Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn2O4 Lithium-Ion Battery Cathodes

被引:38
|
作者
Warburton, Robert E. [1 ]
Young, Matthias J. [2 ,3 ,4 ]
Letourneau, Steven [2 ]
Elam, Jeffrey W. [2 ]
Greeley, Jeffrey [1 ]
机构
[1] Purdue Univ, Davidson Sch Chem Engn, W Lafayette, IN 47907 USA
[2] Argonne Natl Lab, Appl Mat Div, Lemont, IL 60439 USA
[3] Univ Missouri, Dept Chem Engn, Columbia, MO 65211 USA
[4] Univ Missouri, Dept Chem, Columbia, MO 65211 USA
关键词
DENSITY-FUNCTIONAL THEORY; DEGENERATE ELECTRONIC STATES; VOLTAGE CYCLING PERFORMANCE; TOTAL-ENERGY CALCULATIONS; POLYATOMIC-MOLECULES; POSITIVE ELECTRODE; SURFACE-CHEMISTRY; MANGANESE OXIDE; GRAPHITE ANODE; STABILITY;
D O I
10.1021/acs.chemmater.9b03809
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn2O4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al2O3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al2O3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH 3 -aluminum adducts and dissociated CH 3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn3+ content following TMA exposure and shifts in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH3* and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al2O3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.
引用
收藏
页码:1794 / 1806
页数:13
相关论文
共 50 条
  • [41] Conflicting Role of Inversion of the LiMn2O4 Spinel on Lithium-Ion Battery Capacity from First-Principles Calculations
    Wan, Zijing
    Xu, Yaxin
    Sun, Guoqing
    Xu, Dongwei
    Luo, Xiaobing
    JOURNAL OF PHYSICAL CHEMISTRY C, 2022, 126 (17): : 7374 - 7382
  • [42] Synthesis of an efficient LiMn2O4 for lithium-ion cells
    Pistoia, G
    Rosati, R
    JOURNAL OF POWER SOURCES, 1996, 58 (02) : 135 - 138
  • [43] Comparison of LiNi0.5Mn1.5O4 and LiMn2O4 for lithium-ion battery
    Liang, Xinghua
    Shi, Lin
    Liu, Yusi
    Liu, Tianjiao
    Ye, Chaochao
    Zeng, Shuaibo
    ENERGY DEVELOPMENT, PTS 1-4, 2014, 860-863 : 956 - +
  • [44] The electrochemical performance of sodium-ion-modified spinel LiMn2O4 used for lithium-ion batteries
    Xiong, Lilong
    Xu, Youlong
    Lei, Pei
    Tao, Tao
    Dong, Xin
    Song, Jie
    JOURNAL OF SOLID STATE ELECTROCHEMISTRY, 2014, 18 (03) : 713 - 719
  • [45] The electrochemical performance of sodium-ion-modified spinel LiMn2O4 used for lithium-ion batteries
    Lilong Xiong
    Youlong Xu
    Pei Lei
    Tao Tao
    Xin Dong
    Jie Song
    Journal of Solid State Electrochemistry, 2014, 18 : 713 - 719
  • [46] Preparation of LiMn2O4 lithium-ion battery cathode material by the multiple sinter method
    Zhao, M.S.
    Zhai, Y.C.
    Tian, Y.W.
    Guocheng Gongcheng Xuebao/The Chinese Journal of Process Engineering, 2001, 1 (04):
  • [47] Effect of heptamethyldisilazane as an additive on the stability performance of LiMn2O4 cathode for lithium-ion battery
    Li, Yongkun
    Zhang, Ruoxin
    Liu, Jiansheng
    Yang, Chunwei
    JOURNAL OF POWER SOURCES, 2009, 189 (01) : 685 - 688
  • [48] Anode performances of mixed LiMn2O4 and carbon black toward lithium-ion battery
    Chen, Kunfeng
    Xue, Dongfeng
    FUNCTIONAL MATERIALS LETTERS, 2014, 7 (02)
  • [49] Alkylphosphate-based nonflammable gel electrolyte for LiMn2O4 positive electrode in lithium-ion battery
    Yoshimoto, Nobuko
    Gotoh, Daisuke
    Egashira, Minato
    Morita, Masayuki
    JOURNAL OF POWER SOURCES, 2008, 185 (02) : 1425 - 1428
  • [50] A combustion method to prepare spinel phase LiMn2O4 cathode materials for lithium-ion batteries
    Yang, WS
    Zhang, G
    Xie, JY
    Yang, LL
    Liu, QG
    JOURNAL OF POWER SOURCES, 1999, 81 : 412 - 415