Stabilizing Low-Coordinated O Ions To Operate Cationic and Anionic Redox Chemistry of Li-Ion Battery Materials

doi:10.1021/acsami.9b13463

	Stabilizing Low-Coordinated O Ions To Operate Cationic and Anionic Redox Chemistry of Li-Ion Battery Materials
	Qiu, Wujie; Li, Zuosheng; Chen, Keyi; Li, Chilin; Liu, Jianjun; Zhang, Wenqing
刊名	ACS APPLIED MATERIALS & INTERFACES
	2019-10-16
卷号	11 期号:41 页码:37768
关键词	Li+-ion battery DFT proton-coupled charge transfer cationic and anionic electrochemistry high-capacity electrode material
ISSN号	1944-8244
DOI	10.1021/acsami.9b13463
文献子类	Article
英文摘要	Conventional electrochemical processes are mainly operated by cationic redox chemistry. Developing cumulative cationic and anionic redox chemistry offers a transformative approach to increase the energy storage capacity of Li-ion batteries and active sites of catalysts. However, realizing the reversible anionic redox reaction to increase the specific capacity in Li-ion battery materials is a large challenge because uncontrollable anion-anion combination and gas evolutions cause poor cyclic performance. Here, we use open-framework metal-fluorides (FeF3 center dot 0.33H(2)O) to demonstrate cumulative cationic and anionic redox reactions to be realized through O substitution. Experimental studies verified that O substitution could form reductive O ions, and stabilizing this reductive low-coordinated O by p-d orbital hybridization and hydrogen-transfer-mediated O-H bond formation plays an important role in operating anionic electrochemistry. O substitution also exhibits an improved cyclic performance beyond the insertion-reaction capacity (150 mA h/g) of FeF3 center dot 0.33H(2)O (225 and 300 mA h/g). Theoretical calculations show that FeF2.67O0.33 center dot 0.33H(2)O exhibits a 50% higher insertion-reaction capacity (225 mA h/g) than FeF3 center dot 0.33H(2)O (150 mA h/g) before structural collapse, which is attributed to cumulative cationic (Fe3+ <-> Fe2+) and anionic (O- <-> O2-) redox reactions based on our electronic structure analysis. The present study opens a new avenue to develop cationic and anionic electrochemistry to improve the storage capacity and cyclic performance through stabilizing low-coordinated O ions.
WOS研究方向	Science & Technology - Other Topics ; Materials Science
语种	英语
出版者	AMER CHEMICAL SOC
内容类型	期刊论文
源URL	[http://ir.sic.ac.cn/handle/331005/26772]
专题	中国科学院上海硅酸盐研究所
推荐引用方式 GB/T 7714	Qiu, Wujie,Li, Zuosheng,Chen, Keyi,et al. Stabilizing Low-Coordinated O Ions To Operate Cationic and Anionic Redox Chemistry of Li-Ion Battery Materials[J]. ACS APPLIED MATERIALS & INTERFACES,2019,11(41):37768.
APA	Qiu, Wujie,Li, Zuosheng,Chen, Keyi,Li, Chilin,Liu, Jianjun,&Zhang, Wenqing.(2019).Stabilizing Low-Coordinated O Ions To Operate Cationic and Anionic Redox Chemistry of Li-Ion Battery Materials.ACS APPLIED MATERIALS & INTERFACES,11(41),37768.
MLA	Qiu, Wujie,et al."Stabilizing Low-Coordinated O Ions To Operate Cationic and Anionic Redox Chemistry of Li-Ion Battery Materials".ACS APPLIED MATERIALS & INTERFACES 11.41(2019):37768.