Lithium-desorption mechanism in LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4 according to precisely controlled acid treatment and density functional theory calculations

doi:10.1039/c9ta06080d

	Lithium-desorption mechanism in LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4 according to precisely controlled acid treatment and density functional theory calculations
	Gao, Aolei 1,2; Hou, Xinjuan 1,2; Sun, Zhenhua 1; Li, Shaopeng 1; Li, Huiquan 1,2; Zhang, Jianbo 1
刊名	JOURNAL OF MATERIALS CHEMISTRY A
	2019-09-28
卷号	7 期号:36 页码:20878-20890
ISSN号	2050-7488
DOI	10.1039/c9ta06080d
英文摘要	Spinel-type lithium manganese oxides (LMOs) are the most promising lithium-adsorption materials. LMOs can be in the form of solid solutions of LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4. However, uncertainty about the lithium-desorption mechanism restricts material development. The synthesis of intermediate products of spinel-type LMOs during acid treatment is important to investigate such a mechanism. In this work, precisely controlled acid treatment experiments were performed to successfully obtain the intermediate products of LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4. For LiMn2O4, lithium was desorbed with the dissolution of manganese. For Li1.33Mn1.67O4 and Li1.6Mn1.6O4, the lithium-desorption mechanism was an ion-exchange reaction, where lithium ions (Li+) in the 8a sites were prioritized for the ion-exchange reaction compared with Li+ in the 16d sites. Density functional theory (DFT) calculation results confirmed the experimental results and explained that the prioritization of Li+ in the 8a sites arose from its lower reaction-energy barrier, thereby revealing that Li+ preferred to move to the nearest vacant 8a sites when lithium was desorbed because of the lower diffusion-energy barrier. This work is the first to clarify the lithium-desorption mechanism through experiments and DFT calculations, and thus lays a foundation for the further exploitation of LMOs.
资助项目	National Nature Science Foundation of China[U1810205] ; National Nature Science Foundation of China[51804293] ; Shanxi Province Coal Based Low-carbon Technology Major Projects[MC2016-05] ; Chinese Academy of Sciences[ZDRW-ZS-2018-1]
WOS关键词	JAHN-TELLER-DISTORTION ; ION-EXCHANGE ; MANGANESE OXIDES ; LOCAL-STRUCTURE ; STRUCTURE REFINEMENT ; PROTON INSERTION ; LI+ INSERTION ; SPINEL ; EXTRACTION ; RECOVERY
WOS研究方向	Chemistry ; Energy & Fuels ; Materials Science
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000488618600044
资助机构	National Nature Science Foundation of China ; Shanxi Province Coal Based Low-carbon Technology Major Projects ; Chinese Academy of Sciences
内容类型	期刊论文
源URL	[http://ir.ipe.ac.cn/handle/122111/31251]
专题	中国科学院过程工程研究所
通讯作者	Hou, Xinjuan; Li, Shaopeng; Li, Huiquan
作者单位	1.Chinese Acad Sci, Inst Proc Engn, Natl Engn Lab Hydromet Cleaner Prod Technol, CAS Key Lab Green Proc & Engn, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100149, Peoples R China
推荐引用方式 GB/T 7714	Gao, Aolei,Hou, Xinjuan,Sun, Zhenhua,et al. Lithium-desorption mechanism in LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4 according to precisely controlled acid treatment and density functional theory calculations[J]. JOURNAL OF MATERIALS CHEMISTRY A,2019,7(36):20878-20890.
APA	Gao, Aolei,Hou, Xinjuan,Sun, Zhenhua,Li, Shaopeng,Li, Huiquan,&Zhang, Jianbo.(2019).Lithium-desorption mechanism in LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4 according to precisely controlled acid treatment and density functional theory calculations.JOURNAL OF MATERIALS CHEMISTRY A,7(36),20878-20890.
MLA	Gao, Aolei,et al."Lithium-desorption mechanism in LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4 according to precisely controlled acid treatment and density functional theory calculations".JOURNAL OF MATERIALS CHEMISTRY A 7.36(2019):20878-20890.