Lithium Metal Secondary Batteries

Secondary lithium-metal batteries which have a lithium-metal anode are attractive because their energy density is theoretically higher than that of lithium-ion batteries. Lithium-molybdenum disulfide batteries were the world s first secondary cylindrical lithium—metal batteries. However, the batteries were recalled in 1989 because of an overheating defect. Lithium-manganese dioxide batteries are the only secondary cylindrical lithium—metal batteries which are manufactured at present. Lithium-vanadium oxide batteries are being researched and developed. Furthermore, electrolytes, electrolyte additives and lithium surface treatments are being studied to improve safety and recharge-ability. 

One of the most important factors determining whether or not secondary lithium metal batteries become commercially viable is battery safety, which is affected many factors insufficient information is available about safety of practical secondary lithium metal batteries [91]. Vanadium compounds dissolve electrochemi-cally and are deposited on the lithium anode during charge-discharge cycle. The... 

Films on lithium play an important part in secondary lithium metal batteries. Electrolytes, electrolyte additives, and lithium surface treatments modify the lithium surface and change the morphology of the lithium and its current efficiency [93],... 

Various cyclic ethers are reported to be superior solvents for secondary lithium metal batteries. 1,3-Dioxolane [94, 95] and... 

The beneficial effect of fluoroborates lies in the efficiency at higher current densities which is better than that of sulfate electrolytes. The preparation of the appropriate metal salts starts with the dissolution of metal oxides, -hydroxides or -carbonates in fluoboric acid. The quantities vary with bath type and metal used, between 100-400 g/1 of fluoroborates depending on the application [55]. KBF4 has been also used as a conducting salt in nonaqueous electrolytes for secondary lithium-ion batteries [56]. 

The addition of some metal ions, such as Mg2+,Zn2+, In3+,orGa3+, and some organic additives, such as 2-thiophene, 2-methylfuran, or benzene, to propylene carbonate-LiC104 improved the coulombic efficiency for lithium cycling [112]. Lithium deposition on a lithium surface covered with a chemically stable, thin and tight layer which was formed by the addition of HF to electrolyte can suppress the lithium dendrite formation in secondary lithium batteries [113]. 

Because of the importance of high-performance secondary batteries, the techniques of the secondary lithium batteries are still making rapid progresses. Lithium polymer secondary batteries, having gel-polymer electrolytes, are advantageous in that the rigid metal container is not essential. Thus, all-plastic thin lithium secondary batteries are now available. 

Initial development of ambient secondary lithium batteries was based on the primary lithium systems described in Chapter 4, consisting of a lithium metal negative, a non-aqueous lithium ion conducting electrolyte and a positive electrode material which could undergo a reversible electrochemical reaction with lithium ions ... 

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