Combination of first-principles molecular dynamics and XANES simulations for LiCoO2-electrolyte interfacial reactions in a lithium-ion battery

作     者：Tomoyuki Tamura Masanori Kohyama Shuji Ogata 

作者机构：Department of Physical Science and Engineering Nagoya Institute of Technology Nagoya 466-8555 Japan Center for Materials Research by Information Integration Research and Services Division of Materials Data and Integrated System National Institute for Materials Science Tsukuba 305-0047 Japan Research Institute of Electrochemical Energy Department of Energy and Environment National Institute of Advanced Industrial Science and Technology Ikeda 563-8577 Japan 

出 版 物：《Physical Review B》 (Phys. Rev. B)

年 卷 期：2017年第96卷第3期

页      面：035107-035107页

核心收录：

学科分类：0809[工学-电子科学与技术（可授工学、理学学位）] 07[理学] 070205[理学-凝聚态物理] 08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0702[理学-物理学] 

基　　金：Funds for the Development of Human Resources in Science and Technology from Japan Science and Technology Agency (JST) MEXT Kakenhi [25820355, 26249092] Grants-in-Aid for Scientific Research Funding Source: KAKEN 

主　　题：X ray absorption near edge spectroscopy 

摘      要：We performed a first-principles molecular dynamics (FPMD) simulation of the interfacial reactions between a LiCoO2 electrode and a liquid ethylene carbonate (EC) electrolyte. For configurations during the FPMD simulation, we also performed first-principles Co K-edge x-ray absorption near-edge structure (XANES) simulations, which can properly reproduce the bulk and surface spectra of LiCoO2. We observed strong absorption of an EC molecule on the LiCoO2 {110} surface, involving ring opening of the molecule, bond formation between oxygen atoms in the molecule and surface Co ions, and emission of one surface Li ion, while all the surface Co ions remain Co3+. The surface Co ions having the bond with an oxygen atom in the molecule showed remarkable changes in simulated K-edge spectra which are similar to those of the in situ observation under electrolyte soaking [D. Takamatsu et al., Angew. Chem., Int. Ed. 51, 11597 (2012)]. Thus, the local environmental changes of surface Co ions due to the reactions with an EC molecule can explain the experimental spectrum changes.