硅酸盐学报

弹性聚合物固态电解质界面膜保护金属锂负极

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卢微 ¹^,² , 王子豪 ¹^,³ , 赵安顺 ¹^,³ , 于明希 ¹^,³ , 杜米 ¹^,³ , 赵雪 ¹^,³ , 张文静 ¹^,³ , 刘梅 ³ , 冯明 ¹^,³

硅酸盐学报 | 研究论文 2024,52(7): 2187-2196

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硅酸盐学报 |研究论文 2024 , 52 (7) : 2187 -2196

弹性聚合物固态电解质界面膜保护金属锂负极

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卢微¹^,², 王子豪¹^,³, 赵安顺¹^,³, 于明希¹^,³, 杜米¹^,³, 赵雪¹^,³, 张文静¹^,³, 刘梅³, 冯明¹^,³

作者信息

^1．吉林师范大学，功能材料物理与化学教育部重点实验室，长春 130103

^2．吉林师范大学信息技术学院，吉林四平 136000

^3．吉林师范大学物理学院，吉林四平 136000

通讯作者:

刘梅（1976—），女，博士，教授；

冯明（1981—），男，博士，教授。

作者简介:

卢微（1990—），女，博士，讲师。

Elastic Polymer Solid Electrolyte Interphase Protects Lithium Metal Anode

Wei LU¹^,², Zihao WANG¹^,³, Anshun ZHAO¹^,³, Mingxi YU¹^,³, Mi DU¹^,³, Xue ZHAO¹^,³, Wenjing ZHANG¹^,³, Mei LIU³, Ming FENG¹^,³

Affiliations

^1.Key Laboratory of Functional Materials Physics and Chemistry Ministry of Education, Jilin Normal University, Changchun 130103, China

^2.College of Information Technology, Jilin Engineering Research Center of Optoelectronic Materials and Devices, Jilin Normal University, Siping 136000, Jilin, China

^3.College of Physics, Jilin Normal University, Siping 136000, Jilin, China

Corresponding Author:

LIU Mei (1976-), female, Ph.D., Professor. E-mail: liumei@jlnu.edu.cn

FENG Ming (1981-), male, Ph.D., Professor. E-mail: mingfeng@jlnu.edu.cn

LU Wei (1990-), female, Ph.D., Lecturer. E-mail: luwei@jlnu.edu.cn

出版时间: 2024-07-20 doi: 10.14062/j.issn.0454-5648.20240063

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摘要

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固态电解质界面膜（SEI）的性质直接影响着锂金属电池中金属锂负极的稳定性。本文通过原位紫外光聚合方法构筑了弹性聚合物人工固态电解质界面膜（EP-SEI）保护的金属锂负极。这种EP-SEI具有优异的均匀性、稳定性和弹性，在电池循环中促进锂离子均匀沉积。这些特性可以抑制锂枝晶的生成，缓冲金属锂负极在循环时的体积变化，有效保护金属锂负极。这种EP-SEI保护的金属锂负极组装的LFP || Li电池和NCM811 || Li电池在0.5 C倍率下的最高容量分别可达到164.1 mA·h·g^-1和187.1 mA·h·g^-1，并稳定循环500圈。

关键词

人工固态电解质界面 / 金属锂负极 / 锂金属电池 / 聚合物 / 高弹性

Abstract

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Introduction

Lithium metal batteries (LMBs) are regarded as candidates for next-generation batteries due to their low electrochemical potential (i.e., -3.040 V vs. standard hydrogen electrode) and high theoretical specific capacity (i.e., 3 860 mA·h·g^-1). Lithium (Li) metal anode is susceptible to side reactions with organic electrolytes, leading to the uneven formation of the solid electrolyte interphase (SEI). The non-uniformity and fragility of the SEI can aggravate the growth of Li dendrites and excessive electrolyte consumption, ultimately resulting in a rapid attenuation of capacity and safety risks. These issues severely hinder the commercialization of LMBs. The development of an artificial SEI is crucial for protecting Li metal anode, suppressing Li dendrite growth, and accommodating volume changes during cycling. This advancement is essential for improving the stability and cycling life of LMBs.

In this paper, we synthesized an artificial elastic polymer SEI (EP-SEI) constructed on the surface of Li metal anode by an in-situ UV-curing method. The main composition of EP-SEI was poly (ethyleneglycol) diacrylate-co-vinylene carbonate (PEGDA-CO-VC) cross-linking polymer.

Methods

For the synthesis of an artificial elastic polymer SEI (EP-SEI) constructed on the surface of Li metal anode by an in-situ UV-curing method, polyethylene glycol diacrylate (PEGDA) and vinylene carbonate (VC) were mixed in a mass ratio of 4∶1 (i.e., 80 mg and 20 mg) under stirring. Afterwards, 2 mL of dimethoxyethane (DME) was added for dissolution. Subsequently, the mixture was dripped onto Li metal foils, followed by polymerization under a mercury lamp after the addition of 2-hydroxy-2-methylpropiophenone (HMPP). This method utilized UV light to rapidly excite the unsaturated bonds of polymer monomers, thereby shortening the polymerization reaction time and enhancing the preparation efficiency of the artificial SEI. This method was simple to operate, conducive to batch production, and aids in advancing the commercialization of LMB. The LMBs were assembled with LiFePO₄ (LFP) or LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) as a cathode material, Li metal foil as an anode, polypropylene (PP) as a separator, and 1 M LiPF₆ EC/DEC as an electrolyte. The batteries were assembled in a glove box filled with argon to ensure a moisture-free and oxygen-free environment during the process.

Results and discussion

An artificial EP-SEI with PEGDA-co-VC was prepared on the surface of Li metal by an in-situ UV-curing polymerization method. The thickness of EP-SEI is 1.6 μm. The EP-SEI exhibits an uniform and dense morphology and tightly covers the surface of Li metal. In the results of electrochemical test, Li symmetric (Li || Li) cells assembled with EP-SEI protected Li exhibit highly reversible electrochemical behavior and faster charge transfer rates. The Li || Li cells with EP-SEI Li maintain stable cycling at a current density of 1 mA·cm^-2 and a capacity density of 1 mA·h·cm^-2 for over 300 h. And the impedance values of Li || Li cells with EP-SEI Li continuously decrease during the cycle, and eventually stabilize at 15 Ω. This indicates that EP-SEI exhibits a high stability during prolonged electrochemical reactions and a high lithium ion conductivity. In the results of Li ||Cu cells test, the low nucleation overpotential (μ_nuc) and plateau potential (μ_pla) indicate a reduction in the nucleation energy barrier for Li deposition. It is confirmed that EP-SEI can promote the uniform deposition of Li⁺ on the surface of Li metal. After cycling of Li ||Cu cell with EP-SEI Cu, the thickness of Li⁺ deposition approaches the theoretical thickness. The surface of EP-SEI Cu remains smooth and flat without the growth of Li dendrites. In the results of full cell test, the LFP || Li batteries with EP-SEI Li exhibit a discharge specific capacity of 164.1 mA·h·g^-1 and a capacity retention rate of 72% after 500 cycles with a coulombic efficiency of 98.5% at 0.5 C rate. The NCM811 || Li batteries with EP-SEI Li maintain a discharge specific capacity of 100 mA·h·g^-1 after 500 cycles. This demonstrates that EP-SEI effectively reduces electrolyte consumption and improves coulomb efficiency, cycle stability and safety of LMBs.

Conclusions

In this study, an elastic polymer artificial solid electrolyte interphase membrane (EP-SEI) was constructed on the Li metal anode by an in-situ UV-curing polymerization method. This EP-SEI exhibited excellent uniformity, stability and elasticity, promoting the uniform deposition of Li⁺ during cycling. These properties indicated that EP-SEI could inhibit Li dendrite formation, buffer the volume changes of the Li metal anode, and reduce electrolyte consumption. The LFP || Li and NCM811 || Li batteries assembled with EP-SEI-protected Li metal anodes achieved discharge specific capacities of 164.1 mA·h·g^-1 and 187.1 mA·h·g^-1 at 0.5 C rate, respectively. The LMBs maintained stable cycling for 500 cycles. The EP-SEI could effectively protect the Li metal anode, improve the coulombic efficiency and extend the cycling life of LMB. The EP-SEI protected Li metal anode provided the possibilities for the commercialization of LMBs.

Key words

artificial solid electrolyte interphase / lithium metal anode / lithium metal battery / polymer / high elasticity

引用本文

卢微, 王子豪, 赵安顺, 于明希, 杜米, 赵雪, 张文静, 刘梅, 冯明. 弹性聚合物固态电解质界面膜保护金属锂负极. 硅酸盐学报, 2024 , 52 (7) : 2187 -2196 . DOI: 10.14062/j.issn.0454-5648.20240063

Wei LU, Zihao WANG, Anshun ZHAO, Mingxi YU, Mi DU, Xue ZHAO, Wenjing ZHANG, Mei LIU, Ming FENG. Elastic Polymer Solid Electrolyte Interphase Protects Lithium Metal Anode[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (7) : 2187 -2196 . DOI: 10.14062/j.issn.0454-5648.20240063

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吉林省科学技术厅项目(YDZJ202201ZYTS304)

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2024年第52卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240063

接收时间：2024-01-23
首发时间：2026-10-22
出版时间：2024-07-20

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收稿日期：2024-01-23
修回日期：2024-02-09

基金

吉林省科学技术厅项目(YDZJ202201ZYTS304)

作者信息

^1．吉林师范大学，功能材料物理与化学教育部重点实验室，长春 130103

^2．吉林师范大学信息技术学院，吉林四平 136000

^3．吉林师范大学物理学院，吉林四平 136000

通讯作者:

刘梅（1976—），女，博士，教授；

冯明（1981—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240063

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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