Solid cathode lithium batteries

The semiconductive properties and tunnel structure of sulfide and transition-metal oxides led to the use of these materials in lithium power sources (Table 2.5). Several lithium-based chemistries were successfully applied to replace the prior system Zn/AgO and later the lithium-iodine batteries in implantable medical devices [59-61]. For example, Li//CuO, Li//V205, Li//CF and more recently Li// Ag2V40ii couples have been adopted to power cardiac pacemakers requiring less that 200 pW [62,63]. The lithium/carbon monofluoride (Li//CFJ primary cells are very attractive in several applications because of the double energy density with respect to the state-of-the-art LiZ/MnOa primary batteries (theoretically 2203 against 847 Wh kg ). 

Polycarbon fluorides of the general formula CV n can be obtained by direct fluorination of carbon black or other varieties of carbon at high temperatures. Theoretical specific energy density 2600 Wh kg can be achieved with these materials. Lithium cells with polycarbon fluoride cathodes have an open-circuit voltage in the range of 2.8-3.3 V, depending on the composition of the cathode material. A typical cell reaction may be written [64]  

the theoretical specific discharge capacity (2 (in mAh g ) is expressed by  

Cells based on polycarbon fluorides are manufactured commercially in various forms. System developed by Matsushita Electric Industrial Co. is designed as a BR 435 cylindrical cell. Cells constmcted by Nippon Steel Co. use carbon fibers as electrodes they are found to be rechargeable. Cells for military applications have 

Lithium manganese oxide (Li-Mn02) battery is the most common consumer grade battery that covers about 80 % of the lithium battery market. This system includes heat-treated Mn02 as cathode, lithium metal as anode and LiC104 in propylene carbonate/dimethoxyethane as aprotic electrolyte. The overall battery reaction is  

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The solid-cathode lithium batteries are generally used in low- to moderate-drain applications and are manufactured mainly in small flat or cylindrical sizes ranging in capacity from 30 mAh to about 5 Ah, depending on the particular electrochemical system. Larger batteries have been produced in cylindrical and prismatic configurations. A comparison of the performance of solid-cathode lithium batteries and conventional batteries is presented in Chap. 7. 

Although a number of different solid-cathode lithium batteries have been developed and even manufactured, more recently the trend is toward reducing the number of different chemistries that are manufactured. The lithium/manganese dioxide (Li/Mn02) battery was one of the first to be used commercially and is still the most popular system. It is relatively inexpensive, has excellent shelf life, good high-rate and low-temperature performance, and is available in coin and cylindrical cells. The lithium/carbon monofiuoride (LijCFj J battery... 

Other developments in the area of solid state lithium batteries include prototype production and testing of thin-film microbatteries at Oak Ridge National Laboratory in the USA. The fabrication involves electrode and electrolyte film deposition to form compact layers of thickness of the order of few microns. The cell uses a lithium anode, an amorphous Li3 3PO3.9N0.17 solid electrolyte and an amorphous V205 cathode ... 

Huang, F., Z. Fu, and Q. Qin. 2003. A novel Li2Ag05V2O5 composite film cathode for all-solid-state lithium batteries. Electrochem. Comm. 5 262-266. 

FIGURE 19.10 A schematic diagram af a solid-state lithium battery. Lithium metal is the anade, and TiS2 is the cathode. During operation, Li ions migrate through the solid polymer electrolyte from the anode to the cathode while electrons flow externally from the anode to the cathode to complete the circuit. 

Figure 13.12 shows a schematic solid-state lithium battery. The anode is made of a conducting carbonaceous material, usually graphite, which has tiny spaces in its structure that can hold both Li atoms and Li ions. The cathode is made of a transition... 

Like aforementioned organic cathode materials in solid-electrode lithium batteries, tunable molecular structure is their important feature through which their electrochemical properties such as redox potential and solubility can be changed. The active organic materials in flow batteries espouse the same dogma. For example, quinone based molecules are common active species employed in flow batteries and their stmcture can be readily tuned to achieve favorable electrochemical properties [170, 174, 178]. With tuned small organic molecules called 9,10-anthraquinone-2,7-disulphonic acid (AQDS), a team of Harvard scientists demonstrated that AQDS underwent extremely rapid and reversible two-electron two-proton reduction in sulphuric acid [170]. An aqueous flow battery with the quinone/hydroquinone couple as anode and the Br2/Br redox couple as cathode yielded a peak power density exceeding 0.6 W cm at 1.3 A com (Fig. 14). 

Lithiirm Bromine Trifluoride Batteiy Solid State Secondary Lithium Batteries Secondary Insertion Cathode Lithium Batteries... 

Ogumi, Z. Uchimoto, Y. Takehara, Z. Kanamoii, Y. (1989). Preparation of Ultra-Thin Solid-State Lithium Batteries Utilizing a Plasma-Polymerized Solid Polymer Electrolyte. /, Chem. Soc., Chem. Commun., Vol. 21, pp. 1673-1674 Ohnishi, R. Katayama, M. Takanabe, K Kubota, J. Domen, K (2010). Niobium-Based Catalysts Prepared by Reactive Radio-Frequency Magnetron Spnitteiing and Arc Plasma Methods as Non-Noble Metal Cathode Catalysts for Polymer Electrolyte Fuel Cells. Electrochim. Acta, Vol. 55, pp. 5393-5400 Papadopoulos, N.D. Karayiarmi, H.S. Tsakiridis, P.E. Perraki, M. Hiistoforou, E. (2010). 

Souquet JL, Duclot M (2002) Thin film lithium batteries. Solid State Ionics 148 375-379 Whittingham MS (2004) Lithium batteries and cathode materials. Chem Rev 104 4271-4301... 

An example of a layer structure mixed conductor is provided by the cathode material L CoC used in lithium batteries. In this solid the ionic conductivity component is due to the migration of Li+ ions between sheets of electronically conducting C0O2. The production of a successful mixed conductor by doping can be illustrated by the oxide Cei-jPxx02- Reduction of this solid produces oxygen vacancies and Pr3+ ions. The electronic conductivity mechanism in these oxides is believed to be by way of electron hopping between Pr4+ and Pr3+, and the ionic conductivity is essentially vacancy diffusion of O2- ions. 

There have been several papers and patents related to the use of SVO as a high-rate cathode material for the ICD application. In addition to the high-rate capability displayed by SVO as a cathode, this material also displays high-energy density relative to other solid cathode materials used in lithium batteries (see Table 13.1). Additionally, there has also been interest in SVO and related materials as rechargeable cathode materials for lithium and lithium-ion type cells. Literature related to both of these intended applications are reviewed in the following sections. 

Holmes, C.F., P. Keister, and E.S. Takeuchi. 1987. High-rate lithium solid cathode battery for implantable medical devices. 1987. Prog. Batt. Solar Cells. 6 64—66. 

Leising, R.A. and E.S. Takeuchi. 1993. Solid-state cathode materials for lithium batteries Effect of synthesis temperature on the physical and electrochemical properties of silver vanadium oxide. Chem. Mater. 5 738-742. 

Quasi-layered oxides of the type AMO2 (A = Li, Na M = bivalent Ti, V, Cr, Mn, Fe, Co, Ni) prepared by high-temperature solid-state reactions have also been studied as possible cathodes since these materials undergo loss of alkali metal upon treatment with I2 or Br2 in acetonitrile. Of these, LiCo02 is the material of choice in the current generation of lithium batteries. A practical problem here is the expense of Co. However, LiNi02 doped with 10-30 mole% LiCoCh shows promise as a replacement. ... 

The composite cathode usually consists of an inert conducting material, the polymer/salt electrolyte, and the solid active insertion particles. The key requirements for a material to be successfully used as a cathode in a rechargeable lithium battery are as follows ... 

Li, G., Azuma, H., and Tohda, M., LiMnP04 as the cathode for lithium batteries, Electrochem. Solid State Lett, 5, A135, 2002. 

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