宽温域、高电压、安全无EC电解液研究进展

doi:10.19799/j.cnki.2095-4239.2023.0237

摘要/Abstract

摘要：

碳酸乙烯酯（EC）作为性能优良的有机溶剂，因其具备高的介电常数和对于石墨负极良好的兼容性，被广泛认为是可充电锂离子电池电解液的重要组成部分。然而，其自身熔点高、黏度大、电化学窗口窄等一系列问题，使得EC基电解液锂电池无法满足高温、高压、低温等多种苛刻条件下的应用需求。本文通过回顾近期相关文献，首先介绍了目前基于传统EC基电解液在极端应用条件下的失效机理，包括高压下EC与正极相变析出的氧气反应，电极与电解液界面劣化导致电解液持续消耗，高温下电解液分解产生易燃自由基，低温下锂沉积不均匀导致锂枝晶产生等一系列问题；其次，着重阐述了无EC电解液的最新研究动态，包括原位构筑稳定电极界面膜、调节溶剂化结构、调控反应路径、去除反应副产物等优化措施重新设计电解液成分，以达到通过设计改善电解液提高锂电池综合性能的目的；最后，概述了开发高性能无EC电解液当前存在的障碍和可能的发展机会。目的是为研发能够满足军工、航空等苛刻应用场景的锂离子电池提供一些方向指引和理论指导以推动新能源产业发展。

关键词: 锂电池, 无EC电解液, 高温, 高电压, 低温, 安全

Abstract:

Ethylene carbonate (EC), an organic solvent with excellent performance, is widely regarded as an important component of electrolytes used in rechargeable lithium-ion batteries because of its high dielectric constant and good compatibility with graphite anodes. However, various problems related to EC, such as high melting point, high viscosity, and narrow electrochemical window, hinder the operation of lithium-ion batteries using EC-based electrolytes under various harsh operating conditions such as high temperature, high voltage, and low temperature. This study reviews recent literature with respect to EC-based electrolytes. First, this study reports the failure mechanisms related to conventional EC-based electrolytes under extreme operating conditions, including the reaction between EC and oxygen precipitated owing to cathode phase change under high voltage, the continuous consumption of electrolyte owing to the deterioration of the electrode-electrolyte interface, the decomposition of electrolyte under high-temperature conditions resulting in the generation of flammable radicals, and the uneven deposition of lithium under low-temperature conditions resulting in lithium dendrites. Secondly, the latest developments in research related to EC-free electrolytes are highlighted herein. This research includes the in situ construction of stable-electrode interface films, regulation of solvation structures, modulation of reaction paths, removal of reaction byproducts, and other optimization measures to redesign the electrolyte composition to improve the overall performance of Li-ion batteries through the design of electrolytes. Finally, the existing obstacles and possible development opportunities with respect to high-performance EC-free electrolytes are outlined in this study. This study provides a directional and theoretical guidance for developing lithium-ion batteries that can function under harsh operating conditions to meet demands from military and aviation industries.

Key words: lithium battery, EC-free electrolytes, high temperature, high voltage, low temperature, safety

中图分类号:

TQ 152

刘志浩, 杜童, 李瑞瑞, 邓涛. 宽温域、高电压、安全无EC电解液研究进展[J]. 储能科学与技术, 2023, 12(8): 2504-2525.

Zhihao LIU, Tong DU, Ruirui LI, Tao DENG. Developments of wide temperature range， high voltage and safe EC-free electrolytes[J]. Energy Storage Science and Technology, 2023, 12(8): 2504-2525.

图/表 13

图1

图2

图3

图4

图5

图6

图7

图8

图9

表1

不同的无EC电解液配方和特性"

正极\|负极	电解液	性能	机理	参考文献
石墨/金属锂	3.2 mol/dm³ LiTFSA/DMSO 1∶2	抑制了溶剂插层效应，放电容量达300 mAh/g	调节溶剂化结构	[26]
NCM111\|石墨	1 mol/L LiPF₆ in MP∶VC (95∶5，质量比)	提高离子电导率和低温性能。在-14 ℃下，以5 C的放电倍率循环20次，仍可保持约220 MWh的容量	低黏度、低熔点溶剂形成SEI膜	[131]
NCM442\|石墨	1 mol/L LiPF₆ in EMC:FEC (95∶5，质量比)	在不同含量的添加剂中具有最佳的循环性能和最小的阻抗增长	找到能够有效钝化石墨负极的最佳添加剂的含量	[90]
NCM111\|石墨	1 mol/L LiFSI in ADN：DMC 1∶1	在20 ℃时达到5.8 ms/cm的电导率	使用线性溶剂来提高离子传导性	[88]
NCM442\|石墨	1 mol/L LiPF₆ in EMC+2% SA	改善60 ℃下的储存和循环性能，限制气体释放	CEI膜的形成抑制了界面上的副反应	[47]
LiCoO₂\|石墨	1.5 mol/dm³ LiFSI in SL	提高循环性能和高温稳定性	LiFSI和SL的热稳定性优于传统电解液	[68]
NMC442\|石墨	1 mol/L LiPF₆ in DEC/FEC (1∶1，质量比)	在500次循环后，与使用EC-DEC-FEC(45∶45∶10质量比)的电池相比，使用碳酸二乙酯(DEC)-FEC(1∶1质量比)的电池容量保持率增加了88%	调节反应途径以减少不利于锂迁移的聚烯烃的生成	[59]
NCM532\|石墨	1 mol/L LiPF₆ in EMC∶FEC (95∶5，质量比)	线性碳酸盐，如EMC和DMC比环状碳酸盐EC具有更高的氧化稳定性。	机理待解析	[130]
LiNi_0.94Co_0.06O₂\|石墨	1.0 mol/L LiFSI-0.5 mol/L LiPF₆/EMC+3% VC	抑制自产热，提高热稳定性	添加适当浓度的添加剂以提高导电性	[84]
LiCoO₂\|石墨	1.0 mol/L LiDFOB ADN/DMC (1∶1，质量比)+2% FEC	降低界面阻抗，提高负极稳定性	形成富含LiF的高氧化稳定性的SEI膜	[50]
LCO\|石墨	LiFSI/MA/FE(1∶1.5∶2，摩尔比)	在-50 ℃时可提供76%的室温容量	使用低熔点、低黏度的溶剂	[19]
NMA90\|石墨	1.5 mol/L LiPF₆ in EMC with FEC/TDI(20∶1，质量比)	具有高离子传导性、低界面阻抗和良好钝化能力的CEI膜	溶剂与添加剂协同工作	[92]
NCM532\|石墨	1.0 mol/L LiPF₆ in EMC with 1% LiDFP	电解液抑制过渡金属的溶解，改善高压电性能	降解的LiPF₆有效地捕获了溶解的过渡金属，并抑制了有害串扰的影响	[105]
NCM811\|石墨	0.6 mol/L LiBF₄ and 0.6 mol/L LiDFOB in DEC/FEC, 2∶1，体积比)	将电池热失控(TR)的触发温度提高31.1 ℃，热失控最高温度降低76.1 ℃	清除了易燃的EC成分，抑制了电解液分解等副反应	[22]
NMC811\|石墨	0.8 mol/L LiFSI-0.1 mol/L LiTFSI-0.6 mol/L LiPF₆ in EMC	在4.5 V的条件下，经过200次循环，保持大约82.1%的容量	形成稳定CEI膜，在高工作电位下有效稳定NMC811界面	[27]
NMC811\|石墨	1.0 mol/L LiPF₆ in PC/NMP/DMC (2∶1∶3，体积比)	提高PC和石墨负极的兼容性	将NMP溶剂分子引入Li⁺的溶解层，从而降低溶剂化结构中PC的浓度	[118]
NMC811\|石墨	1.0 mol/L LiPF₆-0.2 mol/L LiDFOB in FEC/ EMC/TFA (1∶3∶1，体积比)	在4.6 V电压下具有卓越的循环性(在200次循环中保持81.4%，0.5 C)和倍率性能(5 C时放电容量为154.5 mAh/g)	不同溶剂和锂盐的协同分解	[21]
NMC811\|石墨	1.0 mol/L LiPF₆-0.02 mol/L LiDFOB in FEC/HFE/FEMC (2∶2∶6，体积比)	与传统电解液相比，热失控的触发温度提高了12.5 ℃，热失控的最高温度降低了41.2 ℃	在正极表面形成了一个密集而均匀的含有F和B无机化合物的界面膜	[24]
NMC622\|石墨	1.0 mol/L LiPF₆ in PC/TFA (3∶7，体积比)+2% FEC	与传统电解液相比，这种电解液的热释放量减少到745.2 J/g，显示出良好的热稳定性	用含氟的电解液去除自由基	[66]
LNMO\|石墨	1.0 mol/L LiPF₆ in FEC/F-EMC/ F-EPE(3∶5∶2体积比)	在55 ℃下循环250次后，CE约为99.5%，容量保持率为50%	通过加入含氟电解液抑制电解液高温条件下分解	[50]
NMC442\|石墨	1.5 mol/L LiPF₆ in EMC +2% VC+1% TTSPi	有效地减缓气体的产生，减少容量衰减，降低阻抗，改善循环性能	寻找最佳的盐浓度	[65]
NMC811\|石墨	1.0 mol/L LiFSI /FEC∶TEP∶BTFE(10∶20∶70，体积比)	将热失控的触发温度提高47.3 ℃，将热失控的最高温度降低71.8 ℃	在电极和电解液界面之间形成无机界面膜	[101]
NMC811\|石墨	1.4 mol/L LiFSI in DMC/VC/TTE (2∶0.2∶3，摩尔比)	在60 ℃的条件下，容量仍然可以保持50次循环，而且减缓界面阻抗和溶液阻抗的增加	在正负电极上形成一层薄而稳定的无机界面膜	[74]
NMC811\|石墨	1 mol/L LiFSI in PC/FB (1∶5，摩尔比)	抑制了由PC和Li⁺共嵌入引起的石墨剥落，并实现了宽温度工作范围(-90～90 ℃)	FB削弱了Li⁺和PC之间的相互作用，并在负极表面形成了一层SEI保护膜	[117]
NMC811\|石墨	2 mol/L LiFSI:EMC:TTE (2∶3.3∶3.3，摩尔比)	在-40 ℃时保持78%的室温容量	削弱了溶剂分子和Li⁺之间的离子偶极作用	[120]
NMC811\|石墨	1 mol/L LiPF₆ in FEC/AN (7∶3，体积比)	使得811\|Gr体系电池可以在8 C条件下运行，容量保持率是使用EC基电解液的3倍	采用了一种溶剂辅助的跳跃机制来减少Li⁺的解溶障碍	[122]
Li₂CoPO₄F\|石墨	5.4 mol/L LiBF₄ in PC/FEC (1∶1，摩尔比)	在4.8 V电压下循环600次后容量保持率约为70%	利用高浓度的电解液调节溶剂结构	[78]

表1

图10

图11

图12

参考文献 134

1	TARASCON J M, ARMAND M. Issues and challenges facing rechargeable lithium batteries[M]//Materials for Sustainable Energy, Co-Published with Macmillan Publishers Ltd, UK, 2010: 171-179.
2	LU D B, LIN S X, HU S W, et al. Thermal behavior and failure mechanism of large format lithium-ion battery[J]. Journal of Solid State Electrochemistry, 2021, 25(1): 315-325.
3	CRABTREE G. Perspective: The energy-storage revolution[J]. Nature, 2015, 526(7575): doi: 10.1038/526S92a.
4	ZHOU K, XIE Q, LI B H, et al. An in-depth understanding of the effect of aluminum doping in high-nickel cathodes for lithium-ion batteries[J]. Energy Storage Materials, 2021, 34: 229-240.
5	LI W D, ERICKSON E M, MANTHIRAM A. High-nickel layered oxide cathodes for lithium-based automotive batteries[J]. Nature Energy, 2020, 5(1): 26-34.
6	FAN X L, WANG C S. High-voltage liquid electrolytes for Li batteries: Progress and perspectives[J]. Chemical Society Reviews, 2021, 50(18): 10486-10566.
7	詹元杰, 武怿达, 马晓威, 等. 基于碳酸酯基电解液的4.5 V电池[J]. 储能科学与技术, 2020, 9(2): 319-330.
	ZHAN Y J, WU Y D, MA X W, et al. 4.5 V Li-ion battery with a carbonate ester-based electrolyte[J]. Energy Storage Science and Technology, 2020, 9(2): 319-330.
8	JIA H, XU W. Electrolytes for high-voltage lithium batteries[J]. Trends in Chemistry, 2022, 4(7): 627-642.
9	陈晓霞, 刘凯, 王保国. 高安全性锂电池电解液研究与应用[J]. 储能科学与技术, 2020, 9(2): 583-592.
	CHEN X X, LIU K, WANG B G. Research on high-safety electrolytes and their application in lithium-ion batteries[J]. Energy Storage Science and Technology, 2020, 9(2): 583-592.
10	FENG X N, ZHENG S Q, REN D S, et al. Investigating the thermal runaway mechanisms of lithium-ion batteries based on thermal analysis database[J]. Applied Energy, 2019, 246: 53-64.
11	FENG X N, OUYANG M G, LIU X, et al. Thermal runaway mechanism of lithium ion battery for electric vehicles: A review[J]. Energy Storage Materials, 2018, 10: 246-267.
12	LIN W, ZHU M Y, FAN Y, et al. Low temperature lithium-ion batteries electrolytes: Rational design, advancements, and future perspectives[J]. Journal of Alloys and Compounds, 2022, 905: doi: 10.1016/j.jallcom.2022.164163.
13	FAN J A, TAN S. Studies on charging lithium-ion cells at low temperatures[J]. Journal of the Electrochemical Society, 2006, 153(6): doi: 10.1149/1.2190029.
14	GUPTA A, MANTHIRAM A. Designing advanced lithium-based batteries for low-temperature conditions[J]. Advanced Energy Materials, 2020, 10(38): doi: 10.1002/aenm.202001972.
15	ZHANG N, DENG T, ZHANG S Q, et al. Critical review on low-temperature Li-ion/metal batteries[J]. Advanced Materials, 2022, 34(15): doi: 10.1002/adma.202107899.
16	FONG R, VON SACKEN U, DAHN J R. Studies of lithium intercalation into carbons using nonaqueous electrochemical cells[J]. Journal of the Electrochemical Society, 1990, 137(7): 2009-2013.
17	PELED E. The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems-The solid electrolyte interphase model[J]. Journal of the Electrochemical Society, 1979, 126(12): 2047-2051.
18	PELED E, MENKIN S. Review—SEI: Past, present and future[J]. Journal of the Electrochemical Society, 2017, 164(7): doi: 10.1149/2.1441707jes.
19	YAO Y X, YAO N, ZHOU X R, et al. Ethylene-carbonate-free electrolytes for rechargeable Li-ion pouch cells at sub-freezing temperatures[J]. Advanced Materials, 2022, 34(45): doi: 10.1002/adma.202206448.
20	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.
21	ZHAO Q, WU Y, YANG Z W, et al. A fluorinated electrolyte stabilizing high-voltage graphite/NCM811 batteries with an inorganic-rich electrode-electrolyte interface[J]. Chemical Engineering Journal, 2022, 440: doi: 10.1016/j.cej.2022.135939.
22	WU C J, WU Y, XU X D, et al. Synergistic dual-salt electrolyte for safe and high-voltage LiNi_0.8Co_0.1Mn_0.1O₂//graphite pouch cells[J]. ACS Applied Materials & Interfaces, 2022, 14(8): 10467-10477.
23	AURBACH D, EIN-ELI Y, MARKOVSKY B, et al. The study of electrolyte solutions based on ethylene and diethyl carbonates for rechargeable Li batteries: II. graphite electrodes[J]. Journal of the Electrochemical Society, 1995, 142(9): 2882-2890.
24	SMART M C, RATNAKUMAR B V, SURAMPUDI S. Use of organic esters as cosolvents in electrolytes for lithium-ion batteries with improved low temperature performance[J]. Journal of the Electrochemical Society, 2002, 149(4): doi: 10.1149/1.1453407.
25	SMART M C, RATNAKUMAR B V, SURAMPUDI S. Electrolytes for low-temperature lithium batteries based on ternary mixtures of aliphatic carbonates[J]. Journal of the Electrochemical Society, 1999, 146(2): 486-492.
26	YAMADA Y, USUI K, CHIANG C H, et al. General observation of lithium intercalation into graphite in ethylene-carbonate-free superconcentrated electrolytes[J]. ACS Applied Materials & Interfaces, 2014, 6(14): 10892-10899.
27	WU Y, REN D S, LIU X A, et al. High-voltage and high-safety practical lithium batteries with ethylene carbonate-free electrolyte[J]. Advanced Energy Materials, 2021, 11(47): doi: 10.1002/aenm. 202102299.
28	WU C J, WU Y, YANG X Y, et al. Thermal runaway suppression of high-energy lithium-ion batteries by designing the stable interphase[J]. Journal of the Electrochemical Society, 2021, 168(9): doi: 10.1149/1945-7111/ac285f.
29	LOGAN E R, TONITA E M, GERING K L, et al. A study of the transport properties of ethylene carbonate-free Li electrolytes[J]. Journal of the Electrochemical Society, 2018, 165(3): A705-A716.
30	REN D S, FENG X N, LIU L S, et al. Investigating the relationship between internal short circuit and thermal runaway of lithium-ion batteries under thermal abuse condition[J]. Energy Storage Materials, 2021, 34: 563-573.
31	DENG K R, ZENG Q G, WANG D, et al. Nonflammable organic electrolytes for high-safety lithium-ion batteries[J]. Energy Storage Materials, 2020, 32: 425-447.
32	BALAKRISHNAN P G, RAMESH R, PREM KUMAR T. Safety mechanisms in lithium-ion batteries[J]. Journal of Power Sources, 2006, 155(2): 401-414.
33	HESS S, WOHLFAHRT-MEHRENS M, WACHTLER M. Flammability of Li-ion battery electrolytes: Flash point and self-extinguishing time measurements[J]. Journal of the Electrochemical Society, 2015, 162(2): A3084-A3097.
34	FENG X N, FANG M, HE X M, et al. Thermal runaway features of large format prismatic lithium ion battery using extended volume accelerating rate calorimetry[J]. Journal of Power Sources, 2014, 255: 294-301.
35	LIU X, REN D S, HSU H, et al. Thermal runaway of lithium-ion batteries without internal short circuit[J]. Joule, 2018, 2(10): 2047-2064.
36	SINHA N N, SMITH A J, BURNS J C, et al. The use of elevated temperature storage experiments to learn about parasitic reactions in wound LiCoO₂/Graphite cells[J]. Journal of the Electrochemical Society, 2011, 158(11): A1194.
37	LI Y, LIU X, WANG L, et al. Thermal runaway mechanism of lithium-ion battery with LiNi_0.8Mn_0.1Co_0.1O₂ cathode materials[J]. Nano Energy, 2021, 85: doi: 10.1016/j.nanoen.2021.105878.
38	SHARIFI-ASL S, SOTO F A, NIE A M, et al. Facet-dependent thermal instability in LiCoO₂[J]. Nano Letters, 2017, 17(4): 2165-2171.
39	WANG Y, FENG X N, PENG Y, et al. Reductive gas manipulation at early self-heating stage enables controllable battery thermal failure[J]. Joule, 2022, 6(12): 2810-2820.
40	KIM J, MA H, CHA H, et al. A highly stabilized nickel-rich cathode material by nanoscale epitaxy control for high-energy lithium-ion batteries[J]. Energy & Environmental Science, 2018, 11(6): 1449-1459.
41	OH P, OH S M, LI W D, et al. High-performance heterostructured cathodes for lithium-ion batteries with a Ni-rich layered oxide core and a Li-rich layered oxide shell[J]. Advanced Science, 2016, 3(11): doi: 10.1002/advs.201600184.
42	TEUFL T, PRITZL D, KRIEG P, et al. Operating EC-based electrolytes with Li- and Mn-rich NCMs: The role of O₂-release on the choice of the cyclic carbonate[J]. Journal of the Electrochemical Society, 2020, 167(11): doi: 10.1149/1945-7111/ab9e7f.
43	GALUSHKIN N Е, YAZVINSKAYA N N, GALUSHKIN D N. Mechanism of gases generation during lithium-ion batteries cycling[J]. Journal of the Electrochemical Society, 2019, 166(6): A897-A908.
44	BELHAROUAK I, KOENIG G M Jr, TAN T, et al. Performance degradation and gassing of Li₄Ti₅O₁₂/LiMn₂O₄ lithium-ion cells[J]. Journal of the Electrochemical Society, 2012, 159(8): A1165-A1170.
45	WU Y, LIU X, WANG L, et al. Development of cathode-electrolyte-interphase for safer lithium batteries[J]. Energy Storage Materials, 2021, 37: 77-86.
46	XIA J, GLAZIER S L, PETIBON R, et al. Improving linear alkyl carbonate electrolytes with electrolyte additives[J]. Journal of the Electrochemical Society, 2017, 164(6): A1239-A1250.
47	XIA J, LIU Q Q, HEBERT A, et al. Succinic anhydride as an enabler in ethylene carbonate-free linear alkyl carbonate electrolytes for high voltage Li-ion cells[J]. Journal of the Electrochemical Society, 2017, 164(6): A1268-A1273.
48	JIANG F N, CHENG X B, YANG S J, et al. Thermoresponsive electrolytes for safe lithium-metal batteries[J]. Advanced Materials, 2023, 35(12): doi: 10.1002/adma.202209114.
49	ZHANG J N, WU H, DU X F, et al. Smart deep eutectic electrolyte enabling thermally induced shutdown toward high-safety lithium metal batteries[J]. Advanced Energy Materials, 2023, 13(3): doi: 10.1002/aenm.202202529.
50	EHTESHAMI N, IBING L, STOLZ L, et al. Ethylene carbonate-free electrolytes for Li-ion battery: Study of the solid electrolyte interphases formed on graphite anodes[J]. Journal of Power Sources, 2020, 451: doi: 10.1016/j.jpowsour.2020.227804.
51	KRUEGER S, KLOEPSCH R, LI J, et al. How do reactions at the anode/electrolyte interface determine the cathode performance in lithium-ion batteries?[J]. Journal of the Electrochemical Society, 2013, 160(4): A542-A548.
52	VETTER J, NOVÁK P, WAGNER M R, et al. Ageing mechanisms in lithium-ion batteries[J]. Journal of Power Sources, 2005, 147(1/2): 269-281.
53	ZHENG Y J, SHI Z H, REN D S, et al. In-depth investigation of the exothermic reactions between lithiated graphite and electrolyte in lithium-ion battery[J]. Journal of Energy Chemistry, 2022, 69: 593-600.
54	NAGASUBRAMANIAN G, FENTON K. Reducing Li-ion safety hazards through use of non-flammable solvents and recent work at Sandia National Laboratories[J]. Electrochimica Acta, 2013, 101: 3-10.
55	CHEN S Y, WANG Z X, ZHAO H L, et al. A novel flame retardant and film-forming electrolyte additive for lithium ion batteries[J]. Journal of Power Sources, 2009, 187(1): 229-232.
56	MCMILLAN R, SLEGR H, SHU Z X, et al. Fluoroethylene carbonate electrolyte and its use in lithium ion batteries with graphite anodes[J]. Journal of Power Sources, 1999, 81: 20-26.
57	CHAWLA N, BHARTI N, SINGH S. Recent advances in non-flammable electrolytes for safer lithium-ion batteries[J]. Batteries, 2019, 5(1): 19.
58	ZOU Y G, MA Z, LIU G, et al. Non-flammable electrolyte enables high-voltage and wide-temperature lithium-ion batteries with fast charging[J]. Angewandte Chemie, 2023, 135(8): doi: 10.1002/anie.202216189.
59	YAO K, ZHENG J P, LIANG R. Ethylene carbonate-free fluoroethylene car bonate-based electrolyte works better for freestanding Si-based composite paper anodes for Li-ion batteries[J]. Journal of Power Sources, 2018, 381: 164-170.
60	XU K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J]. Chemical Reviews, 2004, 104(10): 4303-4417.
61	XU K. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chemical Reviews, 2014, 114(23): 11503-11618.
62	ZHANG S S. A review on electrolyte additives for lithium-ion batteries[J]. Journal of Power Sources, 2006, 162(2): 1379-1394.
63	CAMPION C L, LI W T, LUCHT B L. Thermal decomposition of LiPF₆-based electrolytes for lithium-ion batteries[J]. Journal of the Electrochemical Society, 2005, 152(12): A2327.
64	YANG H, ZHUANG G V, ROSS P N. Thermal stability of LiPF₆ salt and Li-ion battery electrolytes containing LiPF₆[J]. Journal of Power Sources, 2006, 161(1): 573-579.
65	XIONG D J, HYNES T, DAHN J R. Dramatic effects of low salt concentrations on Li-ion cells containing EC-free electrolytes[J]. Journal of the Electrochemical Society, 2017, 164(9): A2089-A2100.
66	AN K, TRAN Y H T, KWAK S, et al. Design of fire-resistant liquid electrolyte formulation for safe and long-cycled lithium-ion batteries[J]. Advanced Functional Materials, 2021, 31(48): doi: 10.1002/adfm.202106102.
67	REN X D, GAO P Y, ZOU L F, et al. Role of inner solvation sheath within salt-solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries[J]. Proceedings of the National Academy of Sciences of the United States of America, 2020, 117(46): 28603-28613.
68	HIRATA K, MORITA Y, KAWASE T, et al. Electrochemical performance of an ethylene carbonate-free electrolyte based on lithium bis (fluorosulfonyl) imide and sulfolane[J]. Journal of Power Sources, 2018, 395: 163-170.
69	SUN X G, ANGELL C A. New sulfone electrolytes for rechargeable lithium batteries. part I. oligoether-containing sulfones[J]. Electrochemistry Communications, 2005, 7(3): 261-266.
70	李放放, 陈仕谋. 高压锂离子电池电解液添加剂研究进展[J]. 储能科学与技术, 2016, 5(4): 436-442.
	LI F F, CHEN S M. Research progress on electrolyte additives for high voltage lithium-ion batteries[J]. Energy Storage Science and Technology, 2016, 5(4): 436-442.
71	YANG L, RAVDEL B, LUCHT B L. Electrolyte reactions with the surface of high voltage LiNi_0.5Mn_1.5O₄ cathodes for lithium-ion batteries[J]. Electrochemical and Solid-State Letters, 2010, 13(8): A95.
72	GUO K L, QI S H, WANG H P, et al. High-voltage electrolyte chemistry for lithium batteries[J]. Small Science, 2022, 2(5): doi: 10.1002/smsc.202100107.
73	LASZCZYNSKI N, SOLCHENBACH S, GASTEIGER H A, et al. Understanding electrolyte decomposition of graphite/NCM811 cells at elevated operating voltage[J]. Journal of the Electrochemical Society, 2019, 166(10): A1853-A1859.
74	ZHANG X H, ZOU L F, XU Y B, et al. Electrolytes: Advanced electrolytes for fast-charging high-voltage lithium-ion batteries in wide-temperature range (adv. energy mater. 22/2020)[J]. Advanced Energy Materials, 2020, 10(22): doi: 10.1002/aenm. 202070098.
75	KUNDURACI M, AMATUCCI G G. Synthesis and characterization of nanostructured 4.7 V LixMn_1.5Ni_0.5O₄ spinels for high-power lithium-ion batteries[J]. Journal of the Electrochemical Society, 2006, 153(7): A1345.
76	CHOI N S, HAN J G, HA S Y, et al. Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries[J]. RSC Advances, 2015, 5(4): 2732-2748.
77	LI W D, DOLOCAN A, OH P, et al. Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries[J]. Nature Communications, 2017, 8(1): 1-10.
78	PIECZONKA N P W, LIU Z Y, LU P, et al. Understanding transition-metal dissolution behavior in LiNi_0.5Mn_1.5O₄ high-voltage spinel for lithium ion batteries[J]. The Journal of Physical Chemistry C, 2013, 117(31): 15947-15957.
79	EDSTRÖM K, GUSTAFSSON T, THOMAS J O. The cathode-electrolyte interface in the Li-ion battery[J]. Electrochimica Acta, 2004, 50(2/3): 397-403.
80	MARKEVICH E, SHARABI R, GOTTLIEB H, et al. Reasons for capacity fading of LiCoPO₄ cathodes in LiPF₆ containing electrolyte solutions[J]. Electrochemistry Communications, 2012, 15(1): 22-25.
81	SLOOP S E, KERR J B, KINOSHITA K. The role of Li-ion battery electrolyte reactivity in performance decline and self-discharge[J]. Journal of Power Sources, 2003, 119: 330-337.
82	MANTHIRAM A. A reflection on lithium-ion battery cathode chemistry[J]. Nature Communications, 2020, 11: 1550.
83	XIA L, TANG B C, YAO L B, et al. Oxidation decomposition mechanism of fluoroethylene carbonate-based electrolytes for high-voltage lithium ion batteries: A DFT calculation and experimental study[J]. ChemistrySelect, 2017, 2(24): 7353-7361.
84	LI W D, DOLOCAN A, LI J Y, et al. Ethylene carbonate-free electrolytes for high-nickel layered oxide cathodes in lithium-ion batteries[J]. Advanced Energy Materials, 2019, 9(29): doi: 10.1002/aenm.201901152.
85	ZHANG T, PAILLARD E. Recent advances toward high voltage, EC-free electrolytes for graphite-based Li-ion battery[J]. Frontiers of Chemical Science and Engineering, 2018, 12(3): 577-591.
86	贠娇娇, 刘红梅, 郑会元, 等. 无机添加剂用于锂离子电池电解液的研究进展[J]. 储能科学与技术, 2014, 3(6): 584-589.
	YUN J J, LIU H M, ZHENG H Y, et al. Research progress on inorganic additives for lithium-ion battery electrolytes[J]. Energy Storage Science and Technology, 2014, 3(6): 584-589.
87	XIA J, PETIBON R, XIONG D J, et al. Enabling linear alkyl carbonate electrolytes for high voltage Li-ion cells[J]. Journal of Power Sources, 2016, 328: 124-135.
88	EHTESHAMI N, PAILLARD E. Ethylene carbonate-free, adiponitrile-based electrolytes compatible with graphite anodes[J]. ECS Transactions, 2017, 77(1): 11-20.
89	DOSE W M, LI W Q, TEMPRANO I, et al. Onset potential for electrolyte oxidation and Ni-rich cathode degradation in lithium-ion batteries[J]. ACS Energy Letters, 2022, 7(10): 3524-3530.
90	MA L, GLAZIER S L, PETIBON R, et al. A guide to ethylene carbonate-free electrolyte making for Li-ion cells[J]. Journal of the Electrochemical Society, 2016, 164(1): A5008-A5018.
91	LEE Y, LEE T K, KIM S, et al. Fluorine-incorporated interface enhances cycling stability of lithium metal batteries with Ni-rich NCM cathodes[J]. Nano Energy, 2020, 67: doi: 10.1016/j.nanoen.2019.104309.
92	ZENG G F, AN Y L, XIONG S L, et al. Nonflammable fluorinated carbonate electrolyte with high salt-to-solvent ratios enables stable silicon-based anode for next-generation lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2019, 11(26): 23229-23235.
93	FAN X L, JI X, CHEN L, et al. All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents[J]. Nature Energy, 2019, 4(10): 882-890.
94	CHOUDHURY S. Lithium fluoride additives for stable cycling of lithium batteries at high current densities[M]// Rational design of nanostructured polymer electrolytes and solid-liquid interphases for lithium batteries. Cham: Springer, 2019: 81-94.
95	JIA H P, ZOU L F, GAO P Y, et al. High-performance silicon anodes enabled by nonflammable localized high-concentration electrolytes[J]. Advanced Energy Materials, 2019, 9(31): doi: 10.1002/aenm.201900784.
96	CHEN S R, ZHENG J M, MEI D H, et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes[J]. Advanced Materials, 2018, 30(21): doi: 10.1002/adma.201706102.
97	SU C C, HE M N, REDFERN P C, et al. Oxidatively stable fluorinated sulfone electrolytes for high voltage high energy lithium-ion batteries[J]. Energy & Environmental Science, 2017, 10(4): 900-904.
98	CAO X A, JIA H, XU W, et al. Review—Localized high-concentration electrolytes for lithium batteries[J]. Journal of the Electrochemical Society, 2021, 168(1): doi: 10.1149/1945-7111/abd60e.
99	JIA H, XU Y B, BURTON S D, et al. Enabling ether-based electrolytes for long cycle life of lithium-ion batteries at high charge voltage[J]. ACS Applied Materials & Interfaces, 2020, 12(49): 54893-54903.
100	WU Z C, LI R H, ZHANG S Q, et al. Deciphering and modulating energetics of solvation structure enables aggressive high-voltage chemistry of Li metal batteries[J]. Chem, 2023, 9(3): 650-664.
101	WU Y, FENG X N, YANG M, et al. Thermal runaway of nonflammable localized high-concentration electrolytes for practical LiNi_0.8 Mn_0.1 Co_0.1 O₂ \|Graphite-SiO pouch cells[J]. Advanced Science, 2022, 9(32): doi: 10.1002/advs.202204059.
102	KO S, YAMADA Y, YAMADA A. A 4.8 V reversible Li₂CoPO₄F/graphite battery enabled by concentrated electrolytes and optimized cell design[J]. Batteries & Supercaps, 2020, 3(9): 910-916.
103	HAN J G, JEONG M Y, KIM K, et al. An electrolyte additive capable of scavenging HF and PF₅ enables fast charging of lithium-ion batteries in LiPF₆-based electrolytes[J]. Journal of Power Sources, 2020, 446: doi: 10.1016/j.jpowsour.2019.227366.
104	LU D, LEI X C, WENG S T, et al. A self-purifying electrolyte enables high energy Li ion batteries[J]. Energy & Environmental Science, 2022, 15(8): 3331-3342.
105	KLEIN S, VAN WICKEREN S, RÖSER S, et al. Understanding the outstanding high-voltage performance of NCM523\|\|Graphite lithium ion cells after elimination of ethylene carbonate solvent from conventional electrolyte[J]. Advanced Energy Materials, 2021, 11(14): doi: 10.1002/aenm.202003738.
106	KLEIN S, HARTE P, VAN WICKEREN S, et al. Re-evaluating common electrolyte additives for high-voltage lithium ion batteries[J]. Cell Reports Physical Science, 2021, 2(8): doi: 10.1016/j.xcrp.2021.100521.
107	KLEIN S, HARTE P, HENSCHEL J, et al. Graphite lithium-ion cells: On the beneficial impact of Li₂CO₃ as electrolyte additive in NCM523∥graphite lithium ion cells under high-voltage conditions (adv. energy mater. 10/2021)[J]. Advanced Energy Materials, 2021, 11(10): doi: 10.1002/aenm.202170039.
108	HAN J G, LEE J B, CHA A M, et al. Unsymmetrical fluorinated malonatoborate as an amphoteric additive for high-energy-density lithium-ion batteries[J]. Energy & Environmental Science, 2018, 11(6): 1552-1562.
109	VIDAL C, GROSS O, GU R, et al. xEV Li-ion battery low-temperature effects-Review[J]. IEEE Transactions on Vehicular Technology, 2019, 68(5): 4560-4572.
110	BI K, ZHAO S X, HUANG C, et al. Improving low-temperature performance of spinel LiNi_0.5Mn_1.5O₄ electrode and LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ full-cell by coating solid-state electrolyte Li-Al-Ti-P-O[J]. Journal of Power Sources, 2018, 389: 240-248.
111	RUI X H, JIN Y, FENG X Y, et al. A comparative study on the low-temperature performance of LiFePO₄/C and Li₃V₂(PO₄)₃/C cathodes for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(4): 2109-2114.
112	WANG K J. Study on low temperature performance of Li ion battery[J]. OALib, 2017, 4(11): 1-12.
113	SMART M C, RATNAKUMAR B V, CHIN K B, et al. Lithium-ion electrolytes containing ester cosolvents for improved low temperature performance[J]. Journal of the Electrochemical Society, 2010, 157(12): A1361.
114	SHI P, FANG S H, LUO D, et al. A safe electrolyte based on propylene carbonate and non-flammable hydrofluoroether for high-performance lithium ion batteries[J]. Journal of the Electrochemical Society, 2017, 164(9): A1991-A1999.
115	ZHANG S S, XU K, ALLEN J L, et al. Effect of propylene carbonate on the low temperature performance of Li-ion cells[J]. Journal of Power Sources, 2002, 110(1): 216-221.
116	HU Z L, WANG C, WANG C, et al. Uncovering the critical impact of the solid electrolyte interphase structure on the interfacial stability[J]. InfoMat, 2022, 4(3): doi: 10.1002/inf2.12249.
117	QIN M S, LIU M C, ZENG Z Q, et al. Rejuvenating propylene carbonate-based electrolyte through nonsolvating interactions for wide-temperature Li-ions batteries[J]. Advanced Energy Materials, 2022, 12(48): doi: 10.1002/aenm.202201801.
118	ZHANG Z X, YAO T F, WANG E K, et al. Unlocking the low-temperature potential of propylene carbonate to -30 ℃ via N-methylpyrrolidone[J]. ACS Applied Materials & Interfaces, 2022, 14(40): 45484-45493.
119	LIU X W, SHEN X H, LI H, et al. Ethylene carbonate-free propylene carbonate-based electrolytes with excellent electrochemical compatibility for Li-ion batteries through engineering electrolyte solvation structure[J]. Advanced Energy Materials, 2021, 11(19): doi: 10.1002/aenm.202003905.
120	NAN B, CHEN L, RODRIGO N D, et al. Enhancing Li⁺ transport in NMC811\|\|Graphite lithium-ion batteries at low temperatures by using low-polarity-solvent electrolytes[J]. Angewandte Chemie, 2022, 61(35): doi: 10.1002/anie. 202205967.
121	XU J, WANG X, YUAN N Y, et al. Graphite-based lithium ion battery with ultrafast charging and discharging and excellent low temperature performance[J]. Journal of Power Sources, 2019, 430: 74-79.
122	HUANG X T, LI R H, SUN C C, et al. Solvent-assisted hopping mechanism enables ultrafast charging of lithium-ion batteries[J]. ACS Energy Letters, 2022, 7(11): 3947-3957.
123	GHAUR A, PESCHEL C, DIENWIEBEL I, et al. Effective SEI formation via phosphazene-based electrolyte additives for stabilizing silicon-based lithium-ion batteries [J]. Advanced Energy Materials, 2023, 13(26): doi: 10.1002/aenm.202203503.
124	CAO Z, ZHENG X Y, ZHOU M, et al. Electrolyte solvation engineering toward high-rate and low-temperature silicon-based batteries[J]. ACS Energy Letters, 2022, 7(10): 3581-3592.
125	HUBBLE D, BROWN D E, ZHAO Y Z, et al. Liquid electrolyte development for low-temperature lithium-ion batteries[J]. Energy & Environmental Science, 2022, 15(2): 550-578.
126	FAN X L, CHEN L, BORODIN O, et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries[J]. Nature Nanotechnology, 2018, 13(8): 715-722.
127	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.
128	THENUWARA A C, SHETTY P P, KONDEKAR N, et al. Efficient low-temperature cycling of lithium metal anodes by tailoring the solid-electrolyte interphase[J]. ACS Energy Letters, 2020, 5(7): 2411-2420.
129	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.
130	XIONG D J, BAUER M, ELLIS L D, et al. Some physical properties of ethylene carbonate-free electrolytes[J]. Journal of the Electrochemical Society, 2018, 165(2): A126-A131.
131	PETIBON R, HARLOW J, LE D B, et al. The use of ethyl acetate and methyl propanoate in combination with vinylene carbonate as ethylene carbonate-free solvent blends for electrolytes in Li-ion batteries[J]. Electrochimica Acta, 2015, 154: 227-234.
132	GU Y X, FANG S H, YANG L, et al. A non-flammable electrolyte for long-life lithium ion batteries operating over a wide-temperature range[J]. Journal of Materials Chemistry A, 2021, 9(27): 15363-15372.
133	LAZAR M L, LUCHT B L. Carbonate free electrolyte for lithium ion batteries containing γ-butyrolactone and methyl butyrate[J]. Journal of the Electrochemical Society, 2015, 162(6): A928-A934.
134	PHAM H Q, LEE H Y, HWANG E H, et al. Non-flammable organic liquid electrolyte for high-safety and high-energy density Li-ion batteries[J]. Journal of Power Sources, 2018, 404: 13-19.

[1]	汪红辉, 刘一凡, 储德韧. 不同荷电状态钛酸锂电池高温日历老化研究[J]. 储能科学与技术, 2023, 12(8): 2606-2614.
[2]	黄永浩, 臧国景, 朱霨亚, 廖友好, 李伟善. LiF添加剂改善含锂陶瓷隔膜与4.35 V LiNi_0.8Co_0.1Mn_0.1O₂ 正极的界面稳定性[J]. 储能科学与技术, 2023, 12(8): 2361-2369.
[3]	杨佳兴, 张恒运, 徐屹东. 基于电化学-热耦合模型的锂离子电池组件产热分析[J]. 储能科学与技术, 2023, 12(8): 2615-2625.
[4]	刘欢, 彭娜, 高清雯, 李文鹏, 杨志荣, 王景涛. 冠醚掺杂的聚合物固态电解质对全固态锂电池性能的影响[J]. 储能科学与技术, 2023, 12(8): 2401-2411.
[5]	武明虎, 岳程鹏, 张凡, 李俊晓, 黄伟, 胡胜, 唐靓. 多尺度分解下GRU-MLR组合的锂电池剩余使用寿命预测方法[J]. 储能科学与技术, 2023, 12(7): 2220-2228.
[6]	李晋, 王青松, 孔得朋, 王晓冬, 俞振华, 乐艳飞, 黄鑫炎, 胡振恺, 吴候福, 方华斌, 曹伟, 张少禹, 卓萍, 陈晔, 李紫婷, 梅文昕, 张越, 赵丽香, 唐亮, 黄宗侯, 陈篪, 刘彦辉, 储玉喜, 许晓元, 张晋, 李贻恺, 冯蓉, 杨标, 户波, 杨晓滢. 锂离子电池储能安全评价研究进展[J]. 储能科学与技术, 2023, 12(7): 2282-2301.
[7]	王怡, 陈学兵, 王愿习, 郑杰允, 刘啸嵩, 李泓. 储能锂离子电池多层级失效机理及分析技术综述[J]. 储能科学与技术, 2023, 12(7): 2079-2094.
[8]	张贵萍, 闫筱炎, 王兵, 姚培新, 胡昌杰, 刘奕哲, 李纾黎, 薛建军. 长寿命循环的磷酸铁锂电池及材料、工艺[J]. 储能科学与技术, 2023, 12(7): 2134-2140.
[9]	马敬轩, 宋宇航, 石爽, 吕娜伟, 尹康涌, 王桂荣, 杜开源, 金阳. 基于气压信号突变探测的液冷型磷酸铁锂电池模组热失控预警研究[J]. 储能科学与技术, 2023, 12(7): 2246-2255.
[10]	乔荣涵, 朱璟, 申晓宇, 岑官骏, 郝峻丰, 季洪祥, 田孟羽, 金周, 詹元杰, 武怿达, 闫勇, 贲留斌, 俞海龙, 刘燕燕, 黄学杰. 锂电池百篇论文点评（2023.4.1—2023.5.31）[J]. 储能科学与技术, 2023, 12(7): 2333-2348.
[11]	刘宇龄, 孟锦豪, 彭乔, 刘天琪, 王扬, 蔡永翔. 基于NSGA-II遗传算法的锂电池均衡指标优化[J]. 储能科学与技术, 2023, 12(6): 1946-1956.
[12]	王海, 边煜华, 王佳东, 刘朝阳, 张杰, 姚健, 高宣雯, 刘朝孟, 骆文彬. 退役锂离子电池锂资源回收工艺[J]. 储能科学与技术, 2023, 12(5): 1453-1460.
[13]	胡川, 胡志伟, 李振东, 李帅, 王豪, 王丽平. 调控LiPF₆ 基电解液溶剂化结构稳定富锂锰基正极界面[J]. 储能科学与技术, 2023, 12(5): 1604-1615.
[14]	易永利, 于冉, 李武, 金翼, 戴哲仁. Mo， Al掺杂的Li₇La₃Zr₂O₁₂ 基复合固态电解质的制备及全固态电池性能研究[J]. 储能科学与技术, 2023, 12(5): 1490-1499.
[15]	刘家亮, 郭翠静, 汪奂伶. 基于火灾事故树模型的储能锂离子电池安全性检测方法与验证[J]. 储能科学与技术, 2023, 12(5): 1695-1704.