Lithium rechargeable type

There have been a number of attempts to produce commercial lithium rechargeable batteries. The V205 positive is currently used by the Matsushita Battery Industrial Co in Japan for the production of small capacity, coin-type cells. Fig. 7.24 shows a cross-section of one prototype. For the construction of the battery, V205 and carbon black are mixed together with a binder, moulded and vacuum-dried to form the positive electrode pellet. A solution of LiBF4 in a propylene carbonate-y-butyrolactone-1,2-dimethoxyethane mixture absorbed in a polypropylene separator is used as the electrolyte. 

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. 

While the development of primary cells with a lithium anode has been crowned by relatively fast success and such cells have filled their secure rank as power sources for portable devices for public and special purposes, the history of development of lithium rechargeable batteries was full of drama. Generally, the chemistry of secondary batteries in aprotic electrolytes is very close to the chemistry of primary ones. The same processes occur under discharge in both types of batteries anodic dissolution of lithium on the negative electrode and cathodic lithium insertion into the crystalline lattice of the positive electrode material. Electrode processes must occur in the reverse direction under charge of the secondary battery with a negative electrode of metallic lithium. Already at the end of the 1970s, positive electrode materials were found, on which cathodic insertion and anodic extraction of lithium occur practically reversibly. Examples of such compounds are titanium and molybdenum disulfides. 

Tucker M, Doeff M, Richardson T, Finones R, Caims E, Rermer J (2002) Hyperfine fields at the Li site in LiFeP04-type olivine materials for lithium rechargeable batteries a Li-7 MAS NMR and SQUID study. J Am Chem Soc 124(15) 3832-3833... 

The different types of lithium rechargeable batteries identified in Fig. 34.1 can be classified conveniently into five categories ... 

These lithium coin cells generally use a metal oxide intercalation compound for the positive active material and a hthium alloy, such as lithium aluminum, which is less reactive than metallic lithium, for the negative electrode. An organic solution is used for the electrolyte. The energy density and specific energy of the different rechargeable lithium coin-type batteries are summarized in Fig. 34.36. 

FIGURE 34.36 Energy density and specific energy of rechargeable lithium coin-type batteries. 

Lithium-Aluminum Vanadium Pentoxide Batteries. The LiAl/V205 cell is another rechargeable lithium coin-type battery with a low self-discharge rate (2% per year at 20°C) which can be used for low-drain loads. Over 1000 cycles can be obtained at 10% depth of discharge. The construction is similar to the one illustrated in Fig. 34.37, except that V2OS is used for the active positive material. 

FIGURE 34.45 Discharge characteristics of carbon-lithium rechargeable coin-type battery (CL2020 size) (a) discharge at 20°C, (b) discharge at 10 kfl. (From Panasonic Division of Matsushita Electric Corp. of America.)... 

TABLE 34.22 Rechargeable Carbon-Lithium Coin-Type Batteries... 

Lithium s 47% fraction of the 3.61 bilUon rechargeable battery market in 1999s had become 52% and 3 billion by itself in 2002. Sony Corp. had about 33% of this market, and Sanyo Electric Company 23% in 2000. Sony originally developed the lithium-ion batteries, but in 2000 began converting much of its manufacturing capacity to the more profitable lithium polymer type. Sanyo Electric also produced about 32% of the nickel-cadmium, and 46% of the nickel hydride batteries in 2000 (Lerner, 2001 Jarvis, 2000). Considerable research has been conducted on rechargeable lithium batteries for automobiles, but by 2002 there were still major safety and construction problems. 

A second type of soHd ionic conductors based around polyether compounds such as poly(ethylene oxide) [25322-68-3] (PEO) has been discovered (24) and characterized. These materials foUow equations 23—31 as opposed to the electronically conducting polyacetylene [26571-64-2] and polyaniline type materials. The polyethers can complex and stabilize lithium ions in organic media. They also dissolve salts such as LiClO to produce conducting soHd solutions. The use of these materials in rechargeable lithium batteries has been proposed (25). 

Apart from the improvement and scaling up of known systems such as the lead accumulator or the nickel/cadmium cell, new types of cells have also been developed. Here, rechargeable lithium batteries and nickel-systems seem to be the most promising the reason for this will be apparent from the following sections [3]. 

It should be noted that the rechargeable cells discussed later have the same construction and differ only in separator type, electrode composition and cathode / anode balance. For comparison, Fig. 3 shows the design of an AA-size lithium cell. The construction with a spirally rolled electrode increases the power output. 

Table 1. Commercially available rechargeable coin-type cells with lithium-metal alloys...

With regard to rechargeable cells, a number of laboratory studies have assessed the applicability of the rocking-chair concept to PAN-EC/PC electrolytes with various anode/cathode electrode couples [121-123], Performance studies on cells of the type Li°l PAN-EC/PC-based electrolyte lLiMn20 and carbon I PAN-EC/PC-based electrolyte ILiNi02 show some capacity decline with cycling [121]. For cells with a lithium anode, the capacity decay can be attributed mainly to passivation and loss of lithium by its reaction with... 

Manganese dioxide is the most extensively used electrode for different types of power sources (alkaline primary and rechargeable, lithium... 

Sony s Introduction of the rechargeable lithium-ion battery in the early 1990s precipitated a need for new separators that provided not only good mechanical and electrical properties but also added safety through a thermal shutdown mechanism. Although a variety of separators (e.g., cellulose, nonwoven fabric, etc.) have been used in different type of batteries, various studies on separators for lithium-ion batteries have been pursued in past few years as separators for lithium-ion batteries require different characteristics than separators used in conventional batteries. 

ZnO displays similar redox and alloying chemistry to the tin oxides on Li insertion [353]. Therefore, it may be an interesting network modifier for tin oxides. Also, ZnSnOs was proposed as a new anode material for lithium-ion batteries [354]. It was prepared as the amorphous product by pyrolysis of ZnSn(OH)6. The reversible capacity of the ZnSn03 electrode was found to be more than 0.8 Ah/g. Zhao and Cao [356] studied antimony-zinc alloy as a potential material for such batteries. Also, zinc-graphite composite was investigated [357] as a candidate for an electrode in lithium-ion batteries. Zinc parhcles were deposited mainly onto graphite surfaces. Also, zinc-polyaniline batteries were developed [358]. The authors examined the parameters that affect the life cycle of such batteries. They found that Zn passivahon is the main factor of the life cycle of zinc-polyaniline batteries. In recent times [359], zinc-poly(anihne-co-o-aminophenol) rechargeable battery was also studied. Other types of batteries based on zinc were of some interest [360]. 

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