Carbon Nanomaterials for Advanced Energy Systems

Wen Lu, PhD, obtained his BSc and MSc from Yunnan University in China and his PhD at the University of Wollongong in Australia. He has been a Senior Research Scientist and Group Leader leading research in multiple research companies in USA. His research activities have been focused on the applications of electrochemistry and advanced materials to the development of a range of electrochemical devices, including energy conversion and storage devices.Jong-Beom Baek, PhD, is a Professor of the School of Energy and Chemical Engineering/Director of Low-Dimensional Carbon Materials Center (LCMC) in Ulsan National Institute of Science and Technology (UNIST, Korea). He obtained PhD in Polymer Science from the University of Akron (USA). Dr. Baek's current research interests focus on the defect-selective functionalization of carbon-based nanomaterials for application-specific purposes, including energy-related applications.Liming Dai, PhD, is Case Western Reserve University's Kent Hale Smith Professor in the Department of Macromolecular Science and Engineering. He is also director of the Center of Advanced Science and Engineering for Carbon (Case4Carbon). Dr. Dai received a BSc degree from Zhejiang University, and a PhD from the Australian National University.

• List of Contributors xiiiPreface xviiPART I Synthesis and characterization of carbon nanomaterials 11 Fullerenes, Higher Fullerenes, and their Hybrids: Synthesis, Characterization, and Environmental Considerations 31.1 Introduction, 31.2 Fullerene, Higher Fullerenes, and Nanohybrids: Structures and Historical Perspective, 51.2.1 C60 Fullerene, 51.2.2 Higher Fullerenes, 61.2.3 Fullerene-Based Nanohybrids, 71.3 Synthesis and Characterization, 71.3.1 Fullerenes and Higher Fullerenes, 71.3.1.1 Carbon Soot Synthesis, 71.3.1.2 Extraction, Separation, and Purification, 101.3.1.3 Chemical Synthesis Processes, 111.3.1.4 Fullerene-Based Nanohybrids, 121.3.2 Characterization, 121.3.2.1 Mass Spectroscopy, 121.3.2.2 NMR, 131.3.2.3 Optical Spectroscopy, 131.3.2.4 HPLC, 141.3.2.5 Electron Microscopy, 141.3.2.6 Static and Dynamic Light Scattering, 141.4 Energy Applications, 171.4.1 Solar Cells and Photovoltaic Materials, 171.4.2 Hydrogen Storage Materials, 191.4.3 Electronic Components (Batteries, Capacitors, and Open]Circuit Voltage Applications), 201.4.4 Superconductivity, Electrical, and Electronic Properties Relevant to Energy Applications, 201.4.5 Photochemical and Photophysical Properties Pertinent for Energy Applications, 211.5 Environmental Considerations for Fullerene Synthesis and Processing, 211.5.1 Existing Environmental Literature for C60, 221.5.2 Environmental Literature Status for Higher Fullerenes and NHs, 241.5.3 Environmental Considerations, 241.5.3.1 Consideration for Solvents, 261.5.3.2 Considerations for Derivatization, 261.5.3.3 Consideration for Coatings, 27References, 282 Carbon Nanotubes 472.1 Synthesis of Carbon Nanotubes, 472.1.1 Introduction and Structure of Carbon Nanotube, 472.1.2 Arc Discharge and Laser Ablation, 492.1.3 Chemical Vapor Deposition, 502.1.4 Aligned Growth, 522.1.5 Selective Synthesis of Carbon Nanotubes, 572.1.6 Summary, 632.2 Characterization of Nanotubes, 632.2.1 Introduction, 632.2.2 Spectroscopy, 632.2.2.1 Raman Spectroscopy, 632.2.2.2 Optical Absorption (UV]Vis]NIR), 662.2.2.3 Photoluminescence Spectroscopy, 682.2.3 Microscopy, 702.2.3.1 Scanning Tunneling Microscopy and Transmission Electron Microscopy, 702.3 Summary, 73References, 733 Synthesis and Characterization of Graphene 853.1 Introduction, 853.2 Overview of Graphene Synthesis Methodologies, 873.2.1 Mechanical Exfoliation, 903.2.2 Chemical Exfoliation, 933.2.3 Chemical Synthesis: Graphene from Reduced Graphene Oxide, 973.2.4 Direct Chemical Synthesis, 1023.2.5 CVD Process, 1023.2.5.1 Graphene Synthesis by CVD Process, 1033.2.5.2 Graphene Synthesis by Plasma CVD Process, 1093.2.5.3 Grain and GBs in CVD Graphene, 1103.2.6 Epitaxial Growth of Graphene on SiC Surface, 1113.3 Graphene Characterizations, 1133.3.1 Optical Microscopy, 1143.3.2 Raman Spectroscopy, 1163.3.3 High Resolution Transmission Electron Microscopy, 1183.3.4 Scanning Probe Microscopy, 1193.4 Summary and Outlook, 121References, 1224 Doping Carbon Nanomaterials with Heteroatoms 1334.1 Introduction, 1334.2 Local Bonding of the Dopants, 1354.3 Synthesis of Heterodoped Nanocarbons, 1374.4 Characterization of Heterodoped Nanotubes and Graphene, 1394.5 Potential Applications, 1464.6 Summary and Outlook, 152References, 152Part II Carbon Na nomaterials For Energy Conversion 1635 High-Performance Polymer Solar Cells Containing Carbon Nanomaterials 1655.1 Introduction, 1655.2 Carbon Nanomaterials as Transparent Electrodes, 1675.2.1 CNT Electrode, 1685.2.2 Graphene Electrode, 1695.2.3 Graphene/CNT Hybrid Electrode, 1715.3 Carbon Nanomaterials as Charge Extraction Layers, 1715.4 Carbon Nanomaterials in the Active Layer, 1785.4.1 Carbon Nanomaterials as an Electron Acceptor, 1785.4.2 Carbon Nanomaterials as Additives, 1805.4.3 Donor/Acceptor Functionalized with Carbon Nanomaterials, 1835.5 Concluding Remarks, 185Acknowledgments, 185References, 1856 Graphene for Energy Solutions and Its Printable Applications 1916.1 Introduction to Graphene, 1916.2 Energy Harvesting from Solar Cells, 1926.2.1 DSSCs, 1936.2.2 Graphene and DSSCs, 1956.2.2.1 Counter Electrode, 1956.2.2.2 Photoanode, 1986.2.2.3 Transparent Conducting Oxide, 1996.2.2.4 Electrolyte, 2006.3 Opv Devices, 2006.3.1 Graphene and OPVs, 2016.3.1.1 Transparent Conducting Oxide, 2016.3.1.2 BHJ, 2036.3.1.3 Hole Transport Layer, 2046.4 Lithium-Ion Batteries, 2046.4.1 Graphene and Lithium-Ion Batteries, 2056.4.1.1 Anode Material, 2056.4.1.2 Cathode Material, 2096.4.2 Li–S and Li–O2 Batteries, 2116.5 Supercapacitors, 2126.5.1 Graphene and Supercapacitors, 2136.6 Graphene Inks, 2166.7 Conclusions, 219References, 2207 Quantum Dot and Heterojunction Solar Cells Containing Carbon Nanomaterials 2377.1 Introduction, 2377.2 QD Solar Cells Containing Carbon Nanomaterials, 2387.2.1 CNTs and Graphene as TCE in QD Solar Cells, 2387.2.1.1 CNTs as TCE Material in QD Solar Cells, 2397.2.1.2 Graphene as TCE Material in QD Solar Cells, 2407.2.2 Carbon Nanomaterials and QD Composites in Solar Cells, 2417.2.2.1 C60 and QD Composites, 2417.2.2.2 CNTs and QD Composites, 2447.2.2.3 Graphene and QD Composites, 2457.2.3 Graphene QDs Solar Cells, 2477.2.3.1 Physical Properties of GQDs, 2477.2.3.2 Synthesis of GQDs, 2477.2.3.3 PV Devices of GQDs, 2477.3 Carbon Nanomaterial/Semiconductor Heterojunction Solar Cells, 2497.3.1 Principle of Carbon/Semiconductor Heterojunction Solar Cells, 2497.3.2 a-C/Semiconductor Heterojunction Solar Cells, 2507.3.3 CNT/Semiconductor Heterojunction Solar Cells, 2527.3.4 Graphene/Semiconductor Heterojunction Solar Cells, 2537.4 Summary, 261References, 2618 Fuel Cell Catalysts Based on Carbon Nanomaterials 2678.1 Introduction, 2678.2 Nanocarbon-Supported Catalysts, 2688.2.1 CNT-Supported Catalysts, 2688.2.2 Graphene-Supported Catalysts, 2718.3 Interface Interaction between Pt Clusters and Graphitic Surface, 2768.4 Carbon Catalyst, 2818.4.1 Catalytic Activity for ORR, 2818.4.2 Effect of N-Dope on O2 Adsorption, 2838.4.3 Effect of N-Dope on the Local Electronic Structure for Pyridinic-N and Graphitic-N, 2858.4.3.1 Pyridinic-N, 2878.4.3.2 Graphitic-N, 2888.4.4 Summary of Active Sites for ORR, 290References, 291PART III Carbon nanomaterials for energy storage 2959 Supercapacitors Based on Carbon Nanomaterials 2979.1 Introduction, 2979.2 Supercapacitor Technology and Performance, 2989.3 Nanoporous Carbon, 3049.3.1 Supercapacitors with Nonaqueous Electrolytes, 3049.3.2 Supercapacitors with Aqueous Electrolytes, 3119.4 Graphene and Carbon Nanotubes, 3219.5 Nanostructured Carbon Composites, 3269.6 Other Composites with Carbon Nanomaterials, 3279.7 Conclusions, 329References, 33010 Lithium-Ion Batteries Based on Carbon Nanomaterials 33910.1 Introduction, 33910.2 Improving Li-Ion Battery Energy Density, 34410.3 Improvements to Lithium-Ion Batteries Using Carbon Nanomaterials, 34510.3.1 Carbon Nanomaterials as Active Materials, 34510.4 Carbon Nanomaterials as Conductive Additives, 34610.4.1 Current and SOA Conductive Additives, 34610.5 Swcnt Additives to Increase Energy Density, 34810.6 Carbon Nanomaterials as Current Collectors, 35110.6.1 Current Collector Options, 35110.7 Implementation of Carbon Nanomaterial Current Collectors for Standard Electrode Composites, 35410.7.1 Anode: MCMB Active Material, 35410.7.2 Cathode: NCA Active Material, 35610.8 Implementation of Carbon Nanomaterial Current Collectors for Alloying Active Materials, 35610.9 Ultrasonic Bonding for Pouch Cell Development, 35810.10 Conclusion, 359References, 36211 Lithium/Sulfur Batteries Based on Carbon Nanomaterials 36511.1 Introduction, 36511.2 Fundamentals of Lithium/Sulfur Cells, 36611.2.1 Operating Principles, 36611.2.2 Scientific Problems, 36811.2.2.1 Dissolution and Shuttle Effect of Lithium Polysulfides, 36911.2.2.2 Insulating Nature of Sulfur and Li2S, 36911.2.2.3 Volume Change of the Sulfur Electrode during Cycling, 36911.2.3 Research Strategy, 36911.3 Nanostructure Carbon–Sulfur, 37011.3.1 Porous Carbon–Sulfur Composite, 37111.3.2 One-Dimensional Carbon–Sulfur Composite, 37311.3.3 Two-Dimensional Carbon (Graphene)–Sulfur, 37511.3.4 Three-Dimensional Carbon Paper–Sulfur, 37711.3.5 Preparation Method of Sulfur–Carbon Composite, 37711.4 Carbon Layer as a Polysulfide Separator, 38011.5 Opportunities and Perspectives, 381References, 38212 Lithium–air Batteries Based on Carbon Nanomaterials 38512.1 Metal–Air Batteries, 38512.2 Li–Air Chemistry, 38712.2.1 Aqueous Electrolyte Cell, 38712.2.2 Nonaqueous Aprotic Electrolyte Cell, 38912.2.3 Mixed Aqueous/Aprotic Electrolyte Cell, 39112.2.4 All Solid-State Cell, 39112.3 Carbon Nanomaterials for Li–Air Cells Cathode, 39312.4 Amorphous Carbons, 39312.4.1 Porous Carbons, 39312.5 Graphitic Carbons, 39512.5.1 Carbon Nanotubes, 39512.5.2 Graphene, 39812.5.3 Composite Air Electrodes, 40012.6 Conclusions, 403References, 40313 Carbon-Based Nanomaterials for H2 Storage 40713.1 Introduction, 40713.2 Hydrogen Storage in Fullerenes, 40813.3 Hydrogen Storage in Carbon Nanotubes, 41413.4 Hydrogen Storage in Graphene-Based Materials, 41913.5 Conclusions, 427Acknowledgments, 428References, 428Index 439