Investigation of lithium storage mechanisms in liquid metal electrodes with different morphologies

doi:10.19799/j.cnki.2095-4239.2025.0139

Abstract

Abstract:

To harness the excellent fluidity and self-healing characteristics of liquid metal, two novel electrodes, liquid metal nanoparticles (LMNP) and liquid metal film (LMF), were fabricated via probe ultrasonication and doctor-blading methods, respectively. The microstructural features, mechanical properties, and electrochemical performances of these electrodes were comprehensively investigated using focused ion beam milling, scanning electron microscopy, nanoindentation, and electrochemical measurements. The LMNP electrode exhibited a uniform dispersion of nanoparticles within the matrix, forming strong interparticle connections, whereas the LMF electrode formed a continuous film on the substrate, which developed cracks at the interface with the current collector. The LMNP electrode demonstrated superior rate capability and cycling stability compared to the LMF electrode. After 300 cycles at a current density of 2.0 A/g, the LMNP electrode maintained a reversible specific capacity of 399.3 mAh/g with a capacity retention of 86.9%. During cycling, both electrodes underwent particle size reduction and self-healing-induced welding, providing additional conductive pathways that facilitated charge transfer. Moreover, both electrodes exhibited a gradual transition from a soft to a rigid structure during cycling; however, the LMNP electrode achieved this transition more rapidly, resulting in earlier structural stabilization and enhanced electrochemical performance. These findings provide critical insights into the application of liquid metal-based electrodes and offer valuable guidance for designing high-performance anode materials for lithium-ion batteries.

Key words: lithium-ion battery, liquid metal, anode, electrochemical performance, self-healing effect

CLC Number:

TQ 15

Wenyan CHEN, Ruilin HE, Jian CHANG, Yonghong DENG. Investigation of lithium storage mechanisms in liquid metal electrodes with different morphologies[J]. Energy Storage Science and Technology, 2025, 14(9): 3290-3300.

Figures/Tables 9

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References 27

[1]	李文俊, 徐航宇, 杨琪, 等. 高能量密度锂电池开发策略[J]. 储能科学与技术, 2020, 9(2): 448-478. DOI: 10.19799/j.cnki.2095-4239. 2020-0050.
	LI W J, XU H Y, YANG Q, et al. Development of strategies for high-energy-density lithium batteries[J]. Energy Storage Science and Technology, 2020, 9(2): 448-478. DOI: 10.19799/j.cnki.2095-4239.2020-0050.
[2]	ARMAND M, AXMANN P, BRESSER D, et al. Lithium-ion batteries—Current state of the art and anticipated developments[J]. Journal of Power Sources, 2020, 479: 228708. DOI: 10.1016/j.jpowsour.2020.228708.
[3]	MIAO Y P, LIU L L, ZHANG Y P, et al. An overview of global power lithium-ion batteries and associated critical metal recycling[J]. Journal of Hazardous Materials, 2022, 425: 127900. DOI: 10.1016/j.jhazmat.2021.127900.
[4]	杜进桥, 田杰, 李艳, 等. 锂离子电池石墨负极失效及其先进表征方法[J]. 储能科学与技术, 2024, 13(10): 3467-3479. DOI: 10.19799/j.cnki.2095-4239.2024.0284.
	DU J Q, TIAN J, LI Y, et al. Failure of graphite negative electrode in lithium-ion batteries and advanced characterization methods[J]. Energy Storage Science and Technology, 2024, 13(10): 3467-3479. DOI: 10.19799/j.cnki.2095-4239.2024.0284.
[5]	LI J W, WANG T D, WANG Y J, et al. Solid-liquid-solid growth of doped silicon nanowires for high-performance lithium-ion battery anode[J]. Nano Energy, 2025, 133: 110455. DOI: 10.1016/j.nanoen.2024.110455.
[6]	尹坚, 董季玲, 丁皓, 等. 锂离子电池过渡金属氧化物负极材料研究进展[J]. 储能科学与技术, 2021, 10(3): 995-1001. DOI: 10.19799/j.cnki.2095-4239.2020.0412.
	YIN J, DONG J L, DING H, et al. Research progress of transition metal oxide anode materials for lithium-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(3): 995-1001. DOI: 10.19799/j.cnki.2095-4239.2020.0412.
[7]	LI X W, WANG J H, YANG L F, et al. Element screening engineering for high-entropy alloy anodes: Achieving fast and robust Li-storage with optimal working potential[J]. Advanced Materials, 2024, 36(48): 2409278. DOI: 10.1002/adma.202409278.
[8]	PONNURU H, MARRIAM I, RAMBUKWELLA I, et al. Recent advances in liquid metals for rechargeable batteries[J]. Advanced Functional Materials, 2024, 34(31): 2309706. DOI: 10.1002/adfm.202309706.
[9]	陈玉, 夏鑫. 可充电电池的镓基液态金属负极材料研究进展[J]. 电源技术, 2021, 45(1): 132-135.
	CHEN Y, XIA X. Research progress of gallium-based liquid metal anode materials for rechargeable batteries[J]. Chinese Journal of Power Sources, 2021, 45(1): 132-135.
[10]	张剑峰, 陈玉, 刘航, 等. 碳基GaSn合金负极材料的制备及其电化学性能[J]. 化工新型材料, 2024, 52(10): 90-95. DOI: 10.19817/j.cnki.issn1006-3536.2024.10.047.
	ZHANG J F, CHEN Y, LIU H, et al. Preparation and electrochemical performance analysis of carbon-based GaSn alloy anode materials[J]. New Chemical Materials, 2024, 52(10): 90-95. DOI: 10.19817/j.cnki.issn1006-3536.2024.10.047.
[11]	张春小, 崔丹丹, 杜轶, 等. 镓基液态金属的结构与物性[J]. 自然杂志, 2023, 45(5): 340-354. DOI: 10.3969/j.issn.0253-9608.2023.05.003.
	ZHANG C X, CUI D D, DU Y, et al. Structure and physical properties of gallium-based liquid metal[J]. Chinese Journal of Nature, 2023, 45(5): 340-354. DOI: 10.3969/j.issn.0253-9608. 2023.05.003.
[12]	SONG M J, WANG Y, YU B, et al. A high-performance room-temperature magnesium ion battery with self-healing liquid alloy anode mediated with a bifunctional intermetallic compound[J]. Chemical Engineering Journal, 2022, 450: 138176. DOI: 10.1016/j.cej.2022.138176.
[13]	GU J N, TAO Y, CHEN H, et al. Stress-release functional liquid metal-MXene layers toward dendrite-free zinc metal anodes[J]. Advanced Energy Materials, 2022, 12(16): 2200115. DOI: 10. 1002/aenm.202200115.
[14]	FU H, LIU G C, XIONG L Y, et al. A shape-variable, low-temperature liquid metal-conductive polymer aqueous secondary battery[J]. Advanced Functional Materials, 2021, 31(50): 2107062. DOI: 10.1002/adfm.202107062.
[15]	WEI C L, TAN L W, TAO Y, et al. Interfacial passivation by room-temperature liquid metal enabling stable 5 V-class lithium-metal batteries in commercial carbonate-based electrolyte[J]. Energy Storage Materials, 2021, 34: 12-21. DOI: 10.1016/j.ensm.2020. 09.006.
[16]	尹富强, 赵玉辰, 李赵春. 镓基液态金属应用的研究进展[J]. 现代化工, 2022, 42(5): 24-29. DOI: 10.16606/j.cnki.issn0253-4320.2022.05.005.
	YIN F Q, ZHAO Y C, LI Z C. Advances on application of gallium-based liquid metal[J]. Modern Chemical Industry, 2022, 42(5): 24-29. DOI: 10.16606/j.cnki.issn0253-4320.2022.05.005.
[17]	WEI C L, FEI H F, TIAN Y, et al. Room-temperature liquid metal confined in MXene paper as a flexible, freestanding, and binder-free anode for next-generation lithium-ion batteries[J]. Small, 2019, 15(46): 1903214. DOI: 10.1002/smll.201903214.
[18]	ZHANG H N, CHEN P Y, XIA H, et al. An integrated self-healing anode assembled via dynamic encapsulation of liquid metal with a 3D Ti₃C₂Tx network for enhanced lithium storage[J]. Energy & Environmental Science, 2022, 15(12): 5240-5250. DOI: 10.1039/D2EE02147A.
[19]	HUANG C H, GUO B Y, WANG X D, et al. Alkali-ion batteries by carbon encapsulation of liquid metal anode[J]. Advanced Materials, 2024, 36(4): 2309732. DOI: 10.1002/adma.202309732.
[20]	LIN X R, CHEN A, YANG C Y, et al. A room-temperature self-healing liquid metal-infilled microcapsule driven by coaxial flow focusing for high-performance lithium-ion battery anode[J]. Small, 2024, 20(16): 2307071. DOI: 10.1002/smll.202307071.
[21]	WANG K Z, HU J, CHEN T Y, et al. CuGa₂ transition phase anchored liquid GaSn achieves high-performance liquid metal battery cathode[J]. Journal of Energy Storage, 2024, 89: 111879. DOI: 10.1016/j.est.2024.111879.
[22]	YANG J H, ZHOU W, HU J M, et al. Universal renaissance strategy of metal fluoride in secondary ion batteries enabled by liquid metal gallium[J]. Advanced Materials, 2023, 35(28): 2301442. DOI: 10.1002/adma.202301442.
[23]	LIN X R, CHEN A, YANG C Y, et al. A room-temperature self-healing liquid metal-infilled microcapsule driven by coaxial flow focusing for high-performance lithium-ion battery anode[J]. Small, 2024, 20(16): 2307071. DOI: 10.1002/smll.202307071.
[24]	WANG Q Y, ZHU M, CHEN G R, et al. High-performance microsized Si anodes for lithium-ion batteries: Insights into the polymer configuration conversion mechanism[J]. Advanced Materials, 2022, 34(16): 2109658. DOI: 10.1002/adma.202109658.
[25]	HAN B, ZOU Y C, KE R H, et al. Stable lithium metal anodes with a GaOx artificial solid electrolyte interphase in damp air[J]. ACS Applied Materials & Interfaces, 2021, 13(18): 21467-21473. DOI: 10.1021/acsami.1c04196.
[26]	HAN B, XU D W, CHI S S, et al. 500 Wh/kg class Li metal battery enabled by a self-organized core-shell composite anode[J]. Advanced Materials, 2020, 32(42): 2004793. DOI: 10.1002/adma.202004793.
[27]	NI J F, ZHU X C, YUAN Y F, et al. Rooting binder-free tin nanoarrays into copper substrate via tin-copper alloying for robust energy storage[J]. Nature Communications, 2020, 11: 1212. DOI: 10.1038/s41467-020-15045-x.

Materials	Current density/(A/g)	Cycle number	Capacity/capacity retention/%	Ref.
LMNP	2.0	300	399.3/86.9%	this work
LM-Ti₃C₂T _x	5	4500	409.8/90.8%	[18]
EGaIn@C	1	800	644/-	[19]
CF/O-GaSn	0.16	150	364.7/-	[21]
Ga/LiF	0.5	100	712/-	[22]
LMMs	5	5000	413/-	[23]