Structural Exfoliation of Layered Cathode under High Voltage and Its Suppression by Interface Film Derived from Electrolyte Additive.
Layered cathodes for lithium-ion battery, including LiCo1-x-yNixMnyO2and xLi2MnO3·(1-x)LiMO2(M = Mn, Ni, and Co), are attractive for large-scale applications such as electric vehicles, because they can deliver additional specific capacity when the end of charge voltage is improved to over 4.2 V. However, operation under a high voltage might cause capacity decaying of layered cathodes during cycling. The failure mechanisms that have been given, up to date, include the electrolyte oxidation decomposition, the Ni, Co, or Mn ion dissolution, and the phase transformation. In this work, we report a new mechanism involving the exfoliation of layered cathodes when the cathodes are performed with deep cycling under 4.5 V in the electrolyte consisting of carbonate solvents and LiPF6salt. Additionally, an electrolyte additive that can form a cathode interface film is applied to suppress this exfoliation. A representative layered cathode, LiCoO2, and an interface film-forming additive, dimethyl phenylphosphonite (DMPP), are selected to demonstrate the exfoliation and the protection of layered structure. When evaluated in half-cells, LiCoO2exhibits a capacity retention of 24% after 500 cycles in base electrolyte, but this value is improved to 73% in the DMPP-containing electrolyte. LiCoO2/graphite full cell using DMPP behaves better than the Li/LiCoO2half-cell, delivering an initial energy density of 700 Wh kg-1with an energy density retention of 82% after 100 cycles at 0.2 C between 3 and 4.5 V, as compared to 45% for the cell without using DMPP.
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.
Yunmin
Y
Zhu
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.
Xueyi
X
Luo
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.
Huozhen
H
Zhi
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.
Xuerui
X
Yang
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.|Engineering Research Center of MTEES (Ministry of Education), Research Center of BMET (Guangdong Province), Engineering Laboratory of OFMHEB (Guangdong Province), Key Laboratory of ETESPG (GHEI), and Innovative Platform for ITBMD (Guangzhou Municipality), South China Normal University , Guangzhou 510006, China.
Lidan
L
Xing
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.|Engineering Research Center of MTEES (Ministry of Education), Research Center of BMET (Guangdong Province), Engineering Laboratory of OFMHEB (Guangdong Province), Key Laboratory of ETESPG (GHEI), and Innovative Platform for ITBMD (Guangzhou Municipality), South China Normal University , Guangzhou 510006, China.
Youhao
Y
Liao
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.|Engineering Research Center of MTEES (Ministry of Education), Research Center of BMET (Guangdong Province), Engineering Laboratory of OFMHEB (Guangdong Province), Key Laboratory of ETESPG (GHEI), and Innovative Platform for ITBMD (Guangzhou Municipality), South China Normal University , Guangzhou 510006, China.
Mengqing
M
Xu
School of Chemistry and Environment, South China Normal University , Guangzhou 510631, China.|Engineering Research Center of MTEES (Ministry of Education), Research Center of BMET (Guangdong Province), Engineering Laboratory of OFMHEB (Guangdong Province), Key Laboratory of ETESPG (GHEI), and Innovative Platform for ITBMD (Guangzhou Municipality), South China Normal University , Guangzhou 510006, China.
Weishan
http://orcid.org/0000-0002-1495-4441
W
Li
anion insertion; electrolyte additive; exfoliation of layered structure; interface film; lithium cobalt oxide