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Lithium-Ion Batteries: Advances and Applications
Oleh Elsevier Science
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Nilai: 4 dari 5 bintang4/5 (1 penilaian)
Panjangnya: 1,266 halaman
- Penerbit:
- Elsevier Science
- Dirilis:
- Dec 16, 2013
- ISBN:
- 9780444595164
- Format:
- Buku
Deskripsi
Lithium-Ion Batteries features an in-depth description of different lithium-ion applications, including important features such as safety and reliability. This title acquaints readers with the numerous and often consumer-oriented applications of this widespread battery type.
Lithium-Ion Batteries also explores the concepts of nanostructured materials, as well as the importance of battery management systems. This handbook is an invaluable resource for electrochemical engineers and battery and fuel cell experts everywhere, from research institutions and universities to a worldwide array of professional industries.
Contains all applications of consumer and industrial lithium-ion batteries, including reviews, in a single volume Features contributions from the world's leading industry and research experts Presents executive summaries of specific case studies Covers information on basic research and application approachesTindakan Buku
Mulai MembacaInformasi Buku
Lithium-Ion Batteries: Advances and Applications
Oleh Elsevier Science
Nilai:
Nilai: 4 dari 5 bintang4/5 (1 penilaian)
Panjangnya: 1,266 halaman
Deskripsi
Lithium-Ion Batteries features an in-depth description of different lithium-ion applications, including important features such as safety and reliability. This title acquaints readers with the numerous and often consumer-oriented applications of this widespread battery type.
Lithium-Ion Batteries also explores the concepts of nanostructured materials, as well as the importance of battery management systems. This handbook is an invaluable resource for electrochemical engineers and battery and fuel cell experts everywhere, from research institutions and universities to a worldwide array of professional industries.
Contains all applications of consumer and industrial lithium-ion batteries, including reviews, in a single volume Features contributions from the world's leading industry and research experts Presents executive summaries of specific case studies Covers information on basic research and application approaches- Penerbit:
- Elsevier Science
- Dirilis:
- Dec 16, 2013
- ISBN:
- 9780444595164
- Format:
- Buku
Terkait dengan Lithium-Ion Batteries
Pratinjau Buku
Lithium-Ion Batteries
Germany
Preface
Research on lithium-ion batteries (LIBs) began in the early 1980s and the first LIB was commercialized in 1991. Most of the early technological developments concerned portable electronics, but LIBs' performance was soon made to fit medium- and large-scale applications, such as electric vehicles and storage systems (Chapter 1). Indeed, thanks to the use of new electrode materials, such as lithium titanate, fast charge/discharge rates (up to 6C) needed for the above-mentioned applications were made possible (Chapter 3). The use of nanostructured compounds, e.g. the titanate and lithium iron phosphate, has enabled the use of inexpensive, low-conductivity electrode materials and has helped commercialization. Nanostructuring is also beneficially being extended to such materials as carbon and carbon-based nanocomposites (Chapter 4)
A more extended commercialization of LIBs obviously depends on both their performance and their price. The origin of manufacturing costs, pathways to lower them, and how low these may fall in the future are reviewed in Chapter 6. A model enabling the direct evaluation of manufacturing costs is presented, which provides details on the most significant contributions to the total battery cost with a special reference to batteries for electric vehicles (EVs).
In spite of a diffusion thus far limited by cost and range factors, car electrification is progressing. In Chapter 7, a review of regulatory and market trends that are driving electrification of the automotive market and design considerations of LIBs for various types of hybrid vehicles and EVs are presented. Testing requirements for LIBs and the status of industry standard development are analyzed. Voltec vehicles such as Chevrolet Volt and Opel Ampera (Chapter 8) feature an extended driving range: they operate as EVs as long as the battery can deliver energy and, when the battery is depleted, can continue operation by using an internal combustion engine as energy converter.
Chapter 9 provides an overview of diverse transit bus applications of advanced LIBs. Battery safety, cost, reliability, availability, and maintainability issues are discussed. Lessons learned and remaining challenges in the large-scale adoption of LIBs in transit fleets are also discussed. Progress in and prospects for future LIB improvements and remaining bus integration and application challenges are presented. A comprehensive review of the characteristics of hybrid and fully electric vehicles now available in the market, or ready for commercialization, is provided in Chapter 10. Vehicles are classified taking into account the level of electrification of their drivetrain characteristics.
Power supply systems based mainly on renewable energy sources like solar and wind energy require storages on different timescales ranging from seconds to months. In Chapter 13, the lithium-ion technology is shown to be particularly fit for this application, and solutions for decentralized photovoltaic (PV) battery systems and results of simulation studies are presented.
Since the early 2000s, large-sized LIBs have also found applications in Earth-orbit satellites (Chapter 14), thanks to the benefit that they brought in terms of weight and life duration to both rockets and satellites.
The battery management system (BMS) needed for batteries of medium/large dimensions is dealt with in Chapter 15. Different BMS structures are compared and their advantages as a function of the battery system size are discussed.
In Chapter 16, electronic options that can be employed with lithium-ion cells as they are constructed into battery packs are discussed. The functions of measuring, monitoring, calculating, communicating, and controlling still apply from single cells for smartphones to large battery arrays of kilowatt-hour size. Simple and reliable safety components for monitoring and controlling were first developed for video cameras and cell phones. More advanced fuel gauging devices with measuring, calculating, and communicating functions followed in laptop and notebook computers. More recently, high-current devices for power tools and e-bikes have become common. And finally, components for very high-voltage systems for EVs and hybrid vehicles are now available.
Battery safety has been obviously given a special attention in this volume. Commercial lithium-ion cells and batteries are commonly used to power portable equipment, but they are also used to buildup larger batteries for ground (e.g. EVs), space and underwater applications. Chapter 17 provides test data on the safety of commercial lithium-ion cells and recommendations for safe design when these cells are used in much larger battery configurations. Chapter 18 focuses on safety aspects of LIBs at the cell and system level. In particular, abuse tolerance tests are explained with actual cell test data. Furthermore, internal short and lithium deposition occurring in lithium-ion cells and failure mechanism associated with them are discussed. In Chapter 19, the state of the art for safety optimization of all the battery elements is presented. This chapter also reports tests on not yet commercialized batteries, which pass all the security tests without the help of a BMS.
Impact of LIBs on the environment and their recycling are also dealt with. In particular, Chapter 21 deals with the impact of production of automotive LIBs and investigates how it could be reduced by recycling. Making use of recycled materials (cathode, aluminum, copper) could reduce cradle-to-gate energy consumption by up to 50%. In Chapter 22, the question whether enough lithium is available for the production of LIBs and how much battery recycling will contribute to a higher availability of lithium in the future is discussed. An investigated scenario regarding lithium availability and demand suggests that no real lithium scarcity is foreseen in the near future even from the resources policy perspective. After the year 2050, the situation might change when the easily extractable reserves in stable countries will decrease significantly.
In Chapter 23, the cost of battery components is presented together with a discussion on economic, environmental and regulatory aspects of recycling. Furthermore, technologies used for LIBs by the major recycling companies in Europe and the United States are reviewed.
With prices for large format cells for automotive applications of ∼ US$250 in 2015 and even further decreases to US$180–200 later in the decade, margins of cell makers and materials producers will have a limited increase, driven by the introduction of materials with higher capacity and progress in cell production technology. The high margin pressure, accompanied by the need for investments in product and process innovation, will lead to further massive consolidation of the industry (Chapter 24).
February 2013
Gianfranco Pistoia
Consultant, Rome, Italy
Gianfranco.pistoia0@alice.it
1
Development of the Lithium-Ion Battery and Recent Technological Trends
Akira Yoshino, Yoshino Laboratory, Asahi Kasei Corp., 2-1, Samejima, Fuji-Shi, Shizuoka, Japan
Abstract
Lithium-ion batteries (LIBs) feature high energy density, high discharge power, and long service life. These characteristics facilitated a remarkable advance in portable electronics technology and the spread of information technology devices throughout society. Their emerging application to electric vehicles and large-scale storage systems make them a promising solution for challenges of environmental preservation and resource conservation. Research on LIBs started in the early 1980s, and the principle of the current LIB was completed in 1985. Since the LIB was first commercialized in 1991, battery performance has risen dramatically. Most of the technological developments to date have been directed toward the needs of portable electronics, but now the focus tends to be on the performance demands of medium- and large-scale applications. This chapter firstly describes the early technological innovations and then introduces and discusses the latest technology and research on the major battery components, the cathode, anode, electrolyte, and separator.
Keywords
Development; Lithium-ion battery; Origin; Technological trend
Chapter Outline
1. Introduction
2. Development of the Practical LIB
3. Development of Cathode Materials
3.1. History of Cathode Material Development
3.2. Recent Technological Trends of Cathode Materials
3.2.1. Three Morphologies of Cathode Materials
3.2.2. Layered Rock Salt Structure Materials (two dimensional)
3.2.3. Spinel Structure Materials (three dimensional)
3.2.4. Olivine Structure Materials (one dimensional)
3.3. Latest Research on Cathode Materials
3.3.1. Layered LCO Series (two dimensional)
3.3.2. Layered LiNiO2 Series (two dimensional)
3.3.3. Layered Mn Compound Series (two dimensional)
3.3.4. Spinel Structure Cathode Materials (three dimensional)
3.3.5. Olivine Structure Cathode Materials (one dimensional)
4. Development of Anode Materials
4.1. History of Anode Material Development
4.2. Recent Research on Anode Materials
5. Development of Electrolyte Solutions
5.1. History of Electrolyte Solution Development
5.2. Recent Research on Electrolyte Solutions
6. Separator Technology
6.1. Separator Production Methods and Characteristics
6.1.1. Dry-process One-component System
6.1.2. Wet-process Two-component System
6.1.3. Wet-process Three-component System
6.1.4. Shutdown Function
6.2. Recent Separator Developments
6.2.1. New Materials
6.2.2. Inorganic Coating
6.2.3. Separators Containing Inorganic Material
6.2.4. Nonwoven Separators
6.2.5. Laminated Separators
7. Conclusion
References
1 Introduction
In the 1980s, information technology (IT) advanced significantly with the development of portable electronic products such as video cameras, mobile phones, and notebook computers. This technological revolution led to a growing need for rechargeable batteries with greater capacity or with reduced size and weight for a given capacity. Conventional rechargeable batteries available or under development at that time such as lead–acid, nickel–cadmium, and nickel–metal hydride batteries used aqueous electrolytes, which posed limitations on increasing the energy density and reducing the size and weight. Thus, there remained an unmet need for a new, small and lightweight rechargeable battery to be put into practical use. Research on the lithium-ion battery (LIB) started in the early 1980s, and the first commercialization was achieved in 1991. Since then, LIBs have grown to become the dominant power storage solution for portable IT devices. The LIB market has continued to expand rapidly for over 15 years, and its worldwide scale now exceeds JP Yen 10⁶ millions ($13,000 millions) as shown in Figure 1.1.
FIGURE 1.1 Expansion of worldwide LIB demand.
The four major components of the LIB are the cathode, anode, electrolyte, and separator. LIBs generally produce an average cell voltage of around 3.7 V and operate on the relatively simple principle of reversible intercalation of Li ions in the cathode and anode. The most commonly used material for the cathode is lithium cobalt oxide, LiCoO2, and some form of carbon is generally used for the anode. In the completely discharged state, Li atoms are only contained as part of the cathode. On charging, Li ions are released from the cathode and migrate through the electrolyte into the carbon of the anode. The reverse reaction occurs during discharging, and electric energy is stored or released by repeating these reactions reversibly. The rapidly growing LIB market described above owes to this safe and efficient principle. This chapter focuses on two subjects: the development of the first practical LIB configuration in the 1980s and the recent technological trends for LIBs. The principle of the present commercial LIB as described above was completed in 1985 with a patent filed by the author [1]. This invention and other successive patents illustrate the origins of the key LIB components and configuration, as well as the technological requirements associated with them. Since many of the requirements at the time are analogous to the objectives of current research, reviewing the initial stage of LIB development will provide rich context for and insight into the overall technology. Following a brief overview of the initial development, sections devoted to each major LIB component will begin with a description of the early technological innovations followed by a discussion of recent technology and research.
2 Development of the Practical LIB
The author and colleagues focused on creating a practical new nonaqueous electrolyte rechargeable battery to meet the emerging need for a small and lightweight power source for portable electronics. Our essential achievements made in the 1980s were as follows: (1) proposition of fundamental technology for composition of the LIB, in which LiCoO2 is used as the cathode and a carbonaceous material with a certain crystalline structure is used as the anode; (2) invention of essential constituent technologies for the electrodes, electrolyte, and separator; and (3) development of peripheral technology such as safety device technology, protective circuit technology, and charging and discharging technology.
The first step to develop the practical LIBs was the adoption of LiCoO2 for the cathode. LiCoO2 was first disclosed by Goodenough et al. [2,3] and it remains the most commonly used cathode material at present. One anode material that was gaining attention at the time was graphite [4], but it was known that propylene carbonate, which was then the common organic electrolyte solvent, would decompose during charging when graphite was used. Furthermore, the use of a solid electrolyte resulted in electrical resistance which was too high to enable practical charging and discharging. We created a working model LIB using LiCoO2 as the cathode and polyacetylene as the anode, but rejected polyacetylene due to its low density (high bulk) which precluded reduction of cell size. Studying several carbonaceous materials for their suitability as anode, we found that a carbonaceous material with a certain crystalline structure provided greater capacity without causing decomposition of the propylene carbonate electrolyte solvent, as graphite did. The secondary battery which we successfully fabricated based on this new combination of component materials enabled stable charging and discharging, over many cycles for a long period [1].
This combination of electrode materials marked a new concept of a secondary battery based on the transfer of Li ions. Cell reaction without chemical transformation provided stable battery characteristics over a long service life, including excellent cycle durability with little degradation by side reactions, and excellent storage characteristics. Furthermore, this development also enabled simple and efficient assembly in the discharged state, with no special atmosphere required because LiCoO2 is very stable in air, despite containing Li ions, and the anode is composed of carbonaceous material which is also stable.
Another key step was the development of essential constituent technologies including technology for fabricating electrodes and technology for assembling batteries. In the basic structure of the typical LIB, a multilayer electrode assembly (electrode coil), prepared by winding sheets of cathode and anode with separator membrane in between, is inserted into a battery can. This is then infused with nonaqueous electrolyte solution composed of LiPF6 or LiBF4 dissolved in a mixture of carbonate compounds and sealed. Both the cathode and the anode are structured with the electrode material coated on both sides of a current collector. The current collectors conduct electricity from the active electrode materials to tabs connected to the electrode terminals. Aluminum foil is used for the cathode current collector and copper foil is used for the anode current collector, the thickness of each being around 10 μm. Some batteries with this configuration were subjected to abuse test
for safety evaluation and proved that the basic LIB cell design provides the required level of safety, and this cleared the way for the commercialization of the LIB as we know it today.
The ionic conductivity of nonaqueous electrolyte is lower than that of aqueous electrolyte, so in order to obtain discharge power using the former which is comparable to that using the latter, lower current density for a given area of electrode surface was required to prevent the excessive generation of Joule heat. We achieved high current discharge using nonaqueous electrolyte by devising flat-sheet electrodes wound into a coil shape. Practical application was achieved with technology for fabricating thin-film electrodes (100–250 μm) in which a thin metal foil is used as a current collector and both surfaces of the foil are coated with electrode active material. Our selection of aluminum as cathode current collector was one of the most important aspects of this development. Previously, only precious metals such as gold and platinum were considered to be able to withstand a high voltage of 4 V or more. However, we found that aluminum foil was suitable for use as a cathode current collector because a passivation layer forms on the aluminum surface [5].
Another notable invention relating to constituent technologies essential for achieving a practical LIB is a highly functional membrane separator for safety. The use of a microporous polyethylene membrane (20–30 μm thick) for use as separator provides a shutdown
function in which the material of the separator melts to close the micropores and shut off battery operation in the case of abnormal heat generation [6].
In summary, these essential constituent technologies impart the LIB with the following characteristics: (1) high cell voltage of 4 V or more enabled through the use of LiCoO2 as the cathode and aluminum foil as the cathode current collector; (2) high current discharge enabled with large-area thin-film electrodes using metal foil as the current collector with electrode material coated on both sides; (3) efficient, high-speed electrode production; (4) high-density packaging with the coil-shaped, multilayer thin-film electrode assembly emplaced in a battery can; and (5) significantly improved battery safety with a polyethylene microporous membrane having a certain thermal characteristic used as separator.
The final part of our development was the peripheral technology which was instrumental in the development of a practical LIB, including safety device technology, protective circuit technology, and charging and discharging technology. One key example is a positive temperature coefficient device which is sensitive to both electric current and temperature. Incorporation of this device in the LIB results in greatly improved safety, particularly in terms of protection against overcharging [7].
These are the key technological developments that made the current LIB possible. Further developments accelerated quickly with commercialization in the early 1990s, and the pace is picking up again as new applications outside portable electronics come to the fore. Further technological development today is generally focused on novel compositions of the major LIB components, the cathode, anode, electrolyte, and separator. Characteristics of these components are improved either individually or together to enhance the battery performance. For example, the energy density of the LIB has risen from 200 Wh/l in the early 1990s to the current 600 Wh/l, as shown in Figure 1.2. This steady increase in energy density has enabled the power module of portable IT devices to significantly decrease in size and weight, and the major contributor to this development has been the development of high-capacity anode materials. Capacity improvement of carbon-based anodes is, however, thought to be approaching a ceiling lately, and therefore an increasing amount of research is focused on the development of new materials capable of reversibly intercalating Li ions with a higher capacity than carbon.
FIGURE 1.2 Capacity increase of LIB.
A tripling of energy density would, in principle, result in the bare cell price per watt-hour dropping by one-third. Further price reduction is possible by improving material characteristics and cutting production costs. In fact, LIBs have historically achieved an astonishing level of price reduction, far exceeding the rate of increase in capacity. This is illustrated in Figure 1.3, which shows the price trend for bare cylindrical 18,650 cells, the general-purpose LIB configuration. When high-volume production began in earnest around 1994, the bare cell price was ¥300; this dropped to ¥22.5 in the early 2000s. The achievement of such a low price per watt-hour for portable applications is furthermore significant in that it begins to make the LIB affordable for medium- and large-scale applications such as electric vehicles and storage batteries for residential use.
FIGURE 1.3 Trend of LIB bare cell price.
Such dramatic price reduction together with further technological developments are leading the LIB’s rapid advancement into medium- and large-scale applications, most notably hybrid electric vehicle (HEV), plug-in hybrid electric vehicle, battery electric vehicle (BEV), and energy storage system for buildings. The following sections of this chapter review the technological improvements which took place from the start of commercialization to the present and describe recent trends of development for each major LIB component.
3 Development of Cathode Materials
3.1 History of Cathode Material Development
In 1995 when mass production of the LIB was just underway, LiCoO2 (LCO) was by far the dominant cathode material, with the spinel LiMn2O4 (LMO) occupying only a small part of the 650-t total market as shown in Figure 1.4.
FIGURE 1.4 Major materials in the LIB cathode market. LCO, LiCoO2; LMO, LiMn2O4; NMC, LiNi1/3Mn1/3Co1/3O2; NCA, LiNi0.8Co0.15Al0.05O2; LFP, LiFePO4.
Although LCO remains the most common cathode material, its share of the total market has been gradually eroded by other materials due to considerations of cost and resource availability. By 2010, the market share for LCO had declined to 40%, and the use of LiNi1/3Mn1/3Co1/3O2 (NMC), a ternary system with nickel, manganese, and cobalt, had increased dramatically. Although their market shares are relatively small, LiNi0.8Co0.15Al0.05O2 (NCA) and LMO are preferred for certain applications. Although only finding limited use so far, phosphates with an olivine structure are a promising new class of cathode materials with LiFePO4 (LFP) being the most common. As shown in Figure 1.4, total shipments of LIB cathode materials reached 45,000 t in 2010, and this is poised to further expand as other new cathode materials are developed especially for medium- and large-scale applications.
3.2 Recent Technological Trends of Cathode Materials
3.2.1 Three Morphologies of Cathode Materials
The LIB cathode materials are transition metal oxides containing lithium, and they are a type of functional ceramics. For such a material to be used as LIB cathode, the Li ions must be able to diffuse freely through the crystal structure. The morphology of the crystal structure, being one-, two-, or three-dimensional, determines the number of dimensions in which Li ions are able to move. Cathode materials currently in use or under development are described below in accordance with the following three morphologies.
3.2.2 Layered Rock Salt Structure Materials (two dimensional)
This is a group of compounds with a two-dimensional crystal morphology. While the most common example is LCO, LiNiO2 and LiMnO2 are also well known. Although the latter two compounds have proved to be unsuitable for use as LIB cathode in their simple form, performance improvements have been achieved by combining them with other elements to form complex oxides such as NMC, LiNi0.8Co0.2O2, and LiNi0.5Mn0.5O2. Some of these new materials have already been commercialized. Furthermore, solid solution materials indicated by the general formula Li2MnO3–LiMO2 (M being a transition metal such as Ni or Fe) are recently being researched, notably Li1.2Fe0.4Mn0.4O2.
3.2.3 Spinel Structure Materials (three dimensional)
LMO is the most significant compound in this category which enables Li ions to diffuse in all three dimensions. Although spinels provide lower discharge capacity than layered rock salt materials, they do enjoy advantages in terms of lower cost and high stability and are therefore gaining attention in emerging medium- and large-scale LIB applications.
3.2.4 Olivine Structure Materials (one dimensional)
LFP is the most well known of the olivines, which restrict Li ion diffusion to a single linear dimension. Although low ion mobility poses an inherent performance disadvantage, this has been minimized through the development of nanoparticles and other techniques (see Section 3.3.5). Discharge voltage for olivines is relatively low at around 3.5 V, and there is little scope of increasing the energy density. Nevertheless, there has been some commercialization of olivine cathode materials due to the outstanding stability they offer.
3.3 Latest Research on Cathode Materials
3.3.1 Layered LCO Series (two dimensional)
Although LCO has been studied for many years, there is still scope to improve its performance as LIB cathode by employing new synthesis techniques. In one notable example, Yamaki et al. report the synthesis of nanoparticles of overlithiated LCO which provide significantly improved electrochemical properties [8]. They employed a procedure in which lithium acetate and cobalt acetate are mixed in solution, dried, and then calcined at 600 °C for 6 h, in contrast to the general method of obtaining bulk LCO particles by calcining a combination of Co3O4 and Li2CO3 at around 900 °C, which produces material with a primary particle diameter of several micrometers. The new method produced spherical nanoparticles of LCO with a primary particle diameter of 5–25 nm, and the material contained 9–21 times more Li than conventional bulk LCO particles. Notably, spherical nanoparticles with a primary particle diameter of about 25 nm were obtained when the Li content was increased by 8–12 times, while rod-shaped particles of 5 nm diameter and 60 nm length were obtained when the Li content was increased by 21 times. Cathode using the rod-shaped particles provided the greatest improvement in maintaining discharge capacity under high rate conditions and is considered to be particularly suitable for HEV applications.
3.3.2 Layered LiNiO2 Series (two dimensional)
LiNiO2 has been a candidate cathode material for some time. Its low cost and high discharge capacity of 200 mAh/g or more, which is 40% higher than that of LCO, make it attractive. However, it is associated with a number of shortcomings, such as outgassing when stored at high temperature and decreased thermal stability in the charged state. A significant advancement has been reported by researchers at Panasonic, who developed a LiNiO2-based material which appears to be practical for use as LIB cathode [9]. Although the technical details are not disclosed, it is presumed that they stabilized the material by adding cobalt or aluminum. In addition, they report coating the cathode surface with a heat-resistance layer
to improve thermal stability. Using their LiNiO2-based cathode material, they achieved 3.1 Ah capacity in a cylindrical 18650 cell, with energy density of 660 Wh/l and 248 Wh/kg. This outstanding energy density would make such a material suitable for BEV applications.
3.3.3 Layered Mn Compound Series (two dimensional)
Layered LiMnO2 shows poor discharge performance and therefore has not been a practical cathode material. However, many researchers have found that performance can be improved by adding other elements to form more complex compounds, with LiNi0.5Mn0.5O2 being a notable candidate. This material, however, still has poor discharge performance due to low conductivity, so research has broadly turned to the ternary NMC system. Research by Ohzuku et al. [10,11] revealed that NMC provides relatively high discharge capacity of 150 mAh/g together with well-balanced battery characteristics, giving it great potential as an increasingly important cathode material. However, it is to be noted that the characteristics of this material are highly dependent on the method of synthesis.
Conventional cathode materials such as LCO with a single transition metal element are prepared by a simple solid-phase method, in which cobalt acetate and lithium carbonate are calcined at around 900 °C, and consistent product is easily obtained. For materials with multiple transition metal elements like LMO, on the other hand, it is crucial to obtain product composition that is stoichiometrically precise and to obtain the intended crystal structure. Even slight variations can result in widely divergent characteristics when used as cathode material. Strict control of preparation conditions is thus essential for this class of materials.
Idemoto et al. [12] investigated the effect of LMO preparation method on cathode performance. They prepared material using both the solid-phase method and the solution method. In the solution method, Ni, Mn, Co, and Li salts are mixed and dried, and then the mixture is calcined. The researchers found that material prepared with the solution method showed stable characteristics, while that prepared with the solid-phase method was affected by cooling conditions after calcination. Since the solid-phase method is generally used for commercial production, careful control of process conditions is essential for the stable supply of LMO as a practical cathode material.
Another area of research for cathode materials in the Mn group are solid-solution materials described by the general formula Li2MnO3–LiMO2 (see Section 3.2.2). Several such materials have been reported, including Li(Lix/3Mn2x/3Co1−x)O2 (0 < x < 1) by Numata et al. [13] and Li[CrxLi(1/3−x/3)Mn(2/3−2x/3)]O2 (0 < x < 1) by Lu and Dahn [14,15]. With very high discharge capacity, they have great potential for use in future LIBs.
The mechanism by which these materials achieve such high discharge capacity is not yet completely clear, and many aspects of these materials are the subject of active research. There are notable reports focusing on their first-charge electrochemical behavior [16], mechanisms of deterioration [17], mechanisms of high durability [18], mechanisms of high capacity [19], mechanisms of ion transport [20], and the relationships between performance and the crystal structure [21].
3.3.4 Spinel Structure Cathode Materials (three dimensional)
LMO is the most well-established cathode material of this group. The spinel structure is generalized as AB2O4, with MgAl2O4 being a typical example. In the case of LMO, there are Li ion tunnels intersecting three-dimensionally through manganese oxide skeleton. The pioneering research on this material was performed by Thackeray et al. [22,23]. LMO is known to have some shortcomings, including relatively low discharge capacity and the elution of manganese during charging and discharging as well as during storage at high temperature. It has been shown, however, that manganese elution can be suppressed by doping at the Mn site with elements such as Al, Cr, Ti, and Ni, or by increasing the ratio of Li to Mn [24]. Although its discharge capacity is somewhat lower than layered rock salt cathodes, reasonable cost and high safety characteristics make LMO an attractive cathode material for medium- and large-scale LIB applications.
3.3.5 Olivine Structure Cathode Materials (one dimensional)
First reported by a team led by Goodenough [25], LFP is the most well-known olivine cathode material. Because of the one-dimensional crystal morphology, mobility of Li ions is limited. The resulting low ion diffusion rate and low ionic conductivity have made this material difficult to commercialize as cathode. In the early 2000s, A123 Systems, Inc., succeeded in overcoming these hurdles by producing the material in nanoparticle form, coating the cathode surface with a carbon layer, and doping the material with a different element such as niobium, and the material has been used in LIBs for power tools and electric vehicles (EVs). However, the low cell voltage with LFP prevents improvement in energy density, which limits its appeal in medium- and large-scale applications. Other olivines such as LiMnPO4 and LiCoPO4, that provide 4.1 V and 4.8 V, respectively, are therefore gaining attention.
4 Development of Anode Materials
4.1 History of Anode Material Development
In 1995, the major anode materials were graphite and hard carbon. About half of the 450 t of anode material shipped at the time was graphite, either mesophase graphite or synthetic graphite. The former was more popular despite its high price because it more easily enabled stable battery performance characteristics to be obtained. By 2010, shipments of anode material grew to 27,000 t, nearly all being some form of graphite, as shown in Figure 1.5. The reason graphite gained such overwhelming dominance is the superior discharge profile of graphite compared to hard carbon.
FIGURE 1.5 Major materials in the LIB anode market.
Figure 1.6 shows the discharge profile for LIB anode made of graphite, and the curve is characterized by a very broad, flat range. For hard carbon, on the other hand, the discharge profile is characterized by a steadily declining curve across most of the charge range, as shown in Figure 1.7.
FIGURE 1.6 Discharge curve of the graphite anode.
FIGURE 1.7 Discharge curve of the hard carbon anode.
The rapid spread of mobile phones was the main driver of LIB demand during this period, and a flat discharge profile is preferable for mobile phone applications. Graphite thus became the dominant anode material, with many variations developed to achieve lower cost and increased capacity. Among the various types of graphite, modified natural graphite has become the most common.
Natural graphite is the most inexpensive graphite material available, but its high reactivity to electrolyte prevents its use as anode without modification. Technology to coat the graphite surface with thin carbon layer has become widely used, enabling modified natural graphite to replace mesophase graphite as the leading anode material. A more recent development in the anode market is the resurgence of hard carbon. Having once been all but eliminated as an anode material, hard carbon is now making a comeback as its discharge profile has been found to be suitable for HEV applications.
4.2 Recent Research on Anode Materials
As there is little scope to further increase the capacity of graphite anode, research has turned to other new materials including metal oxides such as Co3O4, CoO, CuO, and FeO, and Li metal alloys such as Cu-Sn-Li, Cu-Sb-Li, In-Sn-Li, Si-Li, and Si-C-Li. Li metal alloys provide much higher capacity than graphite as shown in Figure 1.8, but a serious drawback is the large expansion and contraction of volume which occurs during the charge–discharge process, as shown in Figure 1.9. This problem can be diminished by forming the material in nanoparticles or using it as a composite with carbon, and some such materials have begun to be adopted in practical LIBs.
FIGURE 1.8 Theoretical discharge capacity of metal alloy anodes.
FIGURE 1.9 Volume expansion–contraction of metal alloy anodes at charge and discharge.
5 Development of Electrolyte Solutions
5.1 History of Electrolyte Solution Development
The electrolyte for LIBs is a mixture of organic solvents and an electrolyte salt compound. The common solvents are a mixture of cyclic carbonate esters, such as ethylene carbonate and propylene carbonate, and linear carbonate esters, such as dimethyl carbonate and diethyl carbonate. The solution is completed with the addition of a salt compound such as LiPF6 or LiBF4. Electrolyte solutions must enable the Li ions to transport freely, which requires both high dielectric constant and low viscosity. Cyclic carbonate esters have a high dielectric constant but high viscosity, while linear carbonate esters have low viscosity but low dielectric constant. Suitable electrolyte solutions are therefore obtained by mixing the two.
For electrolyte salt, both LiPF6 and LiBF4 were widely used in 1995, but LiPF6 has come to dominate the market as it expanded from 300 to 3700 t, as shown in Figure 1.10.
FIGURE 1.10 Major materials in the LIB electrolyte salt market.
5.2 Recent Research on Electrolyte Solutions
Research on the electrolyte solution is generally focused on one of three areas: functional electrolyte additives, flame-resistant or nonflammable electrolyte solutions, and new electrolyte salts.
Functional electrolyte additives are included in the electrolyte solution to improve battery performance. This concept has been around for some time, and the basic technology is well established. One early example is the addition of propane sultone to the nonaqueous electrolyte solution of a rechargeable battery using a metallic lithium anode. Although this technology was initially developed for metallic lithium batteries, the use of such additives for LIBs began around 1994. Since then a wide range of additives have been developed. So many different compounds have been used as additives that they are too numerous to mention, but notable examples include vinylene carbonate, propane sultone, phenylcyclohexane, and fluoroethylene carbonate. The selection of additives and determination of their appropriate formulations have become a key aspect of the proprietary know-how of each battery manufacturer, and the search for new additives continues apace.
The second area of research is flame-resistant or nonflammable electrolyte solutions. The main approach is to employ phosphate compounds in some way, either by using cyclic phosphoric acid ester as solvent or by adding a phosphazene compound as flame retardant. The next most common approach is to use halogen compounds, especially fluorine compounds such as fluorocarbon ester and fluorinated ether, as solvent. There is also the concept of a new safety mechanism whereby a flame retardant is encased in microcapsules to be released in case of battery malfunction.
The third area of research is new electrolyte salts to replace LiPF6, but there remain many challenges in terms of performance and cost. Figure 1.11 shows some of the newly developed salts which are strong candidates for use in next-generation LIBs. Notable examples include sulfonyl amides such as lithium bis(trifluoromethylsulfonyl) amide (LiTFSA) and lithium bis(pentafluoroethylsulfonyl) amide (LiBETA), lithium fluoroalkylfluorophosphate, lithium bis(oxalate) borate, and lithium perfluorinated boric acid salt cluster. These compounds are currently under evaluation for commercialization. Lithium bis(oxalate) borate in particular is considered promising as it is a low-cost material containing no fluorine and made from abundantly available boric acid and oxalic acid.
FIGURE 1.11 New electrolyte salt materials under development.
6 Separator Technology
6.1 Separator Production Methods and Characteristics
The LIB separator is a thin microporous membrane made of polyolefin. It is placed between the anode and cathode to prevent contact between them while enabling Li ions to pass through. There are three basic categories of separator based on their production methods, and each displays different morphologies and characteristics which are suitable for different battery applications. Scanning electron micrographs of typical separators produced by each of the three methods are shown in Figure 1.12.
FIGURE 1.12 Pore characteristics of microporous separator membrane. (a) Dry-process one-component system, (b) wet-process two-component system and (c) wet-process three-component system.
6.1.1 Dry-process One-component System
With this system, the separator is produced extruding molten polymer as a thin film and then forming pores around spherulites by stretching the film while it cools. It is a dry
process in that no solvent is used, and it is a one-component
system in that only the polymer material of the membrane itself is used. This system enables separator to be produced at relatively low cost because of its simplicity, requiring no additional processing. However, it permits only limited control of pore size and pore structure, and therefore control of physical characteristics of the separator is limited. Notably, it is difficult to endow the separator with the safety shutdown function when this production system is used.
6.1.2 Wet-process Two-component System
With this system, plasticizer is mixed into the polymer before extrusion. Phase separation between the plasticizer and the polymer occurs in microscopic regions within the molten bulk during cooling after extrusion, and the pores are formed by removing the plasticizer. This process is called wet
because solvent is used to remove the plasticizer, and the term two-component
indicates that the polymer and plasticizer are present in the extruded mass. This system enables control of pore size and pore structure by selecting different polymer and plasticizer materials, which in turn allows the production of separators with a wide range of physical characteristics.
6.1.3 Wet-process Three-component System
This is similar to the system described above except that particles of inorganic filler are also mixed into the polymer before extrusion. The particles of filler are removed together with the plasticizer. The advantage of this system is that it is able to form larger pores than the other two systems, providing greater ion mobility.
6.1.4 Shutdown Function
Many separators are designed to have the physical characteristics that endow them with a shutdown function, a safety feature in which the polymer melts to close the micropores and prevent ion transport between the electrodes in the case of abnormal heat generation caused by short circuit or other reasons. This function prevents battery overheating and therefore greatly improves battery safety.
The temperature at which the shutdown function engages is determined by the melting point of the polymer of which the separator is composed. Figure 1.13 shows the degree of impedance to ion transport at different temperatures for polyethylene and polypropylene separators. A rise in impedance at high temperature illustrates that the pores close upon melting and the shutdown function is engaging. The temperature at which the shutdown function engages thus depends on the melting point of the polymer. For polyethylene separators, the impedance rises sharply between 130 °C and 140 °C, which means that the battery temperature will not exceed this range even in the case of a short circuit. For the polypropylene separator, the melting point is 170 °C, so the shutdown function does not engage until the battery temperature approaches this temperature.
FIGURE 1.13 Shutdown temperature for polyethylene separators. Impedance (1 kHz AC) change of electrolyte-penetrated separators at elevated temperature. (a, b) Polyethylene and (c) polypropylene.
It is worth noting that in this graph you can see that one of the polyethylene separators maintains high impedance even when temperature continues to increase, while the impedance for the other one falls off quickly after an initial spike, indicating a rupture of the membrane. The difference between these two different behavior characteristics depends on a complex combination of factors such as pore size, pore structure, and molecular weight of the polymer.
6.2 Recent Separator Developments
6.2.1 New Materials
All commercial separators so far have been made of polyolefins, but they provide only limited heat resistance. Research is now focusing on separators made of different materials which would offer superior heat resistance. These include heat-resistant rubber such as silicone rubber and fluororubber, aromatic polyamide resin, liquid crystalline polyester resin, heat-resistant resin containing polyoxyalkylene, and resin with cross-linked groups. Separators made of such materials are expected to demonstrate not only high temperature stability and safety but also superior ion transportation for better rate capability at high current discharge.
6.2.2 Inorganic Coating
One drawback of polyolefin separators is the possibility of membrane rupture when battery temperature continues to rise after the shutdown function is engaged (see Section 6.1.4). One approach to prevent this is to coat the membrane surface with a heat-resistant inorganic layer. In addition to inorganic materials such as alumina, silica, titania, and magnesia, candidates include vitreous materials, antioxidant ceramic particles, clay minerals, metal salt compounds, and tabular fillers. This technique uses a heat-resistant resin as a binder to hold the layer onto the surface of the separator. Aromatic polyamide resin, polyimide resin, liquid crystalline polyester, and aromatic polyether are used as binder. In addition to providing enhanced safety by preventing rupture of the separator at high temperature and during overcharging, the addition of an inorganic layer with antioxidant properties has been found to improve stability on the side that contacts the cathode. Such coated separators have begun to find limited commercial use in high-power LIBs employing advanced cathode materials, and they are expected to become more prominent as the development of such LIBs continues, but the inevitable added cost entailed by the coating process will pose challenges to widespread adoption.
6.2.3 Separators Containing Inorganic Material
Another approach to obtaining greater heat resistance is mixing inorganic material into the bulk of the separator. This has the additional advantage of increasing ion permeability. Inorganic materials for this purpose need to have antioxidant characteristics and resistance to the electrolyte solution. Alumina, silica, and titania are the leading candidates, although inorganic materials that absorb heat through dehydration reaction are also attracting attention. This technology is applicable not only for polyolefin separators but also for those made from heat-resistant resin as described in Section 6.2.1.
6.2.4 Nonwoven Separators
Nonwoven fabrics have been considered as an alternative type of separator due to their low cost and high ion permeability. Nonwovens under consideration include those made from liquid crystalline polyester, aromatic polyamide, and cellulose due to their heat-resistance characteristics. However, it is not yet possible to obtain nonwovens that are thin enough, and the pore sizes are too large for sufficient electrical insulation. One approach to reduce pore size is to add a porous inorganic layer to close the larger gaps in the fabric. Materials studied for this purpose include alumina, silica, and titania, and it is possible to improve insulation characteristics in this way. Evonik Degussa is the pioneer of this technique. Another way to reduce pore size while also reducing thickness is to form the nonwoven with ultrafine fibers and special spinning technologies such as flash spinning and electrospinning.
6.2.5 Laminated Separators
By laminating conventional polyethylene and polypropylene microporous membranes together, it is possible to obtain a separator with the desired shutdown function together with protection from rupture. Microporous membrane of liquid crystalline polyester, polyphenylene ether, aromatic polyamide, polyimide, polyamide imide resin, acrylic resin, and cross-linked polymer are now being studied as candidates for lamination with polyethylene in order to gain even greater heat resistance.
7 Conclusion
Since its commercialization, the LIB has facilitated a remarkable advance in portable electronics and broadened the accessibility to IT throughout society. The LIB is now used in practically every field of consumer electronics. In accordance with market needs, the development of each of the four major LIB components has historically emphasized characteristics that were suitable to portable electronics applications. As medium- and large-scale LIB applications begin to emerge, both for electric vehicles and for stationary power storage, the required characteristics are evolving. The direction of development of each LIB component is now turning toward the new requirements. Emerging new configurations of the LIB are now expected to facilitate a revolution in these medium- and large-scale applications, just as in portable electronics.
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2
Past, Present and Future of Lithium-Ion Batteries
Can New Technologies Open up New Horizons?
Yoshio Nishi, Sony’s Former Executive Vice President, Wakabadai, Asahi-ku, Yokohama, Kanagawa, Japan
Abstract
Since the first introduction of lithium-ion batteries into the market in 1991 by Sony, extensive improvements in their performances have been carried out. We believed that our LIBs utilizing hard carbon were very desirable for mobile gears. But it was not long before we were made to notice that there existed discrepancies between the required characteristics and our results. Although many novel technologies have been disclosed to improve the LIB performance further, some of them are rather different from the requirements. In this chapter, some new technologies are discussed from this perspective.
Keywords
Average discharge voltage; Charge/discharge efficiency; Gravimetric energy density; Lithium-ion polymer batteries; Volumetric energy density
Chapter Outline
1. Introduction
2. How LIB was Born?
3. Performance that Users Expect from LIB
4. Improvement of LIB
4.1. Sn-based Anode
4.2. Si-based Anode
4.3. Ti-based Anode
4.4. LIB with Gelled Polymer Electrolyte
4.5. LIB with LiFePO4 Cathode
5. Can New Battery Technologies Open up Novel Horizons for
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