Thin-film lithium and lithium-ion batteries
Thin-film lithium and lithium-ion batteries
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DOI：
10.1016/s0167-2738(00)00327-1
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发表时间：
2000-11-01
影响因子：
3.2
通讯作者：
Evans, CD
中科院分区：
文献类型：
--
作者：
Bates, JB;Dudney, NJ;Evans, CD
橡树岭国家实验室过去十年的研究促进了固态薄膜锂和锂离子电池的发展。这些电池厚度小于15微米，在各种消费和医疗产品中具有重要应用，并且它们是表征薄膜形式的锂嵌入化合物特性的有用研究工具。该电池的正极是晶体或纳米晶氧化物基锂嵌入化合物，如LiCoO2和LiMn2O4，负极是锂金属、无机化合物，如硅锡氮氧化物、Sn3N4和Zn3N2，或金属膜，如Cu，其中负极在初始充电时通过镀锂形成。电解质是玻璃态锂磷氮氧化物（“Lipon”）。具有晶体 LiCoO2 阴极的电池在 10 mA/cm(2) 的放电电流下，可在 4.2 至 3 V 之间提供高达最大容量的 30%，并且在更适中的放电-充电速率下，在数千个循环中，容量下降的量可以忽略不计。具有一般组成 Li1+xMn2-yO4 的晶体锂锰氧化物薄膜在初始充电时在 5 V 电压下表现出显着的容量，并且根据沉积过程，在 4.6 V 电压下也表现出显着的容量，这是锰缺乏-锂过量的结果。 5-V平台被认为是由于离子的Mn氧化至高于+4的价态并伴随着晶格的重排。具有沉积纳米晶 Li1+xMn2-yO4 阴极的电池的放电-充电曲线之间的差距是由于真正的滞后现象，而不是在高度结晶薄膜中观察到的动力学受阻松弛。通过观察锂离子嵌入和脱出中间阶段的充电和放电的经典扫描曲线，证实了这种行为。使用这些阴极的锂电池在 25 和 100 摄氏度下的延长循环会导致晶粒生长，并且充放电曲线会朝着结晶良好的薄膜的特征发展。 (C) 2000 年由 Elsevier Science B.V. 出版
Research over the last decade at Oak Ridge National Laboratory has led to the development of solid-state thin-film lithium and lithium-ion batteries. The batteries, which are less than 15 mum thick, have important applications in a variety of consumer and medical products, and they are useful research tools in characterizing the properties of lithium intercalation compounds in thin-film form. The batteries consist of cathodes that are crystalline or nanocrystalline oxide-based lithium intercalation compounds such as LiCoO2 and LiMn2O4, and anodes of lithium metal, inorganic compounds such as silicon-tin oxynitrides, Sn3N4 and Zn3N2, or metal films such as Cu in which the anode is formed by lithium plating on the initial charge. The electrolyte is a glassy lithium phosphorus oxynitride ('Lipon'). Cells with crystalline LiCoO2 cathodes can deliver up to 30% of their maximum capacity between 4.2 and 3 V at discharge currents of 10 mA/cm(2), and at more moderate discharge-charge rates, the capacity decreases by negligible amounts over thousands of cycles. Thin films of crystalline lithium manganese oxide with the general composition Li1+xMn2-yO4 exhibit on the initial charge significant capacity at 5 V and, depending on the deposition process, at 4.6 V as well, as a consequence of the manganese deficiency-lithium excess. The 5-V plateau is believed to be due to oxidation Mn of ions to valence states higher than + 4 accompanied by a rearrangement of the lattice. The gap between the discharge-charge curves of cells with as-deposited nanocrystalline Li1+xMn2-yO4 cathodes is due to a true hysteresis as opposed to a kinetically hindered relaxation observed with the highly crystalline films. This behavior was confirmed by observing classic scanning curves on charge and discharge at intermediate stages of insertion and extraction of Li- ions. Extended cycling of lithium cells with these cathodes at 25 and 100 degreesC leads to grain growth and evolution of the charge-discharge profiles toward those characteristic of well crystallized films. (C) 2000 Published by Elsevier Science B.V.