In the previous paper Ralph Brodd and Martin Winter described the different kinds of batteries and fuel cells. In this paper I will describe lithium batteries in more detail, building an overall foundation for the papers that follow which describe specific components in some depth and usually with an emphasis on the materials behavior. The lithium battery industry is undergoing rapid expansion, now representing the largest segment of the portable battery industry and dominating the computer, cell phone, and camera power source industry. However, the present secondary batteries use expensive components, which are not in sufficient supply to allow the industry to grow at the same rate in the next decade. Moreover, the safety of the system is questionable for the large-scale batteries needed for hybrid electric vehicles (HEV). Another battery need is for a high-power system that can be used for power tools, where only the environmentally hazardous Ni/ Cd battery presently meets the requirements. A battery is a transducer that converts chemical energy into electrical energy and vice versa. It contains an anode, a cathode, and an electrolyte. The anode, in the case of a lithium battery, is the source of lithium ions. The cathode is the sink for the lithium ions and is chosen to optimize a number of parameters, discussed below. The electrolyte provides for the separation of ionic transport and electronic transport, and in a perfect battery the lithium ion transport number will be unity in the electrolyte. The cell potential is determined by the difference between the chemical potential of the lithium in the anode and cathode, ∆G ) -EF. As noted above, the lithium ions flow through the electrolyte whereas the electrons generated from the reaction, Li ) Li+ + e-, go through the external circuit to do work. Thus, the electrode system must allow for the flow of both lithium ions and electrons. That is, it must be both a good ionic conductor and an electronic conductor. As discussed below, many electrochemically active materials are not good electronic conductors, so it is necessary to add an electronically conductive material such as carbon * To whom correspondence should be addressed. Phone and fax: (607) 777-4623. E-mail: stanwhit@binghamton.edu. 4271 Chem. Rev. 2004, 104, 4271−4301

http://www.chemie.uni-regensburg.de/Anorganische_Chemie/Vortrag/StudentenWS06-07/Vortrag_Amereller.pdf

Lithium Batteries and Cathode Materials

Thermal runaway caused fire and explosion of lithium ion battery

Positive electrodes for Li-ion and lithium batteries (also termed “cathodes”) have been under intense scrutiny since the advent of the Li-ion cell in 1991. This is especially true in the past decade. Early on, carbonaceous materials dominated the negative electrode and hence most of the possible improvements in the cell were anticipated at the positive terminal; on the other hand, major developments in negative electrode materials made in the last portion of the decade with the introduction of nanocomposite Sn/C/Co alloys and Si−C composites have demanded higher capacity positive electrodes to match. Much of this was driven by the consumer market for small portable electronic devices. More recently, there has been a growing interest in developing Li−sulfur and Li−air batteries that have the potential for vastly increased capacity and energy density, which is needed to power large-scale systems. These require even more complex assemblies at the positive electrode in order to achieve good properties. This r...

Positive Electrode Materials for Li-Ion and Li-Batteries†

Electrochemical impedance spectroscopy (EIS) is a powerful tool to investigate properties of materials and electrode reactions. This Primer provides a guide to the use of EIS with a comparison to other electrochemical techniques. The analysis of impedance data for reduction of ferricyanide in a KCl supporting electrolyte is used to demonstrate the error structure for impedance measurements, the use of measurement and process models, as well as the sensitivity of impedance to the evolution of electrode properties. This Primer provides guidelines for experimental design, discusses the relevance of accuracy contour plots to wiring and instrumentation selection, and emphasizes the importance of the Kramers-Kronig relations to data validation and analysis. Applications of EIS to battery performance, metal and alloy corrosion, and electrochemical biosensors are highlighted. Electrochemical impedance measurements depend on both the mechanism under investigation and extrinsic parameters, such as the electrode geometry. Experimental complications are discussed, including the influence of nonstationary behaviour at low frequencies and the need for reference electrodes. Finally, emerging trends in experimental and interpretation approaches are also described.

/pdf/electrochemical-impedance-spectroscopy-3e6x9qlxk6.pdf

Electrochemical Impedance Spectroscopy

The olivine LiFePO4 now stands as a competitive candidate of cathode material for the next generation of a green and sustainable lithium-ion battery system due to its long life span, abundant resources, low toxicity, and high thermal stability. In this review, we focus on LiFePO4 and discuss its structure, synthesis, electrochemical behavior, mechanism, and the problems encountered in its application. The major goal is to highlight some recent development of LiFePO4 with high rate capability, high energy density, and excellent cyclability resulting from conductive coating, nanocrystallization, or preparation.

Development and challenges of LiFePO4 cathode material for lithium-ion batteries

Reaction behavior of LiFePO4 as a cathode material for rechargeable lithium batteries

Characterization of LiFePO4 as the cathode material for rechargeable lithium batteries

Lithium ion cell safety

PROBLEM TO BE SOLVED: To enhance charging and discharging capacity of a lithium secondary battery during a large-current charging and discharging, where the lithium secondary battery uses a low-price material of iron phosphate lithium as a positive electrode. SOLUTION: A powder 2 is carried on powder 1, where a powder 1 is formed of iron phosphate lithium series material having an olivine structure, which is indicated by the general expression LizFe1-yXyPO4 (0<=y<=0.3, 0<z<=1, X is at least one selected from among magnesium, cobalt, nickel and zinc), while a powder 2 is formed of a material such that it has conductivity and whose oxidation-reduction potential is higher than that of a material for activating a positive electrode of a lithium secondary battery made of iron phosphate lithium series material. Therefore, a battery can be obtained which has larger charging and discharging capacity compared with others using an iron phosphate lithium series material that does not carry powders thereon, where charging and discharging capacity of the battery in relation to the invention is little decreased, even if charging and discharging current increases.

Koji Takei

Papers

Reaction behavior of LiFePO4 as a cathode material for rechargeable lithium batteries

Characterization of LiFePO4 as the cathode material for rechargeable lithium batteries

Lithium ion cell safety

Material for activating positive electrode of lithium secondary battery and the lithium secondary battery

Structural and Thermal Characteristics of Nickel Dioxide Derived from LiNiO2