Effect of Lithium Salt and Film-Forming Additives on the Low Temperature Electrochemical Performance of Lithium-Ion Batteries

doi:10.16553/j.cnki.issn1000-985x.2024.0195

Abstract

Abstract: A low-temperature electrolyte was constructed with LiPF₆ as the lithium salt, LiDFOB+LiBF₄+LiPO₂F₂ as the lithium salt additives, fluoroethylene carbonate (FEC)+ vinylene carbonate (VC)+tris(trimethylsilyl) phosphae (TMSP) as the film-forming additives, and ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethyl methyl carbonate (EMC) as the solvent, and was used to improve the low-temperature (-20 ℃) performance of NCM811 (LiNi_0.8Co_0.1Mn_0.1O₂) lithium-ion battery. The properties of low-temperature electrolytes were studied by various analytical techniques, and the effects of lithium salts and film-forming additives on the electrochemical properties of lithium-ion batteries were studied. The results show that the low-temperature electrolyte has good cycling stability and lithium deposition performance. Lithium-ion batteries assembled from low-temperature electrolytes have excellent low-temperature electrochemical properties. The first discharge specific capacity is 171.5 mAh/g at -20 ℃ and 0.1 C, and the capacity retention rate is 96.33% for 120 cycles at 1 C. The SEM and TEM results of the electrodes before and after cycling show that the low-temperature electrolyte form a uniform and dense CEI film on the surface of the positive electrode, due to the action of lithium salt and film-forming additives, which restrain the cracking of the positive electrode material and prevent the electrolyte decomposition, effectively improving the cycling stability of lithium-ion batteries at low temperatures.

Key words: lithium-ion battery, lithium salt additive, film-forming additive, low-temperature electrolyte, electrochemical property

CLC Number:

TM912

JIANG Xiaoxue, SONG Fei, HU Guangyu, XU Jinhua, LI Cuiqin. Effect of Lithium Salt and Film-Forming Additives on the Low Temperature Electrochemical Performance of Lithium-Ion Batteries[J]. Journal of Synthetic Crystals, 2025, 54(1): 146-157.

References

[1] WANG W, YANG Q, QIAN K, et al. Impact of evolution of cathode electrolyte interface of Li(Ni_0.8Co_0.1Mn_0.1)O₂ on electrochemical performance during high voltage cycling process[J]. Journal of Energy Chemistry, 2020, 47: 72-78.
[2] LIU B H, JIA Y K, YUAN C H, et al. Safety issues and mechanisms of lithium-ion battery cell upon mechanical abusive loading: a review[J]. Energy Storage Materials, 2020, 24: 85-112.
[3] ZHANG N, DENG T, ZHANG S Q, et al. Critical review on low-temperature Li-ion/metal batteries[J]. Advanced Materials, 2022, 34(15): 2107899.
[4] WANG B, TANG M, WU Y C, et al. A 2D layered natural ore as a novel solid-state electrolyte[J]. ACS Applied Energy Materials, 2019, 2(8): 5909-5916.
[5] TRON A, JEONG S, PARK Y D, et al. Aqueous lithium-ion battery of nano-LiFePO₄ with antifreezing agent of ethyleneglycol for low-temperature operation[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(17): 14531-14538.
[6] LI Q, LIU G, CHENG H R, et al. Low-temperature electrolyte design for lithium-ion batteries: prospect and challenges[J]. Chemistry-A European Journal, 2021, 27(64): 15842-15865.
[7] HAREGEWOIN A M, WOTANGO A S, HWANG B J. Electrolyte additives for lithium ion battery electrodes: progress and perspectives[J]. Energy & Environmental Science, 2016, 9(6): 1955-1988.
[8] CHEN L, WU H L, AI X P, et al. Toward wide-temperature electrolyte for lithium-ion batteries[J]. Battery Energy, 2022, 1(2): 20210006.
[9] QIAN Y X, HU S G, ZOU X S, et al. How electrolyte additives work in Li-ion batteries[J]. Energy Storage Materials, 2019, 20: 208-215.
[10] ZHANG Z Y, HU T S, SUN Q M, et al. The optimized LiBF₄ based electrolytes for TiO₂(B) anode in lithium ion batteries with an excellent low temperature performance[J]. Journal of Power Sources, 2020, 453: 227908.
[11] WOTANGO A S, SU W N, HAREGEWOIN A M, et al. Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance[J]. ACS Applied Materials & Interfaces, 2018, 10(30): 25252-25262.
[12] 赵伟, 赵阳雨, 李步成, 等. 新型锂盐二氟草酸硼酸锂的研究进展[J]. 化工新型材料, 2013, 41(4): 21-23.
ZHAO W, ZHAO Y Y, LI B C, et al. Research progress of a new lithium salt lithium oxalyldifluoroborate[J]. New Chemical Materials, 2013, 41(4): 21-23 (in Chinese).
[13] CHENG F Y, ZHANG X Y, WEI P, et al. Tailoring electrolyte enables high-voltage Ni-rich NCM cathode against aggressive cathode chemistries for Li-ion batteries[J]. Science Bulletin, 2022, 67(21): 2225-2234.
[14] LI L C, LV W X, CHEN J, et al. Lithium difluorophosphate (LiPO₂F₂): an electrolyte additive to help boost low-temperature behaviors for lithium-ion batteries[J]. ACS Applied Energy Materials, 2022, 5(9): 11900-11914.
[15] JIANG B, LI J R, LUO B, et al. LiPO₂F₂ electrolyte additive for high-performance Li-rich cathode material[J]. Journal of Energy Chemistry, 2021, 60: 564-571.
[16] BIAN X F, GE S X, PANG Q, et al. A novel lithium difluoro(oxalate) borate and lithium hexafluoride phosphate dual-salt electrolyte for Li-excess layered cathode material[J]. Journal of Alloys and Compounds, 2018, 736: 136-142.
[17] CHEN H X, LIU B, WANG Y, et al. Insight into wide temperature electrolyte based on lithiumdifluoro(oxalate)borate for high voltage lithium-ion batteries[J]. Journal of Alloys and Compounds, 2021, 876: 159966.
[18] CHE Y X, LIN X Y, XING L D, et al. Protective electrode/electrolyte interphases for high energy lithium-ion batteries with p-toluenesulfonyl fluoride electrolyte additive[J]. Journal of Energy Chemistry, 2021, 52: 361-371.
[19] GAUTHIER M, CARNEY T J, GRIMAUD A, et al. Electrode-electrolyte interface in Li-ion batteries: current understanding and new insights[J]. The Journal of Physical Chemistry Letters, 2015, 6(22): 4653-4672.
[20] SHEN C, WANG S W, JIN Y, et al. In situ AFM imaging of solid electrolyte interfaces on HOPG with ethylene carbonate and fluoroethylene carbonate-based electrolytes[J]. ACS Applied Materials & Interfaces, 2015, 7(45): 25441-25447.
[21] CRESCE A V, RUSSELL S M, BAKER D R, et al. In situ and quantitative characterization of solid electrolyte interphases[J]. Nano Letters, 2014, 14(3): 1405-1412.
[22] 吕晓伟. 添加剂TMSP,TMSB对三元正极材料电化学性能影响的研究[D]. 徐州: 中国矿业大学, 2018.
LYU X W. Effect of additives TMSP and TMSB on electrochemical properties of ternary cathode materials[D]. Xuzhou: China University of Mining and Technology, 2018 (in Chinese).
[23] 梁倩雯. 基于界面调控和电解液优化构筑高性能锂金属负极[D]. 广州: 华南理工大学, 2023.
LIANG Q W. Construction of high performance lithium metal anode based on interface regulation and electrolyte optimization[D]. Guangzhou: South China University of Technology, 2023 (in Chinese).
[24] JURNG S, BROWN Z L, KIM J, et al. Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes[J]. Energy & Environmental Science, 2018, 11(9): 2600-2608.
[25] LI Y K, CHENG B, JIAO F P, et al. The roles and working mechanism of salt-type additives on the performance of high-voltage lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(14): 16298-16307.