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Double the Capacity of Manganese Spinel for Lithium‐Ion Storage by Suppression of Cooperative Jahn–Teller Distortion
Author(s) -
Zuo Changjian,
Hu Zongxiang,
Qi Rui,
Liu Jiajie,
Li Zhibo,
Lu Junliang,
Dong Cheng,
Yang Kai,
Huang Weiyuan,
Chen Cong,
Song Zhibo,
Song Sicheng,
Yu Yaoming,
Zheng Jiaxin,
Pan Feng
Publication year - 2020
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.202000363
Subject(s) - jahn–teller effect , spinel , octahedron , materials science , lithium (medication) , distortion (music) , ion , manganese , intercalation (chemistry) , cationic polymerization , capacity loss , chemical physics , crystallography , nanotechnology , condensed matter physics , inorganic chemistry , electrochemistry , chemistry , physics , quantum mechanics , electrode , optoelectronics , medicine , amplifier , cmos , metallurgy , endocrinology , polymer chemistry
Abstract The relatively low capacity and capacity fade of spinel LiMn 2 O 4 (LMO) limit its application as a cathode material for lithium‐ion batteries. Extending the potential window of LMO below 3 V to access double capacity would be fantastic but hard to be realized, as it will lead to fast capacity loss due to the serious Jahn–Teller distortion. Here using experiments combined with extensive ab initio calculations, it is proved that there is a cooperative effect among individual Jahn–Teller distortions of Mn 3+ O 6 octahedrons in LMO, named as cooperative Jahn–Teller distortion (CJTD) in the text, which is the difficulty to access the capacity beyond one lithium intercalation. It is further proposed that the cationic disordering (excess Li at Mn sites and Li/Mn exchange) can intrinsically suppress the CJTD of Mn 3+ O 6 octahedrons. The cationic disordering can break the symmetry of Mn 3+ arrangements to disrupt the correlation of distortions arising from individual JT centers and prevent the Mn 3+ O bonds distorting along one direction. Interestingly, with the suppressed CJTD, the original octahedral vacancies in spinel LMO are activated and can serve as extra Li‐ion storage sites to access the double capacity with good reversible cycling stability in microsized LMO.