抑制锂金属负极枝晶的电解液调控策略

doi:10.19799/j.cnki.2095-4239.2023.0892

摘要/Abstract

摘要：

锂金属负极因高理论比容量(3860 mAh/g)与低氧化还原电位(-3.04 V vs. SHE)等优势，吸引了高比能电池领域的广泛关注。然而，锂金属负极的实际应用仍面临着诸多难点与挑战，其中锂枝晶生长问题尤为突出。在众多解决策略中，电解液调控策略因工艺简便、系统兼容性强、成本低廉、效果显著等特性，被认为是抑制锂枝晶生长最具应用前景的策略之一。本文首先总结了几种锂枝晶生长模型，包括固体电解质界面扩散控制模型、表面形核生长扩散模型、电荷诱导模型和空间电荷模型等，着重讨论了电解液调控策略抑制枝晶生长的模型基础，结果说明了电极界面层(SEI)的物化性能决定了金属锂的沉积行为，而SEI层的组分、力学性能、脱溶剂化过程等受电解液组分影响。随后系统地归纳了电解液优化策略的研究进展，主要介绍了成膜添加剂、溶剂化调控SEI型添加剂、电荷诱导型添加剂、合金型添加剂、高浓盐电解液和局部高浓盐电解液等，对比了各种策略的优缺点。最后，对电解液优化策略进行了总结并对未来发展方向进行了展望。

关键词: 锂金属负极, 枝晶, 电解液优化, 生长模型, 添加剂

Abstract:

Lithium metal anodes have attracted extensive research attention because of their high theoretical capacity (3860 mAh/g) and low redox potential (-3.04 V vs. SHE). However, the current practical application of lithium metal anodes still faces various challenges, among which the problem of lithium dendrite growth is notable. Among several solution strategies, electrolyte optimization is a promising strategy for inhibiting lithium dendrite growth because of its simple preparation process, strong system compatibility, low cost, and remarkable effect. In this study, we summarize several lithium dendrite growth models, including the solid electrolyte interface diffusion model, surface nucleation growth diffusion model, charge induction model, and space charge model, focusing on the model basis for electrolyte regulation strategies to inhibit dendrite growth. As a result, the physical and chemical properties of the electrode interface layer (SEI) determine the deposition behavior of metallic lithium, and the SEI composition, mechanical properties, and desolvation process are affected by the electrolyte components. Next, the research progress on electrolyte optimization strategies is systematically reviewed, mainly considering film-forming additives, solvent-regulated SEI additives, charge-induced additives, alloy additives, high-concentration salt electrolytes, and local high-concentration salt electrolytes. The advantages and disadvantages of various optimization strategies are summarized. Finally, future research directions for electrolyte optimization strategies are suggested.

Key words: lithium metal anode, dendrite, electrolyte optimization, growth model, additive

中图分类号:

TQ 152

石敏, 蒋鹏杰, 徐琛, 贺鑫, 梁宵. 抑制锂金属负极枝晶的电解液调控策略[J]. 储能科学与技术, 2024, 13(5): 1620-1634.

Min SHI, Pengjie JIANG, Chen XU, Xin HE, Xiao LIANG. Advancements in electrolyte optimization strategies for inhibiting lithium dendrite growth[J]. Energy Storage Science and Technology, 2024, 13(5): 1620-1634.

图/表 9

图1

图2

图3

图4

图 5

图6

图7

图8

图9

参考文献 81

1	DUNN B, KAMATH H, TARASCON J M. Electrical energy storage for the grid: A battery of choices[J]. Science, 2011, 334(6058): 928-935.
2	JANEK J, ZEIER W G. A solid future for battery development[J]. Nature Energy, 2016, 1(9): 16141.
3	LIN D C, LIU Y Y, CUI Y. Reviving the lithium metal anode for high-energy batteries[J]. Nature Nanotechnology, 2017, 12(3): 194-206.
4	CHEN K H, WOOD K N, KAZYAK E, et al. Dead lithium: Mass transport effects on voltage, capacity, and failure of lithium metal anodes[J]. Journal of Materials Chemistry A, 2017, 5(23): 11671-11681.
5	HARRY K J, HALLINAN D T, PARKINSON D Y, et al. Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes[J]. Nature Materials, 2014, 13(1): 69-73.
6	GUO Y P, LI H Q, ZHAI T Y. Reviving lithium-metal anodes for next-generation high-energy batteries[J]. Advanced Materials, 2017, 29(29): 1700007.
7	ZHANG C F, LIU Y Y, JIAO X X, et al. In situ volume change studies of lithium metal electrode under different pressure[J]. Journal of the Electrochemical Society, 2019, 166(15): A3675-A3678.
8	XU W, WANG J L, DING F, et al. Lithium metal anodes for rechargeable batteries[J]. Energy & Environmental Science, 2014, 7(2): 513-537.
9	XIAO J, LI Q Y, BI Y J, et al. Understanding and applying coulombic efficiency in lithium metal batteries[J]. Nature Energy, 2020, 5: 561-568.
10	CHENG X B, ZHANG R, ZHAO C Z, et al. Toward safe lithium metal anode in rechargeable batteries: A review[J]. Chemical Reviews, 2017, 117(15): 10403-10473.
11	WANG A P, KADAM S, LI H, et al. Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries[J]. NPJ Computational Materials, 2018, 4: 15.
12	LEUNG K, LEENHEER A. How voltage drops are manifested by lithium ion configurations at interfaces and in thin films on battery electrodes[J]. The Journal of Physical Chemistry C, 2015, 119(19): 10234-10246.
13	LING C, BANERJEE D, MATSUI M. Study of the electrochemical deposition of Mg in the atomic level: Why it prefers the non-dendritic morphology[J]. Electrochimica Acta, 2012, 76: 270-274.
14	JÄCKLE M, GROß A. Microscopic properties of lithium, sodium, and magnesium battery anode materials related to possible dendrite growth[J]. The Journal of Chemical Physics, 2014, 141(17): 174710.
15	LIU F F, ZHANG Z W, YE S F, et al. Challenges and improvement strategies progress of lithium metal anode[J]. Acta Physico Chimica Sinica, 2021,37(1): 2006021.
16	DING F, XU W, CHEN X L, et al. Effects of cesium cations in lithium deposition via self-healing electrostatic shield mechanism[J]. The Journal of Physical Chemistry C, 2014, 118(8): 4043-4049.
17	CHAZALVIEL J. Electrochemical aspects of the generation of ramified metallic electrodeposits[J]. Physical Review A, Atomic, Molecular, and Optical Physics, 1990, 42(12): 7355-7367.
18	WANG H, YU Z, KONG X, et al. Liquid electrolyte: The nexus of practical lithium metal batteries[J]. Joule, 2022, 6(3): 588-616.
19	LU D P, SHAO Y Y, LOZANO T, et al. Failure mechanism for fast-charged lithium metal batteries with liquid electrolytes[J]. Advanced Energy Materials, 2015, 5(3): 1400993.
20	REN X D, ZHANG Y H, ENGELHARD M H, et al. Guided lithium metal deposition and improved lithium coulombic efficiency through synergistic effects of LiAsF₆ and cyclic carbonate additives[J]. ACS Energy Letters, 2018, 3(1): 14-19.
21	HIRANKUMAR G, MEHTA N. Effect of incorporation of different plasticizers on structural and ion transport properties of PVA-LiClO₄ based electrolytes[J]. Heliyon, 2018, 4(12): e00992.
22	XIE Y, XIANG H, SHI P, et al. Enhanced separator wettability by LiTFSI and its application for lithium metal batteries[J]. Journal of Membrane Science, 2017, 524: 315-320.
23	LU H, ZHU Y, YUAN Y, et al. LiFSI as a functional additive of the fluorinated electrolyte for rechargeable Li-S batteries[J]. Journal of Materials Science: Materials in Electronics, 2021, 32(5): 5898-5906.
24	MIAO R R, YANG J, FENG X J, et al. Novel dual-salts electrolyte solution for dendrite-free lithium-metal based rechargeable batteries with high cycle reversibility[J]. Journal of Power Sources, 2014, 271: 291-297.
25	LI F, LIU J D, HE J, et al. Additive-assisted hydrophobic Li⁺-solvated structure for stabilizing dual electrode electrolyte interphases through suppressing LiPF₆ hydrolysis[J]. Angewandte Chemie, 2022, 134(27): e202205091.
26	AURBACH D, GAMOLSKY K, MARKOVSKY B, et al. On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries[J]. Electrochimica Acta, 2002, 47(9): 1423-1439.
27	ZHANG X Q, CHENG X B, CHEN X, et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries[J]. Advanced Functional Materials, 2017, 27(10): 1605989.
28	JOTE B A, BEYENE T T, SAHALIE N A, et al. Effect of diethyl carbonate solvent with fluorinated solvents as electrolyte system for anode free battery[J]. Journal of Power Sources, 2020, 461: 228102.
29	SUN B, MINDEMARK J, EDSTRÖM K, et al. Polycarbonate-based solid polymer electrolytes for Li-ion batteries[J]. Solid State Ionics, 2014, 262: 738-742.
30	CHANG D R, LEE S H, KIM S W, et al. Binary electrolyte based on tetra(ethylene glycol) dimethyl ether and 1, 3-dioxolane for lithium-sulfur battery[J]. Journal of Power Sources, 2002, 112(2): 452-460.
31	NIE G M, XU J K, ZHANG S S, et al. Electrodeposition of high-quality polycarbazole films in composite electrolytes of boron trifluoride diethyl etherate and ethyl ether[J]. Journal of Applied Electrochemistry, 2006, 36(8): 937-944.
32	KERANGUEVEN G, COUTANCEAU C, SIBERT E, et al. Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells[J]. Journal of Power Sources, 2006, 157(1): 318-324.
33	YOO D J, YANG S, YUN Y S, et al. Tuning the electron density of aromatic solvent for stable solid-electrolyte-interphase layer in carbonate-based lithium metal batteries[J]. Advanced Energy Materials, 2018, 8(33): 1802365.
34	CARBONE L, GOBET M, PENG J, et al. Polyethylene glycol dimethyl ether (PEGDME)-based electrolyte for lithium metal battery[J]. Journal of Power Sources, 2015, 299: 460-464.
35	TAO R, BI X X, LI S, et al. Kinetics tuning the electrochemistry of lithium dendrites formation in lithium batteries through electrolytes[J]. ACS Applied Materials & Interfaces, 2017, 9(8): 7003-7008.
36	ZHANG G, PENG H J, ZHAO C Z, et al. The radical pathway based on a lithium-metal-compatible high-dielectric electrolyte for lithium-sulfur batteries[J]. Angewandte Chemie (International Ed in English), 2018, 57(51): 16732-16736.
37	SCHIELE A, BREITUNG B, HATSUKADE T, et al. The critical role of fluoroethylene carbonate in the gassing of silicon anodes for lithium-ion batteries[J]. ACS Energy Letters, 2017, 2(10): 2228-2233.
38	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, 81/82: 20-26.
39	WANG Z J, WANG Y Y, WU C, et al. Constructing nitrided interfaces for stabilizing Li metal electrodes in liquid electrolytes[J]. Chemical Science, 2021, 12(26): 8945-8966.
40	LIANG X, WEN Z Y, LIU Y, et al. Improved cycling performances of lithium sulfur batteries with LiNO₃-modified electrolyte[J]. Journal of Power Sources, 2011, 196(22): 9839-9843.
41	LIU Y Y, LIN D C, LI Y Z, et al. Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode[J]. Nature Communications, 2018, 9(1): 3656.
42	SHI Q W, ZHONG Y R, WU M, et al. High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes[J]. Proceedings of the National Academy of Sciences of the United States of America, 2018, 115(22): 5676-5680.
43	YAN C, YAO Y X, CHEN X, et al. Lithium nitrate solvation chemistry in carbonate electrolyte sustains high-voltage lithium metal batteries[J]. Angewandte Chemie, 2018, 130(43): 14251-14255.
44	LI S Y, ZHANG W D, WU Q, et al. Synergistic dual-additive electrolyte enables practical lithium-metal batteries[J]. Angewandte Chemie (International Ed in English), 2020, 59(35): 14935-14941.
45	LIU S F, JI X, PIAO N, et al. An inorganic-rich solid electrolyte interphase for advanced lithium-metal batteries in carbonate electrolytes[J]. Angewandte Chemie (International Ed in English), 2021, 60(7): 3661-3671.
46	YANG S T, HAO M T, WANG Z, et al. 2, 2, 2-Trifluoroethyl trifluoroacetate as effective electrolyte additive for uniform Li deposition in lithium metal batteries[J]. Chemical Engineering Journal, 2022, 435: 134897.
47	WANG Q D, YAO Z P, ZHAO C L, et al. Interface chemistry of an amide electrolyte for highly reversible lithium metal batteries[J]. Nature Communications, 2020, 11(1): 4188.
48	ZHANG S J, YIN Z W, WU Z Y, et al. Achievement of high-cyclability and high-voltage Li-metal batteries by heterogeneous SEI film with internal ionic conductivity/external electronic insulativity hybrid structure[J]. Energy Storage Materials, 2021, 40: 337-346.
49	KIM H J, UMIROV N, PARK J S, et al. Lithium dendritic growth inhibitor enabling high capacity, dendrite-free, and high current operation for rechargeable lithium batteries[J]. Energy Storage Materials, 2022, 46: 76-89.
50	ZOU Y G, CAO Z, ZHANG J L, et al. Interfacial model deciphering high-voltage electrolytes for high energy density, high safety, and fast-charging lithium-ion batteries[J]. Advanced Materials, 2021, 33(43): e2102964.
51	BEZABH H K, CHIU S F, HAGOS T M, et al. Bridging role of ethyl methyl carbonate in fluorinated electrolyte on ionic transport and phase stability for lithium-ion batteries[J]. Journal of Power Sources, 2021, 494: 229760.
52	SU C C, HE M N, CAI M, et al. Solvation-protection-enabled high-voltage electrolyte for lithium metal batteries[J]. Nano Energy, 2022, 92: 106720.
53	ZHANG W N, YANG T, LIAO X B, et al. All-fluorinated electrolyte directly tuned Li⁺ solvation sheath enabling high-quality passivated interfaces for robust Li metal battery under high voltage operation[J]. Energy Storage Materials, 2023, 57: 249-259.
54	WANG Z S, WANG H P, QI S H, et al. Structural regulation chemistry of lithium ion solvation for lithium batteries[J]. EcoMat, 2022, 4(4): e12200.
55	ZHANG X Q, CHEN X, HOU L P, et al. Regulating anions in the solvation sheath of lithium ions for stable lithium metal batteries[J]. ACS Energy Letters, 2019, 4(2): 411-416.
56	WU J R, GAO Z Y, WANG Y, et al. Electrostatic interaction tailored anion-rich solvation sheath stabilizing high-voltage lithium metal batteries[J]. Nano-Micro Letters, 2022, 14(1): 147.
57	YOON B, KIM S, LEE Y M, et al. Effect of the quantity of liquid electrolyte on self-healing electrostatic shield mechanism of CsPF₆ additive for Li metal anodes[J]. ACS Omega, 2019, 4(7): 11724-11727.
58	WANG Q, YANG C K, YANG J J, et al. Dendrite-free lithium deposition via a superfilling mechanism for high-performance Li-metal batteries[J]. Advanced Materials, 2019, 31(41): 1903248.
59	QI S H, WANG H P, HE J, et al. Electrolytes enriched by potassium perfluorinated sulfonates for lithium metal batteries[J]. Science Bulletin, 2021, 66(7): 685-693.
60	GAO Y, YI R, LI Y C, et al. General method of manipulating formation, composition, and morphology of solid-electrolyte interphases for stable Li-alloy anodes[J]. Journal of the American Chemical Society, 2017, 139(48): 17359-17367.
61	LIANG X, PANG Q, KOCHETKOV I R, et al. A facile surface chemistry route to a stabilized lithium metal anode[J]. Nature Energy, 2017, 2(9): 17119.
62	XU B, LIU Z, LI J, et al. Engineering interfacial adhesion for high-performance lithium metal anode[J]. Nano Energy, 2020, 67: 104242.
63	GU Y, WANG W W, LI Y J, et al. Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes[J]. Nature Communications, 2018, 9(1): 1339.
64	XUE P, LIU S R, SHI X L, et al. A hierarchical silver-nanowire-graphene host enabling ultrahigh rates and superior long-term cycling of lithium-metal composite anodes[J]. Advanced Materials, 2018, 30(44): 1804165.
65	WANG H S, LI Y Z, LI Y B, et al. Wrinkled graphene cages as hosts for high-capacity Li metal anodes shown by cryogenic electron microscopy[J]. Nano Letters, 2019, 19(2): 1326-1335.
66	GUO F H, WU C, CHEN H, et al. Dendrite-free lithium deposition by coating a lithiophilic heterogeneous metal layer on lithium metal anode[J]. Energy Storage Materials, 2020, 24: 635-643.
67	SHI H D, QIN J Q, HUANG K, et al. A two-dimensional mesoporous polypyrrole-graphene oxide heterostructure as a dual-functional ion redistributor for dendrite-free lithium metal anodes[J]. Angewandte Chemie (International Ed in English), 2020, 59(29): 12147-12153.
68	MA C W, LIU C C, ZHANG Y X, et al. A dual lithiated alloy interphase layer for high-energy–density lithium metal batteries[J]. Chemical Engineering Journal, 2022, 434: 134637.
69	ZHENG J M, LOCHALA J A, KWOK A, et al. Research progress towards understanding the unique interfaces between concentrated electrolytes and electrodes for energy storage applications[J]. Advanced Science, 2017, 4(8): 1700032.
70	LIU B, XU W, YAN P F, et al. Enhanced cycling stability of rechargeable Li-O₂ batteries using high-concentration electrolytes[J]. Advanced Functional Materials, 2016, 26(4): 605-613.
71	JIANG G X, LI F, WANG H P, et al. Perspective on high-concentration electrolytes for lithium metal batteries[J]. Small Structures, 2021, 2(5): 2000122.
72	XU K, LAM Y, ZHANG S S, et al. Solvation sheath of Li⁺ in nonaqueous electrolytes and its implication of graphite/electrolyte interface chemistry[J]. The Journal of Physical Chemistry C, 2007, 111(20): 7411-7421.
73	CHEN J, LI Q, POLLARD T P, et al. Electrolyte design for Li metal-free Li batteries[J]. Materials Today, 2020, 39: 118-126.
74	MAEYOSHI Y, DING D, KUBOTA M, et al. Long-term stable lithium metal anode in highly concentrated sulfolane-based electrolytes with ultrafine porous polyimide separator[J]. ACS Applied Materials & Interfaces, 2019, 11(29): 25833-25843.
75	LI J, DOWNIE L E, MA L, et al. Study of the failure mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode material for lithium ion batteries[J]. Journal of the Electrochemical Society, 2015, 162(7): A1401-A1408.
76	PHAM T D, BIN FAHEEM A, KIM J, et al. Practical high-voltage lithium metal batteries enabled by tuning the solvation structure in weakly solvating electrolyte[J]. Small, 2022, 18(14): e2107492.
77	CAO X, REN X D, ZOU L F, et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization[J]. Nature Energy, 2019, 4: 796-805.
78	REN X D, ZOU L F, CAO X, et al. Enabling high-voltage lithium-metal batteries under practical conditions[J]. Joule, 2019, 3(7): 1662-1676.
79	REN X D, CHEN S R, LEE H, et al. Localized high-concentration sulfone electrolytes for high-efficiency lithium-metal batteries[J]. Chem, 2018, 4(8): 1877-1892.
80	XIA M, LIN M, LIU G P, et al. Stable cycling and fast charging of high-voltage lithium metal batteries enabled by functional solvation chemistry[J]. Chemical Engineering Journal, 2022, 442: 136351.
81	ZHANG G Z, DENG X L, LI J W, et al. A bifunctional fluorinated ether co-solvent for dendrite-free and long-term lithium metal batteries[J]. Nano Energy, 2022, 95: 107014.

[1]	姜媛媛, 屠芳芳, 张芳平, 王盈来, 蔡佳文, 杨东辉, 李艳红, 相佳媛, 夏新辉, 傅继澎. 高性能磷酸铁锂电池补锂技术及机制[J]. 储能科学与技术, 2024, 13(5): 1435-1442.
[2]	陶致格, 朱顺兵, 侯双平, 李可, 王赫. 锂电池储能电站火灾与消防安全防护技术综合研究[J]. 储能科学与技术, 2024, 13(2): 536-545.
[3]	贾铭勋, 吴桐, 杨道通, 秦小茜, 刘景海, 段莉梅. 锂硫电池电解液多功能添加剂：作用机制及先进表征[J]. 储能科学与技术, 2024, 13(1): 36-47.
[4]	陈珊珊, 郑翔, 王若, 原铭蔓, 彭威, 鲁博明, 张光照, 王朝阳, 王军, 邓永红. 锂离子电池硅基负极电解液添加剂研究进展：挑战与展望[J]. 储能科学与技术, 2024, 13(1): 279-292.
[5]	李文彪, 耿海涛, 高一博, 高召顺, 王宝. Cu-In/Bi合金中亲锂位点诱导均匀锂成核实现高倍率锂金属电池[J]. 储能科学与技术, 2023, 12(9): 2735-2745.
[6]	韩雨, 曹盛玲, 宁靖, 王康丽, 蒋凯, 周敏. 聚合物改性锂金属电池界面策略研究综述[J]. 储能科学与技术, 2023, 12(8): 2491-2503.
[7]	夏恒恒, 梁鹏程, 安仲勋. 硫系电解液添加剂对镍钴锰酸锂//石墨锂离子电池性能的影响[J]. 储能科学与技术, 2023, 12(8): 2390-2400.
[8]	徐冲, 徐宁, 蒋志敏, 李中凯, 胡洋, 严红, 马国强. 锂离子电池产气机制及基于电解液的抑制策略[J]. 储能科学与技术, 2023, 12(7): 2119-2133.
[9]	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.
[10]	黄凌锋, 韩东梅, 黄盛, 王拴紧, 肖敏, 孟跃中. 含有机硼的锂离子电池聚合物电解质的研究进展[J]. 储能科学与技术, 2023, 12(6): 1815-1830.
[11]	时文超, 刘宇, 张博冕, 李琪, 韩春华, 麦立强. 电解液添加剂稳定水系电池锌负极界面的研究进展[J]. 储能科学与技术, 2023, 12(5): 1589-1603.
[12]	余永诗, 夏先明, 黄弘扬, 姚雨, 芮先宏, 钟国彬, 苏伟, 余彦. 钠金属负极人工界面保护层的研究进展[J]. 储能科学与技术, 2023, 12(5): 1380-1391.
[13]	封迈, 陈楠, 陈人杰. 锂离子电池低温电解液的研究进展[J]. 储能科学与技术, 2023, 12(3): 792-807.
[14]	袁紫微, 林楚园, 袁紫嫣, 孙晓丽, 钱庆荣, 陈庆华, 曾令兴. 锌离子电池低温性能研究进展[J]. 储能科学与技术, 2023, 12(1): 278-298.
[15]	沈馨, 张睿, 赵辰孜, 武鹏, 张羽彤, 张俊东, 范丽珍, 刘全兵, 陈爱兵, 张强. 金属锂电池中力-电化学机制研究进展[J]. 储能科学与技术, 2022, 11(9): 2781-2797.