Lithium-Ion Batteries

LITHIUM-ION BATTERIES Advanced Materials and Technologies

GREEN CHEMISTRY AND CHEMICAL ENGINEERING Series Editor: Sunggyu Lee Ohio University, Athens, Ohio, USA Proton Exchange Membrane Fuel Cells: Contamination and Mitigation Strategies Hui Li, Shanna Knights, Zheng Shi, John W. Van Zee, and Jiujun Zhang Proton Exchange Membrane Fuel Cells: Materials Properties and Performance David P. Wilkinson, Jiujun Zhang, Rob Hui, Jeffrey Fergus, and Xianguo Li Solid Oxide Fuel Cells: Materials Properties and Performance Jeffrey Fergus, Rob Hui, Xianguo Li, David P. Wilkinson, and Jiujun Zhang Efficiency and Sustainability in the Energy and Chemical Industries: Scientific Principles and Case Studies, Second Edition Krishnan Sankaranarayanan, Jakob de Swaan Arons, and Hedzer van der Kooi Nuclear Hydrogen Production Handbook Xing L. Yan and Ryutaro Hino Magneto Luminous Chemical Vapor Deposition Hirotsugu Yasuda Carbon-Neutral Fuels and Energy Carriers Nazim Z. Muradov and T. Nejat Vezirogˇ lu Oxide Semiconductors for Solar Energy Conversion: Titanium Dioxide Janusz Nowotny Lithium-Ion Batteries: Advanced Materials and Technologies Xianxia Yuan, Hansan Liu, and Jiujun Zhang

GREEN CHEMISTRY AND CHEMICAL ENGINEERING

LITHIUM-ION BATTERIES Advanced Materials and Technologies

Edited by

Xianxia Yuan, Hansan Liu, and Jiujun Zhang

CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2011 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20131107 International Standard Book Number-13: 978-1-4398-4129-7 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright. com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com

Contents Preface .................................................................................................................... vii Editors ......................................................................................................................ix Contributors ......................................................................................................... xiii 1. Material Challenges and Perspectives ....................................................... 1 Daiwon Choi, Wei Wang, and Zhenguo Yang 2. Cathode Materials for Lithium-Ion Batteries ......................................... 51 Zhumabay Bakenov and Izumi Taniguchi 3. Anode Materials for Lithium-Ion Batteries ............................................ 97 Ricardo Alcántara, Pedro Lavela, Carlos Pérez-Vicente, and José L. Tirado 4. Electrolytes for Lithium-Ion Batteries.................................................... 147 Alexandra Lex-Balducci, Wesley Henderson, and Stefano Passerini 5. Separators for Lithium-Ion Batteries ...................................................... 197 Shriram Santhanagopalan and Zhengming (John) Zhang 6. First-Principles Methods in the Modeling of Li-Ion Battery Materials .................................................................................................... 253 John S. Tse and Jianjun Yang 7. A Multidimensional, Electrochemical-Thermal Coupled Lithium-Ion Battery Model ...................................................................... 303 Gang Luo and Chao-Yang Wang 8. State-of-the-Art Production Technology of Cathode and Anode Materials for Lithium-Ion Batteries ......................................... 327 Guoxian Liang and Dean D. MacNeil

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Preface Energy conversion and energy storage are becoming more and more important in today’s society due to the increased demand for stationary and mobile power. In particular, electrochemical energy conversion and storage devices using battery technologies have recently attracted attention worldwide in terms of technology development and commercialization. For example, lithium-ion batteries have been considered one of the most promising energy conversion and storage devices due to their intrinsic advantages such as high energy density, high efficiency, superior rate capability, and long cycling life compared with other batteries. Since their commercialization in 1991, lithium-ion batteries have been widely used as power sources for portable devices, cordless tools, and laptops. Furthermore, in recent years, great advancements in lithium-ion batteries have made this technology feasible in some special applications such as electric vehicle power sources, stationary energy storage systems for solar and wind energy, and smart grids. Due to their significant roles in global energy conversion and storage, the investment in research and development (R&D) from governments, industries, and the public has increased considerably in recent years. This book is designed to draw a clear picture of the current status of ­lithium-ion batteries, with a focus on the technical progress, challenges, and perspectives in the field of cathode materials, anode materials, electrolytes, separators, numerical modeling and theoretical calculation, and state-ofthe-art manufacturing processes. Design of safe and powerful lithium-ion batteries and the methods/approaches for enhancing the performance of next-generation lithium-ion battery technology are also presented and discussed in this book. A group of top scientists and engineers working on ­lithium-ion batteries with not only excellent academic records but also strong industrial expertise were invited to contribute chapters. In this book, these leading experts from universities, government laboratories, and lithium-ion battery industries in North America, Europe, and Asia share their knowledge, information, and insights on recent advances in the fundamental theories, experimental methodologies, and research achievements in lithium-ion battery technology. In Chapter 1, Choi, Wang, and Yang discuss the challenges of and perspectives for lithium-ion battery materials including cathode materials, anode materials, electrolytes, and separators, in addition to providing a comprehensive review in principle, history, and current status of lithiumion battery technology. The necessities and the corresponding performance requirements for next-generation lithium-ion batteries are also described. In Chapter 2, Bakenov and Taniguchi survey the research progress of cathode materials with layered, spinel, and olivine structures for lithium-ion batteries vii

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Preface

and highlight their work on using spray pyrolysis technique to prepare highperformance cathode materials. In Chapter 3, Tirado and coworkers overview the research progress of lithium-ion battery anode materials, including carbon materials, transition metal oxides, nitrides, phosphides, antimonides, silicon/silicon-based compounds, and tin/tin-based compounds. In Chapter 4, Passerini and his colleagues describe the current status of electrolytes for lithium-ion batteries. Organic solvent–based liquid electrolytes, ionic liquids, polymer electrolytes, aqueous electrolytes, glass, and ceramic electrolytes are covered. In Chapter 5, Santhanagopalan and Zhang provide a comprehensive review of separators for diverse rechargeable lithium batteries, including lithium-ion batteries, lithium-polymer batteries, and lithiumion gel polymer batteries. Future directions for separator development are also discussed. In Chapter 6, Tse and Yang survey the application of first principles to theoretically predict material properties of lithium-ion batteries. They discuss the advantages and disadvantages of each first-principles method in the calculation of electrode materials and perspective future research directions. In Chapter 7, Luo and Wang present their effort in developing a three-dimensional electrochemical-thermal coupled lithium-­ion battery model based on computational fluid dynamics techniques for largeformat automotive batteries. The strategies for performance enhancement of large-format lithium-ion batteries are also proposed. In Chapter 8, Liang and MacNeil give a detailed description of state-of-the-art production technologies for lithium-ion battery cathode and anode materials. In particular, they introduce the required technologies and principles for material quality and process control in manufacturing electrode materials. We hope this book will be a good resource for electrochemists, material scientists, students, industrial professionals, manufacturers, and the public, providing comprehensive and up-to-date information on lithium-ion battery principles, current status, and future prospects. The information in this book will be very helpful for readers in selecting existing materials/technologies and developing new materials/technologies to improve lithium-ion battery performance. We anticipate that this book will also be used as a reference by postsecondary undergraduate and graduate students and scientists and engineers who work in the areas of energy and electrochemical science/ technology. We express our appreciation to CRC Press for inviting us to lead this book project, and we thank Allison Shatkin and Jessica Vakili for their guidance and support in smoothing the book preparation process. We gratefully acknowledge all the chapter authors for their enthusiastic, collaborative, and reliable contributions. Finally, our deepest special appreciation goes to our families for their understanding and their ongoing support. Xianxia Yuan Hansan Liu Jiujun Zhang

Editors Dr. Xianxia Yuan is an associate professor in the Department of Chemical Engineering, Shanghai Jiao Tong University, China. She received her BS and MS in electrochemistry from Harbin Engineering University in 1996 and 1999, respectively, and her PhD in material physics and chemistry from Shanghai Institute of Microsystem and Information Technology, Chinese Academics of Sciences in 2002. She has been on the faculty at Shanghai Jiao Tong University since then. Dr. Yuan worked as visiting professor in Chao-Yang Wang’s group at Pennsylvania State University in 2008–2009. Dr. Yuan has 16 years of research experience on materials and technology for the lithium-ion battery, proton-exchange membrane fuel cell, direct methanol fuel cell, and nickel metal hydride battery. She has led or been involved in over 20 national and international projects funded by governments or industries in China, the United States, and Japan. Dr. Yuan has published more than 70 research papers in peer-reviewed journals and authored two patents and two book chapters on batteries and fuel cells. Dr. Yuan is an active member of the Electrochemical Society and the International Society of Electrochemistry.

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Editors

Dr. Hansan Liu is a research scientist working in the Oak Ridge National Laboratory (ORNL), U.S. Department of Energy. He obtained his PhD in electrochemistry from Xiamen University, where he studied cathode materials for lithium-ion batteries. After graduation, he worked at the Hong Kong Polytechnic University and the National Research Council of Canada on photoelectrocatalysis and fuel cell electrocatalysis, respectively. He is currently working on next-generation, high-performance batteries at the Oak Ridge National Laboratory. Dr. Liu has 14 years of research experience in the field of electrochemical energy storage and conversion. His research interests mainly include lithium-ion batteries, metal-air batteries, protonexchange membrane fuel cells, and high–surface area materials for energy applications. He has authored and coauthored over 70 publications, including 3 books, 4 book chapters, and 4 patent applications relating to batteries and fuel cells. Dr. Liu is an active member of the Electrochemical Society, the International Society of Electrochemistry, and the Material Research Society.

Editors

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Dr. Jiujun Zhang is a senior research officer and PEM catalysis core competency leader at the Institute for Fuel Cell Innovation, the National Research Council of Canada (NRC-IFCI). Dr. Zhang received his BS and MS in electrochemistry from Peking University in 1982 and 1985, respectively, and his PhD in electrochemistry from Wuhan University in 1988. After completing his PhD, he took a position as an associate professor at the Huazhong Normal University for 2 years. Starting in 1990, he carried out three terms of postdoctoral research at the California Institute of Technology, York University, and the University of British Columbia. Dr. Zhang has over 28 years of R&D experience in theoretical and applied electrochemistry, including over 14 years of experience in fuel cell R&D (among these, 6 years at Ballard Power Systems and 7 years at NRC-IFCI) and 3 years of experience in electrochemical sensors. Dr. Zhang holds several adjunct professorships, including one at the University of Waterloo and one at the University of British Columbia. Dr. Zhang has coauthored 240 publications, including 160 refereed journal papers, 6 edited books, 11 conference proceeding papers, 12 book chapters, and 50 conference and invited oral presentations. He also holds over 10 U.S./ EU/WO/JP/CA patents and 9 U.S. patent publications, and he has produced in excess of 80 industrial technical reports. Dr. Zhang is an active member of the Electrochemical Society, the International Society of Electrochemistry, and the American Chemical Society.

Contributors

Ricardo Alcántara Department of Inorganic Chemistry and Chemical Engineering Universidad de Córdoba Córdoba, Spain Zhumabay Bakenov Department of Chemical Engineering Tokyo Institute of Technology Tokyo, Japan Daiwon Choi Pacific Northwest National Laboratory Richland, Washington Wesley Henderson Ionic Liquids and Electrolytes for Energy Technologies Laboratory Department of Chemical and Biomolecular Engineering North Carolina State University Raleigh, North Carolina Pedro Lavela Department of Inorganic Chemistry and Chemical Engineering Universidad de Córdoba Córdoba, Spain Alexandra Lex-Balducci Institute of Physical Chemistry Muenster Electrochemical Energy Technology University of Muenster Muenster, Germany Guoxian Liang St-Bruno de Montarville Phostech Lithium Inc. Quebec, Canada

Gang Luo Department of Mechanical and Nuclear Engineering, and Electrochemical Engine Center (ECEC) Pennsylvania State University University Park, Pennsylvania Dean D. MacNeil Département de chimie Université de Montréal Montréal, Quebec, Canada Stefano Passerini Institute of Physical Chemistry Muenster Electrochemical Energy Technology University of Muenster Muenster, Germany Carlos Pérez-Vicente Department of Inorganic Chemistry and Chemical Engineering Universidad de Córdoba Córdoba, Spain Shriram Santhanagopalan National Renewable Energy Laboratory Golden, Colorado Izumi Taniguchi Department of Chemical Engineering Tokyo Institute of Technology Tokyo, Japan

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José L. Tirado Department of Inorganic Chemistry and Chemical Engineering Universidad de Córdoba Córdoba, Spain John S. Tse Department of Physics University of Saskatchewan Saskatoon, Saskatchewan, Canada Chao-Yang Wang Department of Mechanical and Nuclear Engineering, and Electrochemical Engine Center (ECEC) Pennsylvania State University University Park, Pennsylvania

Contributors

Wei Wang Pacific Northwest National Laboratory Richland, Washington Jianjun Yang Department of Physics University of Saskatchewan Saskatoon, Saskatchewan, Canada Zhenguo Yang Pacific Northwest National Laboratory Richland, Washington Zhengming (John) Zhang Celgard, LLC Charlotte, North Carolina

1 Material Challenges and Perspectives Daiwon Choi, Wei Wang, and Zhenguo Yang

CONTENTS 1.1 Principle of Lithium-Ion Batteries ............................................................... 1 1.2 Current Status of Lithium-Ion Battery Technology ..................................9 1.2.1 Cathode Materials ............................................................................ 11 1.2.2 Anode Materials............................................................................... 13 1.2.3 Electrolyte ......................................................................................... 17 1.2.3.1 Liquid Electrolytes ............................................................ 17 1.2.3.2 Ionic Liquids ...................................................................... 18 1.2.3.3 Solid Polymer Electrolyte ................................................. 18 1.2.3.4 Inorganic Solid Electrolyte .............................................. 19 1.2.3.5 Hybrid Electrolyte ............................................................. 19 1.2.4 Separator ........................................................................................... 19 1.2.5 Battery Cell ....................................................................................... 21 1.3 Material Challenges of Lithium-Ion Batteries .........................................22 1.4 Next Generation of Lithium-Ion Batteries ................................................ 26 1.4.1 Low-Cost, Sustainable, and Greener Lithium-Ion Batteries ......... 31 1.4.2 Improving Safety, Reliability, and Durability .............................34 1.4.3 Improving Energy Density and Capacity .................................... 37 References............................................................................................................... 40

1.1  Principle of Lithium-Ion Batteries The lithium-ion battery is one of the most promising energy storage technologies currently available and widely used in portable electronics. The worldwide market for rechargeable lithium-ion batteries is now valued at 10 billion dollars per annum and is growing. The main reason behind such rapid growth is its high energy density and cycling performance that no other energy storage devices can match. Recent demands on energy and environmental sustainability have further spurred great interest in a larger scale lithium-ion battery system for vehicles and grid load leveling as well as 1

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Lithium-Ion Batteries

complimentary energy storage for renewable energy resources, such as solar and wind power. The energy storage mechanism of lithium-ion batteries is quite straightforward. Lithium-ion batteries store electrical energy in electrodes made of lithium-intercalation (or insertion) compounds with concomitant oxidation and reduction processes occurring at the two electrodes. A lithium-ion battery generally comprises a graphite negative electrode (anode), a nonaqueous liquid electrolyte, and a layered LiCoO2 positive electrode (cathode) as shown in Figure 1.1a. On charging, Li+ ions are (a) e–

e– Electrical connection

Cathode

Anode

Al

Cu +3/+4 Layered compounds Li+ion

Graphite Separator

Electrolyte

(b) SEI

Φc

H+/H2

LUMO

Eg

µc

Cathode

Anode

µA

Voc

HOMO SEI

Oxidant

ΦA

O2/H2O

Electrolyte

Reductant

FIGURE 1.1 Schematic of (a) a traditional lithium-ion battery cell in which, during discharge, Li+ ions migrate through the electrolyte and electrons flow through the external circuit, both moving from the anode (negative) to the cathode (positive) and (b) open circuit energy diagram of an aqueous electrolyte, anode and cathode work functions (ΦA and ΦC). Eg is the electrolyte potential window for thermodynamic stability. (From Goodenough, J.B. and Kim, Y., Chem. Mater., 22, 3, 587–603, 2010. With permission.)

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Material Challenges and Perspectives

deintercalated from the layered LiCoO2 cathode host, transferred across the electrolyte, and intercalated between the graphite layers in the anode. The discharge reverses this process where the electrons pass around the external circuit to power various systems. The rechargeable lithium-ion battery is an ultimate representation of solid-state chemistry in action that started with the discovery of intercalation compounds, such as Li xMO2 (M = cobalt or nickel) which were initially proposed by Goodenough and are still widely used today [1,2]. The discovery of low-voltage, lithiumintercalation, carbonaceous materials that are highly reversible led to the commercialization of Li xC6/Li1−xCoO2 cells by Sony in 1991 [3]. The energy conversion in the so-called rocking-chair cells is completed via the ­following reactions [3]:

Cathode: Li1− x CoO 2 + xLi+ + xe− discharge  → LiCoO 2



→ xLi+ + xe− + C6 Anode: Li x C6 

discharge

(1.1)

(1.2)

Full Cell Reaction:

discharge

LiC6 +CoO 2  → C6 +LiCoO 2

E = 3.7 V at 25°C

(1.3)

Typical lithium-ion cells produce 3.7 V and demonstrate a capacity and power about 150 Ah/kg and over 200 Wh/kg, respectively [4]. The favorable electrochemical performance in energy/power densities and advancements in system design and manufacturing have made the early lithium-ion battery a great success for mobile electronics in spite of the remaining challenges. For a better understanding, a brief historical account of the development of lithium-ion battery technology over the past 30 years is needed. Like most innovations, there were a number of developments that led to mature ­lithium-ion battery technology. Burgeon started unsurprisingly with lithium metal as the preferred working anode. Lithium metal is very attractive, not only because of the most electropositivity (–3.04 V vs. standard hydrogen electrode) and high mobility of lithium ions, but also a high theoretical capacity of 3860 mAh/g, which can lead to very high energy density [2]. Such advantages in using lithium metal for batteries were first demonstrated in the 1970s with primary lithium cells. Sanyo, one of the leading battery manufacturers in Japan, developed one of the earliest primary lithium batteries using a Li/MnO2 system [5,6]. Some early work on ambient systems was also taking place in the United States by 1970, by Dey et al., on the reactivity of lithium with a series of metals, such as aluminum [3,7]. Many primary lithium batteries for medical applications, starting with the lithium iodine cell, have been developed. The majority of the implantable cardiac defibrillators in the last 20 years have used silver

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Lithium-Ion Batteries

vanadium oxide (Ag2V4O11) as the active cathode material with a capacity over 300 mAh/g [8,9]. The presence of silver greatly improves the electronic conductivity and thus the rate capability. On the other hand, most of the early work on rechargeable lithium batteries was based on a molten salt electrolyte with an operating temperature around 450°C [10–12]. Molten lithium and sulfur were used as the two electrodes, but dealing with corrosion, temperature, and other issues proved an insurmountable task. In 1967, the extraordinary electrolytic behavior of the Na-β-alumina, Na1+xAl11O17, at around 300°C was reported by Yao and Kummer [13], making the sodium/sulfur system more promising, and early results on ambient lithium rechargeable systems began to show some promise. However, it is still the dream of battery researchers to develop a lithium/sulfur cell because a much higher energy density can be attained than in most of the cathode materials to be discussed below. These lithium/ sulfur cells with a liquid polysulfide cathode have generated power exceeding 750  W/kg at 25°C [3]. However, these cells still have significant issues with self-discharge on standing, lithium recharging, and the highly resistive nature of the cathode. The earliest concepts for today’s rechargeable lithium-ion battery date back when intercalation phenomena of various alkali ions were studied. Numerous inorganic compounds were shown to react with alkali metals in a reversible way. The discovery of such materials, later known as intercalation compounds, was crucial in the development of the high-energy, rechargeable, lithium-ion battery. The Li/(CF)n battery with a cell potential of 2.8–3.0 V was developed by Matsushita of Japan [14]. It was proposed that lithium ­initially intercalates into the carbon monofluoride lattice, and ­subsequently, the ­lithium fluoride is formed with the following reaction: Li  +  (CF)n → Lix(CF)n → C + LiF [15]. While much work has continued intermittently on the carbon fluorides by others, the major challenge was to facilitate a reversible reaction at lower fluoride levels. Although not widely known, the concept of electrochemical intercalation and its potential use were clearly defined by 1972. Earlier, solid-state chemists had been accumulating structural data on the inorganic layered chalcogenides, and the merging of the research communities studying primary lithium batteries and the intercalation compounds was productive. Around 1970, at Stanford, the possibility of oxide and, subsequently, halide incorporation between the graphite layers was studied [16–18]. Later, the intercalation range of electron-donating molecules and ions into the layered dichalcogenides, TaS2 in particular, was discovered [19]. The other trichalcogenides also readily react with lithium, but not in such a reversible manner. A number of other chalcogenide-rich materials have been studied, but although many of them have a high capacity, their rates of reaction or conductivity are low. In 1972, Exxon initiated a large project using a lithium-metal anode combined with layered TiS2 [20] or MoS2 [21] structures as the cathode electrode, which was known as the best intercalation compound available at the time.

Material Challenges and Perspectives

5

Of all the layered dichalcogenides, TiS2 was the most appealing as an energy storage electrode since it was the lightest, and lithium, over an entire composition range of LixTiS2 (0