期刊
CHEMISTRY OF MATERIALS
卷 29, 期 6, 页码 2550-2562出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.6b04429
关键词
-
资金
- U.S. Deparment of Energy's National Nuclear Security Administration [DE-AC04-94AL85000]
- Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DESC0001160]
Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel LixMn2O4 (001) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on graphite anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is far from sufficient. Key steps that facilitate Mn(II) loss include concerted liquid/solid-state motions; proton-induced weakening of Mn-O bonds forming mobile OH- surface groups; and chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li2CO3 and organic lithium ethylene dicarbonate (LEDC) anode SEI components facilitate electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据