Cu-In/Bi alloys with lithiophilic sites induce uniform lithium nucleation for high-rate lithium-metal batteries

doi:10.19799/j.cnki.2095-4239.2023.0318

Abstract

Abstract:

Lithium metal is an ideal anode material for lithium batteries for its high theoretical specific capacity and low electrochemical potential. However, the commercial application of lithium metal anodes is limited due to problems such as dendrite growth and volume expansion. Therefore, it is particularly important to design a rational three-dimensional framework for the cycling stability of lithium metal anodes.In this work, porous Copper-Indium/Bismuth (Cu-In/Bi) alloy frameworks containing lithiophilic sites were prepared by vapor phase dealloying based on the difference in saturated vapor pressure between various metals and Kirkendall's effect. Then, it was followed by the fabrication of composite lithium metal anodes (3D Cu-InLi-Li and 3D Cu-LiBi-Li) with pre-stored lithium for high-rate lithium-metal batteries by the molten lithium infusion. The samples were characterized by X-ray Diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy(EDS), and the effects of indium and bismuth alloys as lithiophilic sites on the electrochemical performance of the lithium metal anode were researched. The experimental results showed that the porous copper electrodes had a low nucleation overpotential and exhibited excellent cycling stability. Paired with the LiFePO₄ cathode, after 1000 cycling at 10 ℃, the reversible specific capacities of the composite lithium metal anode were 65.7 mAh/g (3D Cu-LiBi-Li) and 61.9 mAh/g (3D Cu-InLi-Li), respectively, significantly higher than that of the commercial lithium foil (55.7 mAh/g). Cycling tests at 10 ℃ showed that indium and bismuth alloys improved the cycling stability oflithium metal anodes.The present work has high application value in preparing lithium metal anode by vapor phase dealloying and molten lithium infusion.

Key words: lithiummetal anode, 3D porous alloy framework, vapor phasede alloying, Li-In alloy, Li-Bi alloy

CLC Number:

O 646.21

Wenbiao LI, Haitao GENG, Yibo GAO, Zhaoshun GAO, Bao WANG. Cu-In/Bi alloys with lithiophilic sites induce uniform lithium nucleation for high-rate lithium-metal batteries[J]. Energy Storage Science and Technology, 2023, 12(9): 2735-2745.

Figures/Tables 8

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Eletrode	Active mass/mg	Area/cm²	Areal capacity /(mAh/g)	N/P
LiFePO₄	2.42	1.13	0.36	—
3D Cu-LiBi-Li	23.04	1.62	54.9	152.50
3D Cu-InLi-Li	30.34	1.66	70.55	195.97

Anodes	0.5C/(mAh/g)	1C/(mAh/g)	2C/(mAh/g)
3D Cu-InLi-Li	149.4	138.5	122.7
3D Cu-LiBi-Li	147.7	137.9	122.9
Cu-Ge@Li^[33]	136	112	70
1D@3D-Cu/Sb-Li^[34]	～135	～122	～105
Li-3D HCu-Ag^[35]	138.4	124.9	107.6
Al-Li^[36]	146.5	137.3	121.3
CNT-Li^[37]	136.3	127.9	118.1

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