Contents Preface .............................................................................................................v Acknowledgments ..............................................................................................vii Chapter 1: Introduction......................................................................................1 1.1 What is graphene?.................................................................................................. 1 1.2 Fundamentals of materials science for carbon materials ..................................... 5 1.2.1 Classi.cation of carbon materials ..................................................................... 5 1.2.2 Structure and nanotexture of carbon materials.................................................6 1.2.3 Carbonization and graphitization ...................................................................... 8 1.2.4 Carbon materials .............................................................................................. 12 1.3 Construction and purposes of the current book..................................................29 References................................................................................................................... 31 Chapter 2: Preparation of graphene .................................................................. 39 2.1 Chemical vapor deposition .................................................................................. 41 2.1.1 Synthesis of graphene .lms............................................................................. 41 2.1.2 Synthesis of graphene .akes ........................................................................... 60 2.1.3 Synthesis of single-walled carbon nanohorns.................................................65 2.1.4 Substitutional doping of heteroatoms.............................................................. 69 2.1.5 Graphene foams ............................................................................................... 80 2.2 Cleavage (peeling) ............................................................................................... 81 2.2.1 Mechanical cleavage........................................................................................81 2.2.2 Cleavage in solution ........................................................................................ 85 2.2.3 Cleavage via intercalation compounds............................................................95 2.3 Exfoliation via graphene oxide.......................................................................... 101 2.3.1 Synthesis of graphene oxide..........................................................................102 2.3.2 Exfoliation of graphene oxide ....................................................................... 105 2.3.3 Reduction of graphene oxide......................................................................... 107 2.3.4 Fabrication of reduced graphene oxide foams (sponges).............................123 2.3.5 Functionalization of reduced graphene oxide...............................................127 2.3.6 Substitutional doping of heteroatoms............................................................ 133 2.3.7 Fabrication of transparent reduced graphene oxide .lms ............................ 135 2.4 Other processes .................................................................................................. 138 2.4.1 Chemical synthesis......................................................................................... 138 i Contents 2.4.2 Synthesis via pyrolysis .................................................................................. 143 2.4.3 Unzipping of carbon nanotubes..................................................................... 147 2.5 Concluding remarks ........................................................................................... 150 References................................................................................................................. 153 Chapter 3: Electrical properties and applications .............................................. 173 3.1 Fundamental electrical properties...................................................................... 174 3.1.1 Electronic structure of graphene ................................................................... 174 3.1.2 Effects of defects and edges..........................................................................181 3.2 Applications to information technology............................................................189 3.2.1 Transistor devices........................................................................................... 189 3.2.2 Spintronics devices ........................................................................................ 207 3.2.3 Transparent electrode.....................................................................................221 3.3 Applications to social .elds .............................................................................. 226 3.3.1 Sensor devices................................................................................................226 3.3.2 Photon detectors.............................................................................................233 3.3.3 Resistance standard........................................................................................237 3.3.4 Electron .eld emission .................................................................................. 242 3.4 Concluding remarks ........................................................................................... 244 References................................................................................................................. 244 Chapter 4: Chemical properties and applications............................................... 251 4.1 Fundamental chemical properties......................................................................252 4.1.1 Hydrogenation................................................................................................253 4.1.2 Oxygenation ................................................................................................... 256 4.1.3 Layer modi.cation.........................................................................................258 4.2 Applications to energy storage and conversion ................................................ 259 4.2.1 Lithium-ion batteries...................................................................................... 259 4.2.2 Electrochemical capacitors ............................................................................ 268 4.2.3 Lithium-ion capacitors...................................................................................278 4.2.4 Lithium-sulfur batteries ................................................................................. 282 4.2.5 Solar cells (photovoltaic cells) ...................................................................... 292 4.2.6 Fuel cells ........................................................................................................ 298 4.2.7 Hydrogen storage ........................................................................................... 306 4.3 Applications to environment remediation ......................................................... 311 4.3.1 Adsorption of polluting molecules and ions.................................................311 4.3.2 Sorption and recovery of oils ........................................................................ 321 4.3.3 Capacitive deionization for water desalination.............................................325 4.3.4 Catalysts ......................................................................................................... 332 4.3.5 Chemical sensors............................................................................................ 341 4.4 Concluding remarks ........................................................................................... 352 References................................................................................................................. 354 ii Contents Chapter 5: Mechanical properties and applications............................................ 373 5.1 Fundamental mechanical properties .................................................................. 374 5.2 Nanolubricants.................................................................................................... 383 5.3 Mechanical sensors ............................................................................................ 387 5.4 Mechanical reinforcement ................................................................................. 393 5.4.1 Reinforcement of plastics .............................................................................. 393 5.4.2 Reinforcement of ceramics............................................................................395 5.4.3 Reinforcement of metals................................................................................ 400 5.5 Reduced graphene oxide .bers.......................................................................... 404 5.6 Concluding remarks ........................................................................................... 409 References................................................................................................................. 410 Chapter 6: Thermal properties and applications................................................ 415 6.1 Fundamental thermal properties ........................................................................ 416 6.2 Thermal interface materials ............................................................................... 422 6.3 Nano.uids........................................................................................................... 429 6.4 Thermoelectric power ........................................................................................ 432 6.5 Thermal energy storage ..................................................................................... 436 6.6 Concluding remarks ........................................................................................... 442 References................................................................................................................. 443 Chapter 7: Biomedical properties and applications ............................................ 449 7.1 Biocompatibility.................................................................................................450 7.2 Cell management................................................................................................ 454 7.2.1 Scaffolds for cell culturing ............................................................................ 454 7.2.2 Stem cell differentiation ................................................................................ 458 7.2.3 Cell imaging...................................................................................................459 7.2.4 Antibacterial activity...................................................................................... 460 7.3 Drug delivery systems........................................................................................ 464 7.4 Biosensors........................................................................................................... 469 7.5 Concluding remarks ........................................................................................... 476 References................................................................................................................. 478 Chapter 8: Beyond graphene........................................................................... 485 8.1 Graphene derivatives..........................................................................................486 8.1.1 Graphane (hydrogenated graphene)............................................................... 487 8.1.2 Fluorographene (.uorinated graphene) ......................................................... 495 8.1.3 Graphene oxide (oxidized graphene) ............................................................ 501 8.1.4 Graphyne and graphdiyne..............................................................................514 8.2 Single-layer materials ........................................................................................ 519 8.2.1 Honeycomb layers of group IV elements...................................................... 519 8.2.2 Honeycomb layers of group IIIeV compounds ........................................... 524 8.2.3 Single layers of transition metal dichalcogenides ........................................ 531 iii Contents 8.3 Layer-by-layer composites................................................................................. 537 8.4 Concluding remarks ........................................................................................... 544 References................................................................................................................. 546 Chapter 9: Summary and prospects.................................................................561 9.1 Summary on graphene ....................................................................................... 561 9.2 Prospects.............................................................................................................565 9.2.1 Importance of number of layers stacked..................................................... 565 9.2.2 Two kinds of graphene materials ................................................................ 570 9.2.3 Field effect and zero bandgap ..................................................................... 572 9.2.4 Extremely high thermal conductivity..........................................................574 9.2.5 Basics for molecular sensing.......................................................................576 9.2.6 Basics for foreign atom doping...................................................................578 9.2.7 Importance of pep interaction................................................................... 580 9.2.8 Biomedical applications............................................................................... 582 9.2.9 New composite materials............................................................................. 585 9.2.10 Extension to organic chemistry ................................................................... 588 References................................................................................................................. 589 Index ............................................................................................................ 593