Special Issue "Lithium-ion Batteries"

Guest Editor
Dr. Izumi Taniguchi
Department of Chemical Engineering, Graduate School of Science and Engineering, Tokyo Institute of Technology 12-1, Ookayama-2, Meguro-ku, Tokyo 152-8552, Tokyo, Japan
Website: http://www.chemeng.titech.ac.jp/~itaniguc/profile.html
E-Mail:
Interests: lithium-ion battery; solid oxides fuel cells; energy storage; fine ceramic particles; aerosol technology; functional material processing

Submission

All papers should be submitted to energies@mdpi.org with copy to the guest editor. To be published continuously until the deadline and papers will be listed together at the special websites.

Submitted papers should not have been previously published nor be currently under consideration for publication elsewhere. All papers are refereed through a peer review process. A guide for authors, sample copies and other relevant information for submitting papers are available on the Instructions for Authors page. Energies is an international peer-reviewed quarterly journal published by Molecular Diversity Preservation International.

Article Processing Charges (APC)

Article Processing Charges (APC) are 300 CHF per paper and additional English correction fees (250 CHF) will be added in certain cases (550 CHF per paper for those papers that require extensive additional formatting and/or English corrections) for paper submitted before 31 December 2009. Starting 1 January 2010, Article Processing Charges are of 800 CHF per accepted article.

• Li-ion battery
• battery design
• battery efficiency
• battery life and life cycle

Type of Paper: Review
Title: Si-based Materials for Lithium Rechargeable Batteries
Author: Hua Kun Liu
Affiliation: Institute for Superconducting and Electronic Materials, University of Wollongong, Squires Way, Fairy Meadow, NSW 2522, Australia; E-Mail: hua@uow.edu.au; phone: +61-2-4221-4547; fax: +61-2-4221-5731
Abstract: Lithium rechargeable batteries are important for electrochemical energy storage and conversion. The energy density and electrochemical performance of lithium ion batteries is strongly dependant on the properties of cathode materials, anode materials and electrolytes. In order to meet global requirements for clean emissions, it is needed to develop new materials and better technologies for hybrid and electric cars, and for improving human well-being. Graphite has been commonly used as the commercial anode material due to its excellent electrochemical properties. However, low theoretical capacity of graphite has remained as an inevitable limitation. Lithium alloys with high specific capacities have attracted much attention to overcome capacity limitation of graphite [372 mA h/g]. In particular, Si alloy has been reported to be one of the most promising anode materials instead of the commercial graphite because of much higher theoretical capacity of Si [4200 mA h/g]. However, large specific volume changes occur during Li insertion and extraction reactions in Si alloy systems, which cause rapid capacity fading during alloying and de-alloying processes by pulverization of electrode materials. This paper will review Si-based materials for lithium rechargeable batteries.

Type of Paper: Review
Title: Electrostatic Spray Deposition Derived Anode Materials for Li Ion Battery Application
Author: Xifei Li, Abirami Dhanabalan, Kevin Bechtold, Chunlei Wang*
Affiliation: Department of Mechanical and Materials Engineering, Florida International University, 10555 W. Flagler St., EC 3463, Miami, FL 33174, USA; *Contact: Email: wangc@fiu.edu
Abstract: Electrostatic spray deposition (ESD) technique is based on using an electrostatic field by applying high voltage to form and accelerate atomic level low viscosity liquid droplets from the tip of a capillary as a result of surface tension. The ESD technique provides a simple and versatile method for generating a rich variety of morphologies, such as thin-films, porous and fibrous matrices, and single or multi-component materials. By this method, we have fabricated various porous and fibrous anode materials, such as: SnO₂, CuO₂, and TiO₂. In this review, the fabrication procedure, material properties, and electrochemical performance of the ESD derived anode materials will be reviewed and discussed.

Type of Paper: Review
Title: High Voltage Spinel Cathode Materials for Li-Ion Batteries
Author: Guoqiang Liu
Affiliation: Northeastern University, Shenyang 110004, P. R. China; E-Mail: liugq@smm.neu.edu.cn
Abstract: In recent years, the spinel material LiNi_0.5Mn_1.5O₄ has attracted much attention because of its advantages of low cost, low toxicity and good electrochemical performances. The most remarkable property of the kind of materials is their higher discharge plateaus at around 5.0 V. The high working voltage can lead to a high power density, so the batteries with this material as cathode will produce a high power output. Until now at least 152 papers regarding this 5.0 V material have been cited by Science Citation Index Expanded. These papers studied the structure and electrochemical properties of LiNi_0.5Mn_1.5O₄ in detail. This review describes the studies including synthesizing method, doping element, coating on surface, analyzing mechanism of high voltage and comparing two kinds structure of primitive simple cubic structure (P4332) and face-centered spinel (Fd3m).

Type of Paper: Review
Title: Recent Development of One-Dimensional Vanadium Oxide Nanomaterials as Positive Electrode Materials for Lithium Ion Batteries
Author: Fu Zhou
Affiliation: Department of Chemistry, China University of Petroleum, Qingdao, Shandong, 266555, P.R. China; E-Mail: boksiczf@ustc.edu
Abstract: The ever growing market of portable electronics requires the development of new generation lithium ion batteries. Vanadium has oxidation states available from +2 to +5, indicating potential large specific capacity. Vanadium oxides have been studied extensively as positive electrode materials for lithium ion batteries, but have met with serious issues such as structure instability during charge/discharge processes, bad cycle performance and so on. In recent years, nanostructured vanadium oxides have been proved to be a possible solution to these problems. Among all types of nanostructures, the one-dimensional (1D) materials are the most favorable candidates because of their short lithium ion diffusion length, good cycle performance and high specific capacity. In this review paper, the up-to-date development of the synthesis and electrochemical study of vanadium oxide based 1D nanostructured electrode materials are discussed.

Title: Effect of impurities (oxides, hydroxides) in molten salt electrolytes on the thermal stability of FeS₂ cathode materials in Li/FeS₂ thermal batteries
Author: Patrick J. Masset
Affiliation: ZIK Virtuhcon - Group "Multiphase Systems", TU Bergakademie Freiberg, Department of Energy Process Engineering and Chemical Engineering, Fuchsmühlenweg 9, Reiche Zeche, D-09596 Freiberg, Germany
Abstract: Thermal activated batteries (thermal batteries) are well suited for military applications especially for their robustness and high reliability. They use molten salts as electrolyte (retained with magnesia particles) due to their high ionic conductivity (approx. 1.5 – 5 S/cm) and their large electrochemical window (approx. 3.5 V for chloride-based electrolyte). After the thermal activation with pyrotechnics, the temperature of functioning ranges between 650 °C and the freezing point of the electrolyte. Pyrite FeS₂ is commonly used as cathode material due to: i) flat discharge plateau (constant voltage), ii) its abundance in ores (competitive price of 0.5 $/kg) and iii) its relative high discharge potential (approx. 2.1 V Li⁺/Li). At high temperature, the pyrite decomposes and leads to the formation of a porous structure of FeS_1.14 and releases sulphur gas. The latter reacts with the lithium metal from the anode and it forms an insulating layer of lithium sulphide (Li₂S) in the electrolyte which deteriorates drastically the battery functioning and performances. In addition, it reduces the cathode capacity and the life time of the battery.
The thermal stability of pyrite has been widely investigated. However, its thermal behaviour in the presence of molten salt has been barely investigated and the effect of impurities such as oxides and hydroxides has not yet been studied. The presence of oxide and/or hydroxide may arise: i) from the addition of lithium oxide (Li₂O) as anti-peak in the catholyte’s compartment (pyrite and electrolyte) or ii) as hydrolysis product during the drying process of the salt. In the present work, the thermal stability of the pyrite has been investigated in the presence of either oxide or hydroxide by adding in the electrolyte (LiCl-KCl eutectic) up to 10 wt% of Li₂O or LiOH, respectively. In presence of oxide or hydroxide, it was shown that the decomposition of the pyrite was lowered. In addition, a mechanism based on the reaction between dissolved oxide and sulphide is proposed to explain the pyrite decomposition.

Type of Article: review
Title: Advanced Li-ion battery materials for plug-in hybrid electric vehicles
Authors: Yaser Abu-Lebdeh, Fabrice Courtel, Hugues Duncan, Isobel Davidson
Affiliation: National Research Council Canada, M12-1200 Montreal Road, Ottawa, Ontario K1A 0R6, Canada; E-mail: Yaser.Abu-Lebdeh@nrc.gc.ca
Abstract: Li-ion batteries are successfully used in various electronic devices and are strongly considered for the next generation of hybrid electric vehicles (HEV) and also projected to power plug-in hybrid electric vehicles (PHEV). In this review we discuss the development of new materials for Li-ion batteries that will help meet the requirements for PHEVs that are more demanding in terms of energy and power density and also more challenging to enhance their safety and lower their cost.
Current research in our group and other research groups in the world are focused on investigating materials that will enhance the inherent safety and performance (power/energy density, cycle/calendar life, low temperature performance, etc. ) of the batteries by modifying the chemistry of current materials or introducing new generation of materials with different chemistry. The review will discuss the current state of development of the chemistry and battery performance of the three key materials of the Li ion battery (cathode, anode electrolyte) and how they meet the goals and requirements for PHEVs.
This paper will show the results of our own investigations and that of others on certain Lithium metal oxides and phosphate cathode materials such as the high voltage LiNi_0.5Mn_1.5O₄. It will also discuss the results of current efforts to improve the capacity and cycle life of batteries made with these types of materials and different synthetic methods currently used to vary the morphology of the particles. One aspect is the synthesis of the materials as nanoparticles that will enhance the batteries’ power density. The potential use of high capacity cathode materials based on Li₂MSiO₄ (M: Mn, Fe, Co, Ni) will be also discussed.
On the anode side, extensive R&D is taking place on the use of metal oxides and metal alloys as alternatives to graphite. The two materials undergo a large volume expansion during cycling that leads to poor cycle life. Efforts to mitigate this effect are focused on the synthesis of certain oxides such as SnO₂ in the nanoscale and also on the use of new organic binders to replace the conventional PVDF. This will lead to anode composite materials that better accommodate the volume expansion and exhibit improved cycle life.
One of the main contributors to the safety issues in current batteries is the volatile and flammable components of the electrolytes that are the carbonate solvents. One serious alternative is ionic liquids based on the ringed aliphatic ammonium cation that have no volatility and are not flammable. This paper will review the different type of ionic liquids investigated in Li-ion batteries and also focus more on the effect of molecular engineering of the organic cation on the electrochemical performance of the electrolyte, most important is its cathodic stability. Brief comparisons will be made of other types of electrolytes such as polymer and glass electrolytes as well as conventional electrolytes with more thermally and electrochemically stable solvents.

Type of Article: article
Title: A High Capacity Li-ion Cathode: The Fe(III/VI) Super-iron Cathode
Author: Stuart Licht
Affiliation: Department of Chemistry and Institute of Basic Energy Science and Technology, George Washington University, Washington, DC 20052, USA
Abstract: A super-iron Li-ion cathode with a 3-fold higher reversible capacity (a storage capacity of 485 mAh/g) is presented. One of the principle constraints to vehicle electrification is that the Li-ion cathode battery chemistry is massive, and expensive. Demonstrated is a 3^e- storage lithium cathodic chemistry, and a reversible Li super-iron battery, which has a significantly higher capacity than contemporary Li-ion batteries. The super-iron Li-ion cathode consists of the hexavlanent iron (Fe(VI)) salt, Na₂FeO₄, and is formed from inexpensive and clean materials. The charge storage mechanism is fundamentally different from those of traditional lithium ion intercalation cathodes. Instead, charge storage is based on multi-electron faradaic reduction, which considerably enhances the intrinsic charge storage capacity.

Type of Paper: Article
Title: Optimization and Characterization of Lithium Ion Cathode Materials in the System Li_(3+x)/3Ni_(1-x-y)Co_yMn_2x/3O₂
Authors: V. Manivannan, M. Chennabasappa and J. Garrett
Affiliation: Department of Mechanical Engineering, Colorado State University, Fort Collins, Colorado, 80523, USA; E-Mail: mani@engr.colostate.edu
Abstract: Technological improvements in energy storage are being driven by the rising demand for portable electronics, an uncertain fossil fuel industry, the need to store energy locally and ever-increasing energy consumption^1-2. Yet, much improvement is needed before lithium-ion batteries can be viable options in many products. LiCoO₂ is the current state of the art material that is used (capacity 140 mAh/g) where the constituent Co is too toxic and expensive. The metrics of cost, safety, and energy density need to be improved in addition to charge/discharge rates and lifespan of the batteries. There is ongoing effort to identify novel materials that have performance better than LiCoO₂. The objective of this thesis work is to explore materials in the Li_(3+x)/3Ni_(1-x-y)Co_yMn_2x/3O₂ system which is derived from LiNiO₂, Li₂MnO₃ and LiCoO_2³. A ternary composition diagram was used to identify sample points, and compositions for testing were initially chosen in an arrangement conducive to mathematical modeling. The system allowed samples to be synthesized by conventional solid-state method and initial capacities on the order of ~250 mAh/g were obtained. Preliminary results showed that these materials exhibit superior safety features in addition to the cost-competiveness thereby positioning these materials as promising for Li-ion battery applications.
References: 1. Tarascon, J.-M. and Armand, M. Nature 2001, 414, 359-367; 2. Lu, Z.; Beaulier, L.Y.; Donaberver, R.A; Thomas, CL; Dahn, J.R. J. Electrochem. Soc. 2002, 149, A778; 3. Zhang et al. J. Electrochem. Soc. 2005, 152, A171-A178

Type of Paper: Article
Title: Surface-modified Membrane as a Separator For Lithium-ion Polymer Battery
Authors: Jun Young Kim ^1,2 and Dae Young Lim ³
Affiliation: ¹ Material Laboratory, Corporate R&D Center, Samsung SDI Co., Ltd., 575, Shin-dong, Yeongtong-gu, Suwon-si, Gyeonggi-do, 443-731, Republic of Korea; ² Department of Materials Science & Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA; ³ Fusion Textile Technology Team, Korea Institute of Industrial Technology, 1271-18, Sa-1 dong, Sangrok-gu, Ansan-si, Gyeonggi-do 426-791, Republic of Korea; E-mails: junykim74@hanmail.net (J.Y.K.), zoro1967@kitech.re.kr (D.Y.L.)
Abstract: This paper describes the fabrication of a surface-modified polyethylene membrane using plasma technology to create high-performance separators for practical applications in rechargeable lithium-ion polymer battery. The surface of polyethylene membranes was modified with acrylonitrile via plasma-induced coating technique. The plasma-induced acrylonitrile coated polyethylene membrane was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and contact angle measurement. The electrochemical performance of lithium-ion polymer cell assembly fabricated with surface-modified membranes was also analyzed. The surface characterization demonstrates that the enhanced adhesion of modified polyethylene membrane resulted from the increased polar component of surface energy. The presence of plasma-induced acrylonitrile formed on the surface of polyethylene membrane via plasma modification process plays a critical role in improving the wettability and electrolyte retention, the interfacial adhesion between the electrodes and the separator, the cycle performance of the resultant lithium-ion polymer cell assembly. This surface-modified membrane holds a great potential to be a promising polymer membrane as high-performance and cost-effective separators for lithium-ion polymer battery. This paper also suggests that the performance of lithium-ion polymer battery can be greatly enhanced by plasma modification of commercial separators with proper materials for targeted application.

Type of paper: Article
Title: Aqueous Lithium-ion Battery of LiV₃O₈//LiMn₂O₄ with high discharge specific capacity
Authors: Mingshu Zhao ¹, Weimin Dai ¹, Qingyang Zheng ², Fei Wang ¹, Xiaoping Song ¹
Affiliations: ¹ MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, School of Science, Xi’an Jiaotong University, 710049, Xi’an, China; E-Mail: zhaomshu@email.xjtu.edu.cn (M.S.Z.); daiwm@163.com (W.M.D.); feiwang@email.xjtu.edu.cn (F.W.); songxp email.xjtu.edu.cn (X.P.S.)
² Xi'an High-tech Research Institute, 710025, Xi’an, China; E-Mail: zqymail@yahoo.com.cn (Q.Y.Z.)
Abstract: An aqueous lithium-ion battery system consisting a LiV₃O₈ (negative electrode) and LiMn₂O₄ (positive electrode) in saturated LiNO₃ aqueous electrolyte was constructed and studied. Cyclic voltammetry results show that both LiV₃O₈ and LiMn₂O₄ are very stable in this aqueous electrolyte and can be used as the negative and positive electrode material without evident hydrogen or oxygen evolution. The cell delivers a high capacity of 113.5 mAhg^-1 based on the weight of the positive electrode. It also exhibits good cycling stability with a capacity retention of 88.1% (100.3 mAhg^-1) over 25 charge/discharge cycles. Between the cycle number of 60 and 120, maintained at about 60 mAhg^-1, corresponding to 53% of the original value. After 150 cycles, the discharge capacity is still 45.1 mAhg^-1, which is much better than many aqueous lithium-ion battery reported.
Keywords: Lithium ion battery; Aqueous electrolyte; Lithium manganese oxides; Electrochemical properties.