Graphene-based Energy Devices

List of Contributors XIII
Preface XIX

1 Fundamental of Graphene 1
Seong C. Jun

1.1 Introduction 1
1.2 Synthesis of Graphene 3
1.2.1 Mechanical Cleavage 3
1.2.2 Epitaxial Growth 4
1.2.3 CVD Growth of Graphene 4
1.2.4 Solution-Based Graphene 5
1.2.5 Synthesis of Composite Material Based on Graphene Oxide 8
1.3 Characterization of Graphene 12
1.3.1 AFM (Atomic Force Microscopy) 14
1.3.2 SEM 16
1.3.3 TEM/SEAD/EELS 16
1.3.4 XPS 20
1.3.5 XRD 21
1.3.6 Raman 23
1.3.7 Photoluminesces (PL) Measurement 23
1.4 Optical Property Modification of Graphene 25
1.4.1 Absorption Property Modification of Graphene (Terahertz, UV–Visible–NIR) 25
1.4.2 PL Property Modification of Graphene 29
1.5 Optoelectric Application of Graphene 39
References 45

2 Graphene-Based Electrodes for Lithium Ion Batteries 49
RonghuaWang,Miaomiao Liu, and Jing Sun

2.1 Introduction 49
2.2 TheWorking Principle of LIBs 50
2.3 Graphene-Based Cathode Materials for LIBs 51
2.4 Graphene-Based Anode Materials for LIBs 53
2.4.1 Graphene as Anodes for LIBs 54
2.4.2 Graphene-Based Composites as Anodes for LIBs 56
2.5 Two-Dimensional (2D) Flexible and Binder-Free Graphene-Based Electrodes 67
2.5.1 Graphene-Based Flexible Anode Materials for LIBs 67
2.5.2 Graphene-Based Flexible Cathode Materials for LIBs 73
2.6 Three-Dimensional Macroscopic Graphene-Based Electrodes 74
2.7 Summary and Perspectives 78
References 79

3 Graphene-Based Energy Devices 85
Wei-Ren Liu

3.1 Introduction 85
3.2 Graphene for Li-Ion Batteries 85
3.2.1 Anode Materials 85
3.2.2 Cathode Materials 100
3.3 Graphene for Supercapacitors 105
3.4 Graphene for Li–Sulfur Batteries 111
3.5 Graphene for Fuel Cells 114
3.6 Graphene for Solar Cells 116
3.7 Summary 118
References 118

4 Graphene-Based Nanocomposites for Supercapacitors 123
Xuanxuan Zhang, Tao Hu, andMing Xie

4.1 Introduction 123
4.2 Graphene-Based Supercapacitors 124
4.2.1 EDLCs 125
4.2.2 Graphene/Metal Oxide Nanocomposites 128
4.2.3 Graphene/Conducting Polymer Composites 129
4.2.4 Atomic Layer Deposition for Graphene/Metal Oxide Nanocomposites 134
4.3 Issues and Perspectives 136
References 138

5 High-Performance Supercapacitors Based on Novel Graphene Composites 145
Junwu Xiao, Yangyang Xu, and Shihe Yang

5.1 Introduction 145
5.2 Graphene Synthesis Methods 148
5.2.1 The “Top-Down” Approach 148
5.2.2 The “Bottom-Up” Approach 150
5.3 Graphene-Based Electrodes for Supercapacitors 151
5.3.1 Graphene 151
5.3.2 Graphene-Based Composites 152
5.4 Conclusions and Prospects 165
References 166

6 Graphene for Supercapacitors 171
Richa Agrawal, Chunhui Chen, Yong Hao, Yin Song, and ChunleiWang

6.1 Introduction 171
6.1.1 Electrochemical Capacitors 171
6.1.2 Graphene as a Supercapacitor Material 175
6.2 Electrode Materials for Graphene-Based Capacitors 176
6.2.1 Double-Layer Capacitance-Based Graphene Electrode Materials 176
6.2.2 Graphene/Pseudocapacitive Material Composite Based Electrode Materials 183
6.3 Graphene-Based Asymmetric Supercapacitors 189
6.3.1 Asymmetric Capacitors Based on Graphene and Pseudocapacitive Materials 193
6.3.2 Graphene-Based Lithium-Ion Capacitors 195
6.4 Graphene-Based Microsupercapacitors 199
6.5 Summary and Outlook 204
Acknowledgments 205
References 205

7 Graphene-Based Solar-DrivenWater-Splitting Devices 215
Jian Ru Gong

7.1 Introduction 215
7.2 Basic Architectures of Solar-DrivenWater-Splitting Devices 216
7.3 Promising Prospects of Graphene in Solar-DrivenWater-Splitting Devices 217
7.4 Graphene-Based Integrated Photoelectrochemical Cells 219
7.5 Graphene-Based Mixed-Colloid Photocatalytic Systems 227
7.6 Graphene-Based Photovoltaic/Electrolyzer Devices 235
7.7 Conclusions and Perspectives 241
References 241

8 Graphene Derivatives in Photocatalysis 249
Luisa M. Pastrana-Martínez, Sergio Morales-Torres, José L. Figueiredo, Joaquim L. Faria, and Adrián M.T. Silva

8.1 Introduction 249
8.2 Graphene Oxide and Reduced Graphene Oxide 250
8.2.1 Synthesis 250
8.2.2 Properties 252
8.3 Synthesis of Graphene-Based Semiconductor Photocatalysts 254
8.3.1 Mixing Method 255
8.3.2 Sol–Gel Process 255
8.3.3 Hydrothermal and Solvothermal Methods 256
8.4 Photocatalytic Applications 257
8.4.1 Photodegradation of Organic Pollutants 258
8.4.2 Photocatalytic Splitting of H2O 262
8.4.3 Photocatalytic Reduction of CO2 264
8.4.4 Other Applications: Dye-Sensitized Solar Cells 266
8.5 Conclusions and Outlook 267
Acknowledgments 268
References 268

9 Graphene-Based Photocatalysts for Energy Applications: Progress and Future Prospects 277
WanjunWang, Donald K.L. Chan, and Jimmy C. Yu

9.1 Introduction 277
9.1.1 Synthesis of Graphene-Based Photocatalysts 278
9.1.2 Ex Situ Hybridization Strategy 279
9.1.3 In Situ Growth Strategy 279
9.2 Energy Applications 283
9.2.1 Photocatalytic Hydrogen Evolution 283
9.2.2 Photocatalytic Reduction of Carbon dioxide 285
9.2.3 Environmental Remediation 286
9.3 Conclusions and Outlook 287
References 288

10 Graphene-Based Devices for Hydrogen Storage 295
HouWang and Xingzhong Yuan

10.1 Introduction 295
10.2 Storage of Molecular Hydrogen 297
10.2.1 Graphene-Based Metal/Metal Oxide 299
10.2.2 Doped Graphene 300
10.3 Storage of Atomic Hydrogen Based on Hydrogen Spillover 301
References 304

11 Graphene-Supported Metal Nanostructures with Controllable Size and Shape as Advanced Electrocatalysts for Fuel Cells 307
Minmin Liu andWei Chen

11.1 Introduction 307
11.2 Fuel Cells 308
11.2.1 Configuration and Design of PEMFCs 309
11.2.2 Direct Methanol Fuel Cells (DMFCs) 310
11.2.3 Direct Formic Acid Fuel Cells (DFAFCs) 313
11.2.4 Direct Alcohol Fuel Cells (DAFCs) and Biofuel Cells 314
11.3 Graphene-Based Metal Nanostructures as Electrocatalysts for Fuel Cells 315
11.3.1 Graphene-Supported Metal Nanoclusters 315
11.3.2 Graphene-Supported Monometallic and Alloy Metal Nanoparticles (NPs) 317
11.3.3 Graphene-Supported Core–shell Nanostructures 321
11.3.4 Graphene-Supported Hollow Nanostructures 322
11.3.5 Graphene-Supported Cubic Nanostructures 325
11.3.6 Graphene-Supported Nanowires and Nanorods 326
11.3.7 Graphene-Supported Flower-Like Nanostructures 329
11.3.8 Graphene-Supported Nanodendrites 331
11.3.9 Other Graphene-Supported 2D or 3D Nanostructures 333
11.4 Conclusions 333
Acknowledgments 334
References 335

12 Graphene-BasedMicrobial Fuel Cells 339
Yezhen Zhang and Jian S. Ye

12.1 Introduction 339
12.2 MFC 340
12.2.1 TheWorking Principle of MFC 340
12.2.2 The Advantages of MFCs 341
12.2.3 The Classification of MFCs 342
12.3 The Development History of MFCs 345
12.4 The Application Prospect of MFC 346
12.4.1 Micro Batteries Embedded in the Body 346
12.4.2 Mobile Power Supply 346
12.4.3 Photosynthesis to Produce Electricity 346
12.4.4 Biosensor 347
12.4.5 Power Supply in Remote Areas or Open Sea 347
12.4.6 Treatment of OrganicWastewater 347
12.5 Problems Existing in the MFCs 348
12.6 Graphene-Based MFC 348
12.6.1 Anode 348
12.6.2 Membrane 350
12.6.3 Cathode 350
References 351

13 Application of Graphene-Based Materials to Improve Electrode Performance in Microbial Fuel Cells 355
Li Xiao and Zhen He

13.1 Introduction 355
13.2 Graphene Materials for Anode Electrodes in MFCs 357
13.2.1 Graphene Nanosheets 357
13.2.2 Three-Dimensional Graphene 359
13.2.3 Graphene Oxide 361
13.3 Graphene Materials for Cathode Electrodes in MFCs 361
13.3.1 Bare Graphene 362
13.3.2 Polymer Coating with Graphene as a Dopant 363
13.3.3 Metal Coating with Graphene as a Supporter 363
13.3.4 Nitrogen-Doped Graphene 364
13.4 Outlook 366
References 367

14 Applications of Graphene and Its Derivative in Enzymatic Biofuel Cells 371
A. Rashid bin Mohd Yusoff

14.1 Introduction 371
14.2 Membraneless Enzymatic Biofuel Cells 372
14.3 Modified Bioanode and Biocathode 375
14.3.1 Electrochemically Reduced Graphene Oxide and Multiwalled Carbon Nanotubes/Zinc Oxide 375
14.3.2 Graphene/Single-Walled Carbon Nanotubes 376
14.4 Conclusion 376
Acknowledgment 377
References 377

15 Graphene and Its Derivatives for Highly Efficient Organic Photovoltaics 379
Seung J. Lee and A. Rashid bin Mohd Yusoff

15.1 Introduction 379
15.2 Various Applications in Solar Cells 380
15.2.1 Conductive Electrodes 380
15.2.2 Active Layer 385
15.2.3 Charge Transport Layer 390
15.2.4 Electron Transport Layer 395
15.3 Conclusion 402
Acknowledgment 402
References 402

16 Graphene as Sensitizer 407
Mohd A. Mat-Teridi, Mohd A. Ibrahim, Norasikin Ahmad-Ludin, Siti Nur Farhana Mohd Nasir, Mohamad Yusof Sulaiman, and Kamaruzzaman Sopian

16.1 Graphene as Sensitizer 407
16.2 Graphene as Storage Current Collector 410
16.2.1 Anode Current Collector 411
16.2.2 Cathode Current Collector 413
16.3 Graphene as Photoanode Additive 415
16.3.1 DSSC Application 415
16.3.2 OPV Application 416
16.3.3 Lithium-Ion Battery 417
16.3.4 Sensor Application 418
16.3.5 Transparent Conductive Films 419
16.3.6 Photocatalytic Application 420
16.4 Graphene as Cathode Electrocatalyst 420
16.4.1 N-Doped Graphene 421
16.4.2 B-, P-, S-, and Se-Doped Graphene 422
16.5 Conclusions 423
Acknowledgment 424
References 424

Index 431