Tài liệu CARBON ALLOYSNOVEL CONCEPTS TO DEVELOP CARBON SCIENCE A N D TECHNOLOGYE. YASUDA, M. INAGAKI

CARBON ALLOYS

NOVEL CONCEPTS TO DEVELOP CARBON

SCIENCE AND TECHNOLOGY

E. YASUDA, M. INAGAKI, K. KANEKO,

0, A. OYA & Y. TAN

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CARBON ALLOYS

Novel Concepts to Develop Carbon

Science and Technology

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CARBON ALLOYS

Novel Concepts to Develop Carbon

Science and Technology

Edited by

Ei-ichi YASUDA

Michio INAGAKI

Katsumi KANEKO

Morinobu END0

Asao OYA

Yasuhiro TANABE

2003

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V

Contents

... Preface ......................................... xiii

Part 1 . Introduction

Chapter 1 . Introduction ................................. 3

1 AShortHistory ............................... 3

2 CarbonFamily ................................ 5

3 CarbonAlloys ................................ 9

References ..................................... 11

Ei-ichi Yasuda and Michio Inagaki

Part 2 . Space Control in Carbon Alloys

Chapter 2 . Hybrid Orbital Control in Carbon Alloys ................ 15

Hybridization in a Carbon Atom ..................... 15

2 Defect StatesandModificationsof theHybridization ......... 27

Spectroscopies for sp” Structure ...................... 33

4 Conclusions ................................. 38

References ..................................... 38

Atomic and Molecular Scales ............................. 41

1 . Introduction 41

2 . Intercalation Compounds 42

Insertion of Li Ions into the Disordered Carbon Materials ....... 44

4 Substitution of Heteroatoms ....................... 46

5 Metal-doped Fullerenes .......................... 49

Metal-doped Carbon Nanotubes ..................... 50

7 Conclusions ................................. 54

Chapter 4 . Surface and Hidden Surface-controlled Carbon Alloys ........ 57

Materials .................................. 57

Carbon Structure of Superhigh Surface Area .............. 64

Design of Hidden Surfaces with Alloying ................ 65

Riichiro Saito

1

3

Chapter 3 . Structural Design and Functions of Carbon Materials by Alloying in

Morinobu Endo. Takuya Hayashi, YoongAhm Kim. Hiroaki Ohta and

Sung Wha Hong ................................ ......................... 3

6

References 54

Katsumi Kaneko

1

2

3

.....................................

Importance of Hidden Surfaces and Confined Spaces in Carbon

vi Contents

4

5

Properties of Hidden Surface- or Pore Space-alloyed Carbons ..... 68

Design of New Porous Carbon with Carbon Alloying Technique ... 76

References ..................................... 77

Chapter 5 . Control of Interface and Microstructure in Carbon Alloys ....... 83

1 Introduction ................................ 83

2 Interface Control .............................. 85

3 Microstructure Control .......................... 89

4 Conclusion ................................. 93

References .................................... 93

Yasuhiro Tanabe and Ei-ichi Yasuda

Part 3 . Typical Carbon Alloys and Processing

Chapter 6 . Intercalation Compounds ......................... 99

1 Introduction ................................ 99

Li-insertion into Carbon Materials ................... 100

Carbon Materials ............................. 103

Alkali Metals ............................... 104

Boehmite with Layered Structure .................... 105

6 Conclusion ................................. 105

References .................................... 106

Chapter 7 . Porous Carbon .............................. 109

1 Introduction ................................ 109

Control of Pore Structure ........................ 110

Performance of Advanced Porous Carbon ............... 118

4 Conclusions. ............................... 123

References .................................... 124

Noboru Akzuawa

2

3

4

5

New Intercalation Compounds Prepared from Unique Host

Host Effect on the lntercalation of Halogen Molecules and

Physical Properties of MC1,. GICs and Alkyl Derivative of

Takashi Kyotani

2

3

Chapter 8 . Polymer Blend Technique €or Designing Carbon Materials ..... 129

Asao @a

2 .

3

5

1 . Introduction ................................ 129

Porous Carbon Materials ......................... 129

4 Carbon Nanofibers and Carbon Nanotubes .............. 133

Other Fibrous Carbon Materials with Unique Shapes ......... 139

6 Conclusions ................................ 141

References .................................... 141

Preferential Support of Metal Particles on Pore Surface ....... 131

Part 4 . The Latest Characterization Techniques

Chapter 9 . Computer Simulations .......................... 145

Shinji Tsuneyuki

1 Methods., ................................ 145

vii

2 Applications ................................ 150

3 Conclusions ................................ 156

References .................................... 156

Chapter 10 . X-ray Diffraction Methods to Study Crystallite Size and Lattice

Constants of Carbon Materials ........................... 161

1 . Introduction ................................ 161

Measurement Method (JSPS Method) ................. 162

Temperatures ............................... 170

References .................................... 173

Scattering ....................................... 175

1 . Introduction ................................ 175

Fundamentals of Small-Angle X-ray Scattering ............ 176

3 Analyses .................................. 180

Examples of Structure Determination ................. 183

References .................................... 187

Minoru Shiraishi and Michio Znagaki

2

3 Characterization of Carbonized Materials Heat-treated at Low

Chapter 11 . Pore Structure Analyses of Carbons by Small-Angle X-ray

Keiko Nishikawa

2 .

4

Chapter 12 . XAFS Analysis and Applications to Carbons and Catalysts ..... 189

Hiromi Yamashita

1 Introduction ................................ 189

2 XAFSAnalysis .............................. 190

Applications to Carbon Related Materials and Catalysts ....... 200

XAFS in the Future ............................ 207

References .................................... 207

3

4

Chapter 13 . X-Ray Photoelectron Spectroscopy and its Application to Carbon . 211

Noboru Suzuki

2

3

1 Introduction and XPS .......................... 211

Cls Binding Energy ............................ 212

Application to Carbon Materials .................... 212

References .................................... 220

Chapter 14 . Transmission Electron Microscopy .................. 223

1 Introduction ................................ 223

Materials Characterization by Means of TEM ............. 223

Specimen Preparation by FIB ...................... 231

In-Situ Heating Experiment ....................... 235

References .................................... 238

Characterization of Carbon Materials ........................ 239

1 Introduction ................................ 239

Basic Principles of EELS and Instrumentation ............. 240

Hiroyasu Saka

2

3

4

Chapter 15 . Electron Energy-Loss Spectroscopy and its Applications to

Hisako Hirai

2

... VI11 Contents

3

4 Applications to Characterizing Carbon Materials ........... 249

5 . Conclusions: The Future of EELS .................... 254

References .................................... 255

The Energy-Loss Spectrum ....................... 242

Chapter 16 . Visualization of the Atomic-scale Structure and Reactivity of

Metal Carbide Surfaces Using Scanning Tunneling Microscopy ......... 257

Ken-ichi Fukui, Rong-Li Lo and Yasuhiro Iwasawa

1 Introduction ................................ 257

2 Principle of Scanning Tunneling Microscopy (STM) .......... 259

3 Preparation of Mo, C Surfaces ...................... 259

4 Visualization of the Atomic-scale Structure and Reactivity of

Molybdenum Carbide Surfaces by STM ................ 260

5 Conclusions and Future Prospects .................... 265

References .................................... 266

Chapter 17 . Infra-Red Spectra. Electron Paramagnetic Resonance. and Proton

Magnetic Thermal Analysis ............................. 269

Osamu Ito. Tadaaki Ikoma and Richard Sakurovs

1 Infra-Red (IR) Spectra .......................... 269

2 EPR .................................... 276

3 Proton Magnetic Resonance Thermal Analysis (PMRTA) ...... 281

References .................................... 283

Chapter 18 . Raman Spectroscopy as a Characterization Tool for Carbon

Materials ........................................ 285

Masato Kakihana and Minoru Osada

1 Introduction ................................ 285

2 Raman Spectra of Carbon Materials .................. 288

3 Remarks about Raman Measurements ................. 290

4 Recent Raman Studies of Carbon Materials .............. 292

References .................................... 297

Chapter 19 . Basics of Nuclear Magnetic Resonance and its Application to

Carbon Alloys ..................................... 299

Takashi Nishizawa

1 Introduction ................................ 299

2 Apparatus ................................. 299

3 Basics of NMR for Spin 112 Nucleus .................. 300

4 Characterization of Pitch ......................... 308

5 Solid-state 'Li-NMR ........................... 313

References .................................... 318

Chapter 20 . Gas Adsorption ............................. 319

Yohko Hanzawa and Katsumi &neb

1 Adsorption, Absorption. Occlusion and Storage ............ 319

2 Classification of Pores and Porosity ................... 320

3 Selection of an Adsorbate Molecule ................... 321

4 Surface Structure and the Adsorption Isotherm ............ 324

ix

References .................................... 331

Chapter 21 . Electrochemical Characterization of Carbons and Carbon Alloys . 335

Tsuyoshi Nakajima

1 Introduction ................................ 335

2 Characterization Techniques ....................... 336

3 Electrochemical Characterization of Carbon Alloys .......... 340

4 Conclusions ................................ 349

References .................................... 349

Mototsugu Sakai

1 Introduction ................................ 351

2 Theoretical Considerations ....................... 353

3 Experimental Details ........................... 360

4 Application to Carbon-related Materials ................ 364

5 Concluding Remarks ........................... 380

References .................................... 382

Chapter 23 . Magnetism of Nano-graphite ..................... 385

Toshiaki Enoki. Bhagvatula L . K Prasad, Yoshiyuki Shibayama.

Kazuyuki Takai and Hirohiko Sat0

1 Introduction ................................ 385

2 Conversion from Diamond to Graphite in Nano-scale Dimension . . 386

3 Nano-graphite Network ......................... 389

4 Fluorinated Nano-graphite ........................ 392

References .................................... 393

Alloys ......................................... 395

2 BackgroundfortheMagnetoresistanceMeasurement ......... 395

3 Measurement of Magnetoresistance .................. 400

High-Quality Graphite Film from Aromatic Polyimide Film ..... 403

5 NegativeMagnetoresistanceinBoron-dopedGraphites ....... 409

Chapter 22 . Mechanical Probe for Micro-mano-characterization ........ 351

Chapter 24 . Magnetoresistance and its Application to Carbon and Carbon

Yoshihiro Hishiyama

1 Introduction ................................ 395

4 Application of Magnetoresistance Technique for Synthesis of

References .................................... 413

Part 5 . Function Developments and Application Potentials

Chapter 25 . Applications of Advanced Carbon Materials to the Lithium Ion

Secondary Battery ................................... 417

2 Characteristics of Li-ion Secondary Battery .............. 420

Carbon and Graphite Host Materials .................. 420

Lithium/Graphite Intercalation Compounds .............. 421

Voltage Profiles of Carbon Electrodes ................. 424

Effect of Microstructure of Carbon Anode on the Capacity ...... 426

Morinobu Endo and Yoong Ahm Kim

1 Introduction ................................ 417

3

4

5

6

X Contents

7 Li Storage Model ............................. 430

8 Conclusions ................................ 431

References .................................... 432

Chapter 26 . Electrochemical Functions ....................... 435

Mikio Miyake

1

2

3

4

Features of Carbon Materials as Electrodes .............. 435

Electrochemical Reactions on Carbon ................. 436

Electrochemical Behavior of Various Carbons ............. 439

Application of Carbon Electrodes .................... 441

References .................................... 444

Chapter 27 . Electric Double Layer Capacitors ................... 447

1 Introduction. ............................... 447

Capacitance ................................ 449

DoubleLayerCapacitanceof Other CarbonMaterials ........ 454

4 Conclusion ................................. 456

References .................................... 456

Chapter28 . FieIdElectronEmissionsfromCarbonNanotubes ......... 459

1 Introduction ................................ 459

FEM Study of Nanotubes ........................ 460

Nanotube-based Display Devices .................... 465

References .................................... 468

Chapter 29 . Gas Separations with Carbon Membranes .............. 469

Katsuki Kusakabe and Shigeham Morooka

1 Properties of Carbon Membranes .................... 469

2 Preparation of Carbon Membranes ................... 472

3 PermeancesofMolecularSievingCarbonMembranes ........ 474

4 Oxidation of Molecular Sieving Carbon Membranes ......... 478

5 Separation Based on Surface Flow ................... 480

6 Conclusions ................................ 481

References .................................... 481

Chapter 30 . Property Control of Carbon Materials by Fluorination ....... 485

Hidekazu Touhara

1 Introduction ................................ 485

2 Control of Carbon Properties by Fluorination ............. 486

3

Alloying by Fluorination ......................... 487

References .................................... 497

Highly Active Catalyst for Reduction of Nitric Oxide (NO) ............ 499

Kouichi Miura and Hiroyuki Nakagawa 1 Introduction ................................ 499

2 Sample Preparation ............................ 500

Soshi Shiraishi

2

3

Influence of Pore Size Distribution of ACFs on Double Layer

Yahachi Saito, Koichi Hata and Sashiro Uemura

2

3

The Chemistry of Carbon Nanotubes with Fluorine and Carbon

Chapter 31 . Preparation of Metal-loaded Porous Carbons and Their Use as a

xi

3 Carbonization Behavior of the Resins .................. 501

4 Characterization of Metal Loaded Porous Carbons .......... 502

5 Nitric Oxide Decomposition on Metal Loaded Porous Carbons ... 504

6 Conclusions ................................ 512

References .................................... 512

Chapter32 . FormationofaSeaweedBedUsingCarbonFibers ......... 515

Minoru Shiraishi

1 Introduction ................................ 515

2 Rapid Fixation of Marine Organisms .................. 515

3 Food Chain Through a Carbon Fiber Seaweed Bed .......... 518

4 Formation of an Artificial Bed of Seaweed Using Carbon Fibers ... 519

References .................................... 521

Chapter 33 . Carbodcarbon Composites and Their Properties .......... 523

Tatsuo Oh

1 Introduction ................................ 523

2 Carbon Fibers and Carbon Coils .................... 524

3 Novel Materials and Control of Micro-structures ........... 527

4

and Microstructures ........................... 531

5 Fracture and its Mechanism ....................... 538

6 Microstructure Observation ....................... 542

7 Concluding Remarks ........................... 542

References .................................... 543

Chapter 34 . Super-hard Materials .......................... 545

1 Super-hard Materials ........................... 545

2 Diamond-like Carbon .......................... 546

3 CarbonNitride .............................. 552

Boron Carbonitride (BxCyNz) ...................... 556

References .................................... 557

Contributing authors .................................. 559

Subject index ...................................... 563

Improvement of Properties and Correlation Between Properties

Osamu Takai

4

5 Conclusion 557 .................................