Elementary Decomposition Mechanisms of Lithium Hexafluorophosphate in Battery Electrolytes and Interphases

被引:73
作者
Spotte-Smith, Evan Walter Clark [1 ,2 ]
Petrocelli, Thea Bee [1 ,2 ,3 ]
Patel, Hetal D. [1 ,2 ]
Blau, Samuel M. [4 ]
Persson, Kristin A. [2 ,5 ]
机构
[1] Lawrence Berkeley Natl Lab, Mat Sci Div, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Mat Sci & Engn, Berkeley, CA 94720 USA
[3] Cabrillo Coll, Aptos, CA 95003 USA
[4] Lawrence Berkeley Natl Lab, Energy Storage & Distributed Resources, Berkeley, CA 94720 USA
[5] Lawrence Berkeley Natl Lab, Mol Foundry, Berkeley, CA 94720 USA
关键词
RECHARGEABLE LI BATTERIES; SOLID-ELECTROLYTE; ION-BATTERY; LIPF6-BASED ELECTROLYTES; ETHYLENE CARBONATE; THERMAL-DECOMPOSITION; DIETHYL CARBONATES; GRAPHITE; STABILITY; LIPF6;
D O I
10.1021/acsenergylett.2c02351
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
Electrolyte decomposition constitutes an outstanding challenge to long-life Li-ion batteries (LIBs) as well as emergent energy storage technologies, contributing to protection via solid electrolyte interphase (SEI) formation and irreversible capacity loss over a battery's life. Major strides have been made to understand the breakdown of common LIB solvents; however, salt decomposition mechanisms remain elusive. In this work, we use density functional theory to explain the decomposition of lithium hexafluorophosphate (LiPF6) salt under SEI formation conditions. Our results suggest that LiPF6 forms POF3 primarily through rapid chemical reactions with Li2CO3, while hydrolysis should be kinetically limited at moderate temperatures. We further identify selectivity in the proposed autocatalysis of POF3, finding that POF3 preferentially reacts with highly anionic oxygens. These results provide a means of interphase design in LIBs, indicating that LiPF6 reactivity may be controlled by varying the abundance or distribution of inorganic carbonate species or by limiting the transport of PF6- through the SEI.
引用
收藏
页码:347 / 355
页数:9
相关论文
共 64 条
  • [1] Lithium Ion Battery Anode Aging Mechanisms
    Agubra, Victor
    Fergus, Jeffrey
    [J]. MATERIALS, 2013, 6 (04) : 1310 - 1325
  • [2] The formation and stability of the solid electrolyte interface on the graphite anode
    Agubra, Victor A.
    Fergus, Jeffrey W.
    [J]. JOURNAL OF POWER SOURCES, 2014, 268 : 153 - 162
  • [3] The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling
    An, Seong Jin
    Li, Jianlin
    Daniel, Claus
    Mohanty, Debasish
    Nagpure, Shrikant
    Wood, David L., III
    [J]. CARBON, 2016, 105 : 52 - 76
  • [4] A comparative study of synthetic graphite and Li electrodes in electrolyte solutions based on ethylene carbonate dimethyl carbonate mixtures
    Aurbach, D
    Markovsky, B
    Shechter, A
    EinEli, Y
    Cohen, H
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (12) : 3809 - 3820
  • [5] Design of electrolyte solutions for Li and Li-ion batteries: a review
    Aurbach, D
    Talyosef, Y
    Markovsky, B
    Markevich, E
    Zinigrad, E
    Asraf, L
    Gnanaraj, JS
    Kim, HJ
    [J]. ELECTROCHIMICA ACTA, 2004, 50 (2-3) : 247 - 254
  • [6] THE STUDY OF ELECTROLYTE-SOLUTIONS BASED ON ETHYLENE AND DIETHYL CARBONATES FOR RECHARGEABLE LI BATTERIES .2. GRAPHITE-ELECTRODES
    AURBACH, D
    EINELI, Y
    MARKOVSKY, B
    ZABAN, A
    LUSKI, S
    CARMELI, Y
    YAMIN, H
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1995, 142 (09) : 2882 - 2890
  • [7] THE STUDY OF ELECTROLYTE-SOLUTIONS BASED ON ETHYLENE AND DIETHYL CARBONATES FOR RECHARGEABLE LI BATTERIES .1. LI METAL ANODES
    AURBACH, D
    ZABAN, A
    SCHECHTER, A
    EINELI, Y
    ZINIGRAD, E
    MARKOVSKY, B
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1995, 142 (09) : 2873 - 2882
  • [8] Barter D., 2022, CHEMRXIV, DOI 10.26434/chemrxiv-2021-c2gp3-v3
  • [9] Stability of Li2CO3 in cathode of lithium ion battery and its influence on electrochemical performance
    Bi, Yujing
    Wang, Tao
    Liu, Meng
    Du, Rui
    Yang, Wenchao
    Liu, Zixuan
    Peng, Zhe
    Liu, Yang
    Wang, Deyu
    Sun, Xueliang
    [J]. RSC ADVANCES, 2016, 6 (23) : 19233 - 19237
  • [10] A chemically consistent graph architecture for massive reaction networks applied to solid-electrolyte interphase formation
    Blau, Samuel M.
    Patel, Hetal D.
    Spotte-Smith, Evan Walter Clark
    Xie, Xiaowei
    Dwaraknath, Shyam
    Persson, Kristin A.
    [J]. CHEMICAL SCIENCE, 2021, 12 (13) : 4931 - 4939