Double the Capacity of Manganese Spinel for Lithium‐Ion Storage by Suppression of Cooperative Jahn–Teller Distortion. Issue 34 (26th July 2020)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: Advanced energy materials. Volume 10:Issue 34(2020)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-07-26
• Subjects: batteries -- doping -- Jahn–Teller distortion -- lithium‐ion storage, spinel; Energy harvesting -- Materials -- Periodicals; Energy conversion -- Materials -- Periodicals; Energy storage -- Materials -- Periodicals; Photovoltaics -- Periodicals; Fuel cells -- Periodicals; Thermoelectric materials -- Periodicals; 621.31
• DOI: 10.1002/aenm.202000363
• Languages: English
• ISSNs: 1614-6832

Abstract

Abstract: The relatively low capacity and capacity fade of spinel LiMn2 O4 (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+ O6 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+ O6 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. Abstract : Using experiments and ab initio calculations, the capacity is doubled by suppressing the cooperative Jahn–Teller distortion (CJTD) in spinel LiMn2 O4 (LMO). It is further shown that the cationic disordering can intrinsically suppress CJTD because it 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.