合金型负极预锂化技术研究进展

doi:10.19799/j.cnki.2095-4239.2021.0570

摘要/Abstract

摘要：

负极是锂离子电池的关键组件，实现高容量合金型负极在锂离子电池中的应用可大幅提升锂离子电池的能量密度。然而目前合金型负极存在严重的低首圈库仑效率问题，致使大量活性锂在循环初期被不可逆消耗，制约了其在提升锂离子电池能量密度方面发挥优势。预锂化技术被认为是解决合金型负极锂损失问题的有效方案，主要分为负极预锂化与正极预锂化。本文通过调研整理近期相关文献，详细分析了不同预锂化技术在合金负极中的研究进展与应用前景。对于负极预锂化技术，主要介绍了电化学预锂化、接触金属锂、化学预锂化以及负极富锂添加剂等策略；对于正极预锂化技术，主要介绍了正极富锂添加剂与正极过锂化两种方法；对于不同预锂化技术的实用化，主要分析了补锂试剂稳定性与安全性、补锂试剂的利用率以及成本等问题。综合分析表明，预锂化技术是弥补不可逆容量损失、提高合金型负极锂离子电池的能量密度与循环寿命的有效方案，低成本与高安全性是预锂化技术实用化的关键所在。

关键词: 预锂化, 库仑效率, 硅负极, 高能量密度, 锂离子电池

Abstract:

The anode is a key component of lithium-ion batteries, and the use of high-capacity alloy-type anodes can significantly improve the energy density of those batteries. However, alloy-type anodes suffer from low initial coulombic efficiency. This problem leads to irreversible consumption of large quantities of active lithium, which offsets the improved battery energy density. Prelithiation technology is considered a promising approach to address this problem, applicable both to anodes and cathodes. This paper summarizes research progress and application prospects for different prelithiation technologies based on a comprehensive analysis of recent literature. For anode prelithiation, the strategies of electrochemical prelithiation, chemical prelithiation, lithium-rich anode additives, and direct contact with metallic lithium, are introduced. For cathode prelithiation, strategies involving lithium-rich additives and over-lithiation are discussed. With a view toward the practical realization of different prelithiation technologies, this analysis focuses on the stability and safety, utilization rate, and cost of each prelithiation reagent. Results demonstrate that prelithiation can be an effective solution to compensate for irreversible capacity loss. Thus, it can contribute to significant improvements in energy density and cycle life of lithium-ion batteries with alloy anodes. Low cost and high safety are the keys to promote the practical application of prelithiation technology.

Key words: pre-lithiation, coulombic efficiency, silicon anode, high energy density, lithium-ion batteries

中图分类号:

TM 911

张策, 李思吾, 谢佳. 合金型负极预锂化技术研究进展[J]. 储能科学与技术, 2022, 11(5): 1383-1400.

Ce ZHANG, Siwu LI, Jia XIE. Research progress on the prelithiation technology of alloy-type anodes[J]. Energy Storage Science and Technology, 2022, 11(5): 1383-1400.

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参考文献 108

1	CABANA J, MONCONDUIT L, LARCHER D, et al. Beyond intercalation-based Li-ion batteries: The state of the art and challenges of electrode materials reacting through conversion reactions[J]. Advanced Materials, 2010, 22(35): E170-E192.
2	NITTA N, WU F X, LEE J T, et al. Li-ion battery materials: Present and future[J]. Materials Today, 2015, 18(5): 252-264.
3	罗飞, 褚赓, 黄杰, 等. 锂离子电池基础科学问题(Ⅷ)——负极材料[J]. 储能科学与技术, 2014, 3(2): 146-163.
	LUO F, CHU G, HUANG J, et al. Fundamental scientific aspects of lithium batteries(‍Ⅷ)‍—Anode electrode materials[J]. Energy Storage Science and Technology, 2014, 3(2): 146-163.
4	明海, 明军, 邱景义, 等. 预锂化技术在能源存储中的应用[J]. 储能科学与技术, 2017, 6(2): 223-236.
	MING H, MING J, QIU J Y, et al. Applications of pre-lithiation technologies in energy storage[J]. Energy Storage Science and Technology, 2017, 6(2): 223-236.
5	JIN L M, SHEN C, WU Q, et al. Pre-lithiation strategies for next-generation practical lithium-ion batteries[J]. Advanced Science, 2021, 8(12): doi:10.1002/advs.202005031.
6	SUN C K, ZHANG X, LI C, et al. Recent advances in prelithiation materials and approaches for lithium-ion batteries and capacitors[J]. Energy Storage Materials, 2020, 32: 497-516.
7	ZHAN R M, WANG X C, CHEN Z H, et al. Promises and challenges of the practical implementation of prelithiation in lithium-ion batteries[J]. Advanced Energy Materials, 2021, 11(35): doi:10.1002/aenm.202101565.
8	WANG F, WANG B, LI J X, et al. Prelithiation: A crucial strategy for boosting the practical application of next-generation lithium ion battery[J]. ACS Nano, 2021, 15(2): 2197-2218.
9	HOLTSTIEGE F, BÄRMANN P, NÖLLE R, et al. Pre-lithiation strategies for rechargeable energy storage technologies: Concepts, promises and challenges[J]. Batteries, 2018, 4(1): 4.
10	KIM H J, CHOI S, LEE S J, et al. Controlled prelithiation of silicon monoxide for high performance lithium-ion rechargeable full cells[J]. Nano Letters, 2016, 16(1): 282-288.
11	ZHOU H T, WANG X H, CHEN D E. Li-metal-free prelithiation of Si-based negative electrodes for full Li-ion batteries[J]. ChemSusChem, 2015, 8(16): 2737-2744.
12	WATANABE T, TSUDA T, ANDO N, et al. An improved pre-lithiation of graphite anodes using through-holed cathode and anode electrodes in a laminated lithium ion battery[J]. Electrochimica Acta, 2019, 324: doi:10.1016/j.electacta.2019. 134848.
13	REZQITA A, KATHRIBAIL A R, KAHR J, et al. Analysis of degradation of Si/Carbon\|\|LiNi_0.5Mn_0.3Co_0.2O₂ Full cells: Effect of prelithiation[J]. Journal of the Electrochemical Society, 2019, 166(3): A5483-A5488.
14	LIU N, HU L B, MCDOWELL M T, et al. Prelithiated silicon nanowires as an anode for lithium ion batteries[J]. ACS Nano, 2011, 5(8): 6487-6493.
15	BÄRMANN P, DIEHL M, GÖBEL L, et al. Impact of the silicon particle size on the pre-lithiation behavior of silicon/carbon composite materials for lithium ion batteries[J]. Journal of Power Sources, 2020, 464: doi:10.1016/j.jpowsour.2020.228224.
16	MENG Q H, LI G, YUE J P, et al. High-performance lithiated SiOx anode obtained by a controllable and efficient prelithiation strategy[J]. ACS Applied Materials & Interfaces, 2019, 11(35): 32062-32068.
17	SHELLIKERI A, WATSON V, ADAMS D, et al. Investigation of pre-lithiation in graphite and hard-carbon anodes using different lithium source structures[J]. Journal of the Electrochemical Society, 2017, 164(14): A3914-A3924.
18	WAN Y X, WANG L J, CHEN Y J, et al. A high-performance tin dioxide@carbon anode with a super high initial coulombic efficiency via a primary cell prelithiation process[J]. Journal of Alloys and Compounds, 2018, 740: 830-835.
19	YERSAK T A, SON S B, CHO J S, et al. An all-solid-state Li-ion battery with a pre-lithiated Si-Ti-Ni alloy anode[J]. Journal of the Electrochemical Society, 2013, 160(9): A1497-A1501.
20	HUANG S Z, ZHANG L, LIU L F, et al. Rationally engineered amorphous TiOx/Si/TiOx nanomembrane as an anode material for high energy lithium ion battery[J]. Energy Storage Materials, 2018, 12: 23-29.
21	WU W, WANG M, WANG J, et al. Green design of Si/SiO₂/C composites as high-performance anodes for lithium-ion batteries[J]. ACS Applied Energy Materials, 2020, 3(4): 3884-3892.
22	RYU J, KANG J, KIM H, et al. Electrolyte-mediated nanograin intermetallic formation enables superionic conduction and electrode stability in rechargeable batteries[J]. Energy Storage Materials, 2020, 33: 164-172.
23	HASSOUN J, KIM J, LEE D J, et al. A contribution to the progress of high energy batteries: A metal-free, lithium-ion, silicon-sulfur battery[J]. Journal of Power Sources, 2012, 202: 308-313.
24	REN Y X, ZENG L, ZHAO C, et al. A safe and efficient lithiated silicon-sulfur battery enabled by a bi-functional composite interlayer[J]. Energy Storage Materials, 2020, 25: 217-223.
25	KIM K H, SHON J, JEONG H, et al. Improving the cyclability of silicon anodes for lithium-ion batteries using a simple pre-lithiation method[J]. Journal of Power Sources, 2020, 459: doi:10.1016/j.jpowsour.2020.228066.
26	SONG B F, DHANABALAN A, BISWAL S L. Evaluating the capacity ratio and prelithiation strategies for extending cyclability in porous silicon composite anodes and lithium iron phosphate cathodes for high capacity lithium-ion batteries[J]. Journal of Energy Storage, 2020, 28: doi:10.1016/j.est.2020.101268.
27	YANG Y X, NI C L, GAO M X, et al. Dispersion-strengthened microparticle silicon composite with high anti-pulverization capability for Li-ion batteries[J]. Energy Storage Materials, 2018, 14: 279-288.
28	WANG G W, LI F F, LIU D, et al. Chemical prelithiation of negative electrodes in ambient air for advanced lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2019, 11(9): 8699-8703.
29	SHEN Y F, ZHANG J M, PU Y F, et al. Effective chemical prelithiation strategy for building a silicon/sulfur Li-ion battery[J]. ACS Energy Letters, 2019, 4(7): 1717-1724.
30	MA R J, LIU Y F, HE Y P, et al. Chemical preinsertion of lithium: An approach to improve the intrinsic capacity retention of bulk Si anodes for Li-ion batteries[J]. The Journal of Physical Chemistry Letters, 2012, 3(23): 3555-3558.
31	YANG Y X, QU X L, ZHANG L C, et al. Reaction-ball-milling-driven surface coating strategy to suppress pulverization of microparticle Si anodes[J]. ACS Applied Materials & Interfaces, 2018, 10(24): 20591-20598.
32	PANG Y P, WANG X T, SHI X X, et al. Solid-state prelithiation enables high-performance Li-Al-H anode for solid-state batteries[J]. Advanced Energy Materials, 2020, 10(12): doi: 10.1002/aenm. 201902795.
33	ALABOINA P K, CHO J S, UDDIN M J, et al. Mechanically prelithiated silicon nano alloy as highly engineered anode material[J]. Electrochimica Acta, 2017, 258: 623-630.
34	SCOTT M G, WHITEHEAD A H, OWEN J R. Chemical formation of a solid electrolyte interface on the carbon electrode of a Li-ion cell[J]. Journal of the Electrochemical Society, 1998, 145(5): 1506-1510.
35	WANG G W, LI F F, LIU D, et al. High performance lithium-ion and lithium-sulfur batteries using prelithiated phosphorus/carbon composite anode[J]. Energy Storage Materials, 2020, 24: 147-152.
36	JANG J, KANG I, CHOI J, et al. Molecularly tailored lithium-arene complex enables chemical prelithiation of high-capacity lithium-ion battery anodes[J]. Angewandte Chemie International Edition, 2020, 59(34): 14473-14480.
37	SHEN Y F, SHEN X H, YANG M, et al. Achieving desirable initial coulombic efficiencies and full capacity utilization of Li-ion batteries by chemical prelithiation of graphite anode[J]. Advanced Functional Materials, 2021, 31(24): doi:10.1002/adfm.202101181.
38	CHOI J, JEONG H, JANG J, et al. Weakly solvating solution enables chemical prelithiation of graphite-SiOx anodes for high-energy Li-ion batteries[J]. Journal of the American Chemical Society, 2021, 143(24): 9169-9176.
39	XU H, LI S, ZHANG C, et al. Roll-to-roll prelithiation of Sn foil anode suppresses gassing and enables stable full-cell cycling of lithium ion batteries[J]. Energy & Environmental Science, 2019, 12(10): 2991-3000.
40	YAN M Y, LI G, ZHANG J, et al. Enabling SiOx/C anode with high initial coulombic efficiency through a chemical pre-lithiation strategy for high-energy-density lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(24): 27202-27209.
41	SHEN Y F, QIAN J F, YANG H X, et al. Chemically prelithiated hard-carbon anode for high power and high capacity Li-ion batteries[J]. Small, 2020, 16(7): doi:10.1002/smll.201907602.
42	TABUCHI T, YASUDA H, YAMACHI M. Li-doping process for LixSiO-negative active material synthesized by chemical method for lithium-ion cells[J]. Journal of Power Sources, 2005, 146(1/2): 507-509.
43	LI F F, WANG G W, ZHENG D, et al. Controlled prelithiation of SnO₂/C nanocomposite anodes for building full lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(17): 19423-19430.
44	HUANG Y M, LIU C, WEI F Y, et al. Chemical prelithiation of Al for use as an ambient air compatible and polysulfide resistant anode for Li-ion/S batteries[J]. Journal of Materials Chemistry A, 2020, 8(36): 18715-18720.
45	陆浩, 李金熠, 刘柏男, 等. 锂离子电池纳米硅碳负极材料研发进展[J]. 储能科学与技术, 2017, 6(5): 864-870.
	LU H, LI J Y, LIU B N, et al. Research and technology progress of nano-Si/C anode materials for lithium ion batteries[J]. Energy Storage Science and Technology, 2017, 6(5): 864-870.
46	YU Y, LI S, FAN H M, et al. Optimal annealing of Al foil anode for prelithiation and full-cell cycling in Li-ion battery: The role of grain boundaries in lithiation/delithiation ductility[J]. Nano Energy, 2020, 67: doi:10.1016/j.nanoen.2019.104274.
47	FAN H M, LI S, YU Y, et al. Air-stable LixAl foil as free-standing electrode with improved electrochemical ductility by shot-peening treatment[J]. Advanced Functional Materials, 2021, 31(29): doi:10.1002/adfm.202100978.
48	XU H, LI S, CHEN X L, et al. Surpassing lithium metal rechargeable batteries with self-supporting Li-Sn-Sb foil anode[J]. Nano Energy, 2020, 74: doi:10.1016/j.nanoen.2020.104815.
49	XU H, LI S, CHEN X L, et al. Sn-alloy foil electrode with mechanical prelithiation: Full-cell performance up to 200 cycles[J]. Advanced Energy Materials, 2019, 9(42): doi: 10.1002/aenm. 201902150.
50	FAN H M, CHEN B, LI S, et al. Nanocrystalline Li-Al-Mn-Si foil as reversible Li host: Electronic percolation and electrochemical cycling stability[J]. Nano Letters, 2020, 20(2): 896-904.
51	FORNEY M W, GANTER M J, STAUB J W, et al. Prelithiation of silicon-carbon nanotube anodes for lithium ion batteries by stabilized lithium metal powder (SLMP)[J]. Nano Letters, 2013, 13(9): 4158-4163.
52	CHEN H, YANG Y, BOYLE D T, et al. Free-standing ultrathin lithium metal-graphene oxide host foils with controllable thickness for lithium batteries[J]. Nature Energy, 2021, 6: 790-798.
53	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.
54	LI Y X, FITCH B. Effective enhancement of lithium-ion battery performance using SLMP[J]. Electrochemistry Communications, 2011, 13(7): 664-667.
55	XIANG B, WANG L, LIU G, et al. Electromechanical probing of Li/Li₂CO₃ Core/shell particles in a TEM[J]. Journal of the Electrochemical Society, 2013, 160(3): A415-A419.
56	HEINE J, RODEHORST U, QI X, et al. Using polyisobutylene as a non-fluorinated binder for coated lithium powder (CLiP) electrodes[J]. Electrochimica Acta, 2014, 138: 288-293.
57	Coated lithium powder (CLiP) electrodes for lithium-metal batteries[J]. Advanced Energy Materials, 2014, 4(5): doi:10.1002/aenm.201400406.
58	KANG T, WANG Y L, GUO F, et al. Self-assembled monolayer enables slurry-coating of Li anode[J]. ACS Central Science, 2019, 5(3): 468-476.
59	LI X M, LI Y S, TANG Y F, et al. Air stable lithium microspheres prelithiation reagents for Li-ion batteries synthesized via electroplating[J]. Journal of Power Sources, 2021, 496: doi: 10.1016/j.jpowsour.2021.229868.
60	HUANG B, HUANG T, WAN L Y, et al. Pre-lithiating SiO anodes for lithium-ion batteries by a simple, effective, and controllable strategy using stabilized lithium metal powder[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(2): 648-657.
61	AI G, WANG Z H, ZHAO H, et al. Scalable process for application of stabilized lithium metal powder in Li-ion batteries[J]. Journal of Power Sources, 2016, 309: 33-41.
62	WANG L, FU Y B, BATTAGLIA V S, et al. SBR-PVDF based binder for the application of SLMP in graphite anodes[J]. RSC Advances, 2013, 3(35): 15022.
63	SEONG I W, YOON W Y. Electrochemical behavior of a silicon monoxide and Li-powder double layer anode cell[J]. Journal of Power Sources, 2010, 195(18): 6143-6147.
64	CAO Z Y, XU P Y, ZHAI H W, et al. Ambient-air stable lithiated anode for rechargeable Li-ion batteries with high energy density[J]. Nano Letters, 2016, 16(11): 7235-7240.
65	ZHAO J, LU Z, LIU N, et al. Dry-air-stable lithium silicide–lithium oxide core-shell nanoparticles as high-capacity prelithiation reagents[J]. Nature Communications, 2014, 5: 5088.
66	ZHAO J, LU Z D, WANG H T, et al. Artificial solid electrolyte interphase-protected LixSi nanoparticles: An efficient and stable prelithiation reagent for lithium-ion batteries[J]. Journal of the American Chemical Society, 2015, 137(26): 8372-8375.
67	ZHAO J, LEE H W, SUN J, et al. Metallurgically lithiated SiOx anode with high capacity and ambient air compatibility[J]. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113(27): 7408-7413.
68	ZHAO J, SUN J, PEI A, et al. A general prelithiation approach for group IV elements and corresponding oxides[J]. Energy Storage Materials, 2018, 10: 275-281.
69	PARK K, YU B C, GOODENOUGH J B. Li₃N as a cathode additive for high-energy-density lithium-ion batteries[J]. Advanced Energy Materials, 2016, 6(10): doi:10.1002/aenm.201502534.
70	SUN Y, LEE H W, SEH Z W, et al. High-capacity battery cathode prelithiation to offset initial lithium loss[J]. Nature Energy, 2016, 1: 15008.
71	LIU Z Z, MA S B, MU X, et al. A scalable cathode chemical prelithiation strategy for advanced silicon-based lithium ion full batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(10): 11985-11994.
72	WANG X Y, LIU C, ZHANG S J, et al. Dual-functional cathodic prelithiation reagent of Li3P in lithium-ion battery for compensating initial capacity loss and enhancing safety[J]. ACS Applied Energy Materials, 2021, 4(5): 5246-5254.
73	SUN Y M, LI Y B, SUN J, et al. Stabilized Li₃N for efficient battery cathode prelithiation[J]. Energy Storage Materials, 2017, 6: 119-124.
74	YANG S Y, YUE X Y, XIA H Y, et al. Battery prelithiation enabled by lithium fixation on cathode[J]. Journal of Power Sources, 2020, 480: doi:10.1016/j.jpowsour.2020.229109.
75	ZHAN Y J, YU H L, BEN L B, et al. Application of Li₂S to compensate for loss of active lithium in a Si-C anode[J]. Journal of Materials Chemistry A, 2018, 6(15): 6206-6211.
76	ZHAN Y J, YU H L, BEN L B, et al. Using Li₂S to compensate for the loss of active lithium in Li-ion batteries[J]. Electrochimica Acta, 2017, 255: 212-219.
77	BIE Y T, YANG J, WANG J L, et al. Li₂O₂ as a cathode additive for the initial anode irreversibility compensation in lithium-ion batteries[J]. Chemical Communications (Cambridge, England), 2017, 53(59): 8324-8327.
78	SUN Y M, LEE H W, ZHENG G Y, et al. In situ chemical synthesis of lithium fluoride/metal nanocomposite for high capacity prelithiation of cathodes[J]. Nano Letters, 2016, 16(2): 1497-1501.
79	SUN Y M, LEE H W, SEH Z W, et al. Lithium sulfide/metal nanocomposite as a high-capacity cathode prelithiation material[J]. Advanced Energy Materials, 2016, 6(12): doi:10.1002/aenm. 201600154.
80	RAO Z X, WU J Y, HE B, et al. A prelithiation separator for compensating the initial capacity loss of lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(32): 38194-38201.
81	DU J M, WANG W Y, ENG A Y S, et al. Metal/LiF/Li₂O nanocomposite for battery cathode prelithiation: Trade-off between capacity and stability[J]. Nano Letters, 2020, 20(1): 546-552.
82	ABOUIMRANE A, CUI Y J, CHEN Z H, et al. Enabling high energy density Li-ion batteries through Li₂O activation[J]. Nano Energy, 2016, 27: 196-201.
83	ZOU K Y, SONG Z R, GAO X, et al. Molecularly compensated pre-metallation strategy for metal-ion batteries and capacitors[J]. Angewandte Chemie International Edition, 2021, 60(31): 17070-17079.
84	FAN L J, TANG D C, WANG D Y, et al. LiCoO₂-catalyzed electrochemical oxidation of Li₂CO₃[J]. Nano Research, 2016, 9(12): 3903-3913.
85	SOLCHENBACH S, WETJEN M, PRITZL D, et al. Lithium oxalate as capacity and cycle-life enhancer in LNMO/graphite and LNMO/SiG full cells[J]. Journal of the Electrochemical Society, 2018, 165(3): A512-A524.
86	SHANMUKARAJ D, GRUGEON S, LARUELLE S, et al. Sacrificial salts: Compensating the initial charge irreversibility in lithium batteries[J]. Electrochemistry Communications, 2010, 12(10): 1344-1347.
87	WANG R, YU X Q, BAI J M, et al. Electrochemical decomposition of Li₂CO₃ in NiO-Li₂CO₃ nanocomposite thin film and powder electrodes[J]. Journal of Power Sources, 2012, 218: 113-118.
88	NOH M, CHO J. Role of Li₆CoO₄Cathode additive in Li-ion cells containing low coulombic efficiency anode material[J]. Journal of the Electrochemical Society, 2012, 159(8): A1329-A1334.
89	PARK H, YOON T, KIM Y U, et al. Li₂NiO₂ as a sacrificing positive additive for lithium-ion batteries[J]. Electrochimica Acta, 2013, 108: 591-595.
90	PARK K S, IM D, BENAYAD A, et al. LiFeO₂-incorporated Li₂MoO₃ as a cathode additive for lithium-ion battery safety[J]. Chemistry of Materials, 2012, 24(14): 2673-2683.
91	JEŻOWSKI P, FIC K, CROSNIER O, et al. Lithium rhenium(vii) oxide as a novel material for graphite pre-lithiation in high performance lithium-ion capacitors[J]. Journal of Materials Chemistry A, 2016, 4(32): 12609-12615.
92	VITINS G, RAEKELBOOM E A, WELLER M T, et al. Li₂CuO₂ as an additive for capacity enhancement of lithium ion cells[J]. Journal of Power Sources, 2003, 119/120/121: 938-942.
93	ZHANG L H, DOSE W M, VU A D, et al. Mitigating the initial capacity loss and improving the cycling stability of silicon monoxide using Li₅FeO₄[J]. Journal of Power Sources, 2018, 400: 549-555.
94	DOSE W M, VILLA C, HU X B, et al. Beneficial effect of Li₅FeO₄ lithium source for Li-ion batteries with a layered NMC cathode and Si anode[J]. Journal of the Electrochemical Society, 2020, 167(16): 160543.
95	ARAVINDAN V, NAN S, KEPPELER M, et al. Pre-lithiated LixMn₂O₄: A new approach to mitigate the irreversible capacity loss in negative electrodes for Li-ion battery[J]. Electrochimica Acta, 2016, 208: 225-230.
96	DOSE W M, BLAUWKAMP J, PIERNAS-MUÑOZ M J, et al. Liquid ammonia chemical lithiation: An approach for high-energy and high-voltage Si-Graphite\|Li₁₊ xNi_0.5Mn_1.5O₄ Li-ion batteries[J]. ACS Applied Energy Materials, 2019, 2(7): 5019-5028.
97	LIU Y, YANG B C, DONG X L, et al. A simple prelithiation strategy to build a high-rate and long-life lithium-ion battery with improved low-temperature performance[J]. Angewandte Chemie International Edition, 2017, 56(52): 16606-16610.
98	YANG L Y, YANG K, ZHENG J X, et al. Harnessing the surface structure to enable high-performance cathode materials for lithium-ion batteries[J]. Chemical Society Reviews, 2020, 49(14): 4667-4680.
99	WANG R, QIAN G Y, LIU T C, et al. Tuning Li-enrichment in high-Ni layered oxide cathodes to optimize electrochemical performance for Li-ion battery[J]. Nano Energy, 2019, 62: 709-717.
100	TANG Z F, WANG S, LIAO J Y, et al. Facilitating lithium-ion diffusion in layered cathode materials by introducing Li⁺/Ni²⁺ antisite defects for high-rate Li-ion batteries[J]. Research (Washington, D C), 2019: doi: 10.34133/2019/2198906.
101	LIU X X, LIU T C, WANG R, et al. Prelithiated Li-enriched gradient interphase toward practical high-energy NMC-silicon full cell[J]. ACS Energy Letters, 2021, 6(2): 320-328.
102	LIU X X, TAN Y C, WANG W Y, et al. Conformal prelithiation nanoshell on LiCoO₂ enabling high-energy lithium-ion batteries[J]. Nano Letters, 2020, 20(6): 4558-4565.
103	SONG Z H, FENG K, ZHANG H Z, et al. “Giving comes before receiving”: High performance wide temperature range Li-ion battery with Li₅V₂(PO₄)₃ as both cathode material and extra Li donor[J]. Nano Energy, 2019, 66: doi:10.1016/j.nanoen.2019. 104175.
104	BETZ J, NOWAK L, WINTER M, et al. An approach for pre-lithiation of Li₁₊ xNi_0.5Mn_1.5O₄ cathodes mitigating active lithium loss[J]. Journal of the Electrochemical Society, 2019, 166(15): A3531-A3538.
105	PERAMUNAGE D, ABRAHAM K M. Preparation and electrochemical characterization of overlithiated spinel LiMn₂O₄[J]. Journal of the Electrochemical Society, 1998, 145(4): 1131-1136.
106	TARASCON J M, GUYOMARD D. Li metal-free rechargeable batteries based on Li₁₊ xMn₂O₄ cathodes (0 ≤x≤ 1) and carbon anodes[J]. Journal of the Electrochemical Society, 1991, 138(10): 2864-2868.
107	MANCINI M, AXMANN P, GABRIELLI G, et al. A high-voltage and high-capacity Li₁₊ xNi_0.5Mn_1.5O₄ cathode material: From synthesis to full lithium-ion cells[J]. ChemSusChem, 2016, 9(14): 1843-1849.
108	MOORHEAD-ROSENBERG Z, ALLCORN E, MANTHIRAM A. In situ mitigation of first-cycle anode irreversibility in a new spinel/FeSb lithium-ion cell enabled via a microwave-assisted chemical lithiation process[J]. Chemistry of Materials, 2014, 26(20): 5905-5913.

负极	方法	电池体系	预锂化前ICE	预锂化后ICE	循环性能	参考文献
c-SiO _x	电化学	NCA\|\|c-SiO _x	58.85%	85.34%	61%(1 C, 100圈)	[10]
SiO _x	接触金属锂	NCM622\|\|SiO _x	68%	87%	74%(200圈)	[16]
P/C	Li-Bp/THF 0.41 V (vs. Li/Li⁺)	P/C\|\|Li	74%	94%	—	[28]
SiO _x /C	Li-Bp/THF 0.41 V (vs. Li/Li⁺)	SiO _x /C\|\|Li	75.6%	90%	～58%(0.5 C, 400圈)	[40]
Si	Li-Naph/DME 0.35 V (vs. Li/Li⁺)	Si\|\|Li	74%	96.1%	—	[29]
SiO _x	Li-Arene <0.2 V (vs. Li/Li⁺)	NCM532\|\|SiO _x	37.8%	86.4%	—	[36]
c-Gr/Si	Li-Bp/2-Me-THF 0.08 V (vs. Li/Li⁺)	NCM622\|\| c-Gr/Si	63.2%	88.3%	87.3%(250圈)	[38]
Sn	机械辊压	LFP\|\|Sn	21%	94%	94.5%(200圈)	[39]
Si-CNT	SLMP	Si-CNT\|\|Li	58%	79%	—	[51]
Si	Li@eGF	Si\|\|Li	79.4%	100.5%	56%(0.05 C, 100圈)	[52]
Si	Li _x Si-Li₂O	Si\|\|Li	76%	94%	—	[65]

补锂试剂	容量	电池	补锂前首圈充电容量	添加量/(%，质量分数)	补锂后首圈充电容量	参考文献
Li₃N	1399.3 mAh/g (截止电位4.2 V)	LCO\|\|Li	149.7 mAh/g	2	178.4 mAh/g	[69]
Fe/LiF/Li₂O	550 mAh/g (截止电位4.4 V)	NCM622\|\|Li	198 mAh/g	4.8	229 mAh/g	[81]
Li₂S-PAN	668 mAh/g (截止电位4.0 V)	LFP\|\|Li	169 mAh/g	4.3	187 mAh/g	[71]
Co/Li₂O	619 mAh/g (截止电位4.1 V)	LFP\|\|Li	163 mAh/g	4.8	183 mAh/g	[70]
Li₃P/rGO (5:1)	1289.7 mAh/g (理论)	LFP\|\|Li	162 mAh/g	5	181.3 mAh/g	[72]
Li₅FeO₄	764 mAh/g (截止电位4.7 V)	NCM523\|\|Li	190 mAh/g	7.1	233 mAh/g	[94]
NiO/Li₂CO₃	240 mAh/g (截止电位4.5 V)	LMO\|\|Li	120 mAh/g	50	410 mAh/g	[87]
Li_1.62Ni_0.5Mn_1.5O₄	截止电位4.55 V	LMO\|\|Li	145 mAh/g	—	217 mAh/g	[96]

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