 CurrentForms 142 Fiberproperties 144 Composite Properties 146 Potential Applications 158 Manufacturing Issues 160 Conclusions 164 References 165 6 Porous Carbon Fiber-Carbon Binder Composites 169 Timothy D . Burchell Introduction 169 Manufacture 169 Carbon Bonded Carbon Fiber 173 Damage Tolerant Light Absorbing Materials 181 Summary and Conclusions 200 Acknowledgments 201 References 201 Carbon Fiber Composite Molecular Sieves 183 7 Coal-DerivedCarbons 205 Peter G . Stansberry. John W . Zondlo and Alfred H . Stiller 1 Review of Coal Derived Carbons 205 2 SolventExtractionofCoal 211 3 Preparation and Characteristics of Cokes Produced from Solvent Extraction 223 4 Preparation and Evaluation of Graphite from Coal-Derived Feedstocks 229 5 Summary 233 6 Acknowledgments 233 7 References 233 8 Activated Carbon for Automotive Applications 235 Philip J. Johnson. David J. Setsuda and Roger S . Williams Background 235 Activated Carbon 239 Vehicle Fuel Vapor Systems 244 Adsorption 246 Carbon Canister Design 252 Application of Canisters in Running Loss Emission Control 257 Application of Canisters in ORVR Control 263 Summary and Conclusions 265 References 266 9 Adsorbent Storage for Natural Gas Vehicles 269 Terv L . Cook. Costa Komodromos. David F . Quinn and Steve Ragun 1 Introduction 269 2 Storage of Natural Gas 274 3 Adsorbents 280 4 Adsorbent Fill-Empty Testing 293 5 GuardBeds 294 6 Summary 298 7 References 299 [...]... a-carbyne P-carbyne Structurea hex hex hex a, /Pm 895 894 824 c /Pm , 14 08 15 36 768 Densityb 3.43 2.68 3 .13 Ref ~ 7 1 E 8 ,19 1 1 [18 ,19 1 carbon VI rhomb 923 12 24 2.90 [20-2 21 Carbolite 1 hex 1I92 10 62 1. 46 [24] a- hex = hexagonal, rhomb =rhombohedral; b, g.crn-’ The hfferent forms of carbynes were assumed to be polytypes with different numbers of carbon atoms in the chains lying parallel to the hexagonal axis... recently, well-graphitised carbons have been formed by heat-treatment of compacted polyimide films [ 15 1 2.3 Carbynes Carbynes are a form of carbon with chains of carbon atoms formed from conjugated C(sp')=C(sp') bonds (polyynes): -c-=C - C=C - or polycumulene C(sp2)=C(spz) double bonds From X-ray diffraction studies of short chain (C,-C,) polyynes [16 1 C=C bond lengths ranged from 11 9 -12 1 pm while C-C bond... engineers for may years to come References 1 Donnet, J-B and Bansal, R.C Carbon Fibers, 2nd Edition, Marcel Dekker, Inc., New York 19 90 2 Thomas, C.R., ed Essentials o Carbon- Carbon Composites,Royal Society of f Chemistry, UK 19 93 3 Buckley, J.D and Edie, D.D Carbon- Carbon Materials and Composites, Noyes Publications, Park Ridge, NJ 19 93 4 Savage, G Carbon- Carbon Composites, Chapman & Hall, London, 19 93... 11 Applications of Carbon in Lithium-Ion Batteries Tao Zheng and Jeff Dahn 1 2 3 4 5 6 7 303 303 306 313 319 322 339 339 3 41 Introduction 3 41 Useful Characterization Methods 347 GraphiticCarbons 353 Hydrogen-Containing Carbons from Pyrolyzed Organic Precursors 358 Microporous Carbons from Pyrolyzed Hard -Carbon. .. known of their properties Table 4 Some properties of crystallineforms of carbon property Bond IengtWpm Density/(g.cm" ) Bulk moduludGPa Young's moduiudGPa Melting pointK Thermal conductivitvd diamond a (cubic) I54 3.52 442 10 54 4500 15 000 e graphite (hexagonal) 14 2,335 2.26 286 10 20,36.3 4450 2800.5 * ca = 6 (fee) 14 6 ,14 4 1. 72 6.8 16 11 80 0.4 g a data fiom [ 5 ] ;b, data from [SI,anisotropic pmperties:... However, the application of carbon materials in many advanced technologies are reported here Carbon has played an important role in mankind's technological and social development In the form of charcoal it was an essential ingredient of gunpowder! The industrial revolution of the 18 * and 19 " centuries was powered by steam raised from the burning of coal! New applications of carbon materials wl surely be... lengths ranged fiom 13 2 -13 8 pm, depending upon the local molecular environment, cf Table 2 In the late 19 60s El Goresy and Donnay [ 17 1 discovered a new form of carbon which they called white carbon or Chaoite in a carbon- rich gneiss in the Ries meteorite crater in Bavaria Chaoite has an hexagonal crystal structure and it 7 was proposed that it consisted of polyyne or polycumulene carbon chains lying... improved adsorbent carbons, advanced cycles, and improved heat transfer in the granular adsorbent carbon beds Chapter 11 reports the use of carbon materials in the fast growing consumer electronics application of lithium-ion batteries The principles of operation of a lithumion battery and the mechanism of Li insertion are reviewed The d u e n c e of the structure of carbon materials on anode performance is... kinks in extended carbon chains, Fig 3A They were able to correlate the c, value for the different carbyne forms with assumed numbers of carbon atoms, n (in the range n = 6 to 12 ), in the linear parts of the chains co A B Fig 3 A, A kinked polyyne chain model for linear carbynes (after [23]); B, cyclo C -18 carbyne [25] 8 Recently, Tanuma and Palnichenko [24] have reported a new form of carbon which they... showing that the hexagonal form is more stable The density of both forms of graphite is 2.26 g ~ m - ~ - For both forms of graphite the in-plane C-C distance is 14 2 pm, i.e., intermediate between Csp3-Csp3and Csp*spz bond lengths, 15 3 and 13 2 pm respectively, Table 1 Consideration of the resonance structures between carbon atoms in the plane show that each C-C bond in the carbon layer plane has about . naney 1 Introduction 1 2 Crystalline Forms of Carbon 3 3 The Phase and Transition Diagram for Carbon 12 4 CarbonFilms 14 5 Carbon Nanoparticles 18 6 Engineering Carbons. Mays 1 Introduction 95 2 Background 96 3 5 Acknowledgments 11 1 6 References 11 1 Applications of Active Carbon Fibers 10 1 4 ConcludingRemarks 11 0 vi 4 High Performance. Carbon Materials for Advanced Technologies Carbon Materials for Advanced Technologies Edited by Timothy D. Burchell Oak Ridge, National Laboratory Oak Ridge, TN 378 31 -6088