定制电解液或隔膜实现锂离子各向异性输运从而抑制枝晶生长：相场模拟研究

doi:10.3866/PKU.WHXB202305053

物理化学学报 >> 2024, Vol. 40 >> Issue (3): 2305053.doi: 10.3866/PKU.WHXB202305053

所属专题：固态电池

定制电解液或隔膜实现锂离子各向异性输运从而抑制枝晶生长：相场模拟研究

李亚捷¹, 陈斌¹, 王依平¹, 邢辉²^,³^,*(), 赵伟¹, 张更⁴^,*(), 施思齐¹^,⁵^,⁶^,*()

¹ 上海大学材料科学与工程学院, 上海 200444
² 西北工业大学超常条件材料物理与化学教育部重点实验室, 西安 710129
³ 西北工业大学陕西省基础学科(液体物理)研究中心, 西安 710129
⁴ 阿卜杜拉国王科技大学物理科学与工程系, 图瓦 23955-6900, 沙特阿拉伯
⁵ 上海大学材料基因组工程研究院, 上海 200444
⁶ 之江实验室, 杭州 311100

收稿日期:2023-05-29 修回日期:2023-07-14 录用日期:2023-07-14 发布日期:2023-07-31
通讯作者: Email: huixing@nwpu.edu.cn (邢辉)geng.zhang@kaust.edu.sa (张更)sqshi@shu.edu.cn (施思齐)
基金资助:
国家自然科学基金(52102280); 国家自然科学基金(U2030206); 国家重点研发计划(2021YFB3802104); 上海市科学技术委员会(19DZ2252600); 上海市浦江人才计划(2019PJD016); 之江实验室科研攻关项目(2021PE0AC02)

Inhibiting Dendrite Growth by Customizing Electrolyte or Separator to Achieve Anisotropic Lithium-Ion Transport: A Phase-Field Study

Yajie Li¹, Bin Chen¹, Yiping Wang¹, Hui Xing²^,³^,*(), Wei Zhao¹, Geng Zhang⁴^,*(), Siqi Shi¹^,⁵^,⁶^,*()

¹ School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
² MOE Key Laboratory of Material Physics and Chemistry under Extraordinary, Northwestern Polytechnical University, Xi'an 710129, China
³ Shaanxi Basic Discipline (Liquid Physics) Research Center, Northwestern Polytechnical University, Xi'an 710129, China
⁴ Physical Science and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
⁵ Materials Genome Institute, Shanghai University, Shanghai 200444, China
⁶ Zhejiang Laboratory, Hangzhou 311100, China

Received:2023-05-29 Revised:2023-07-14 Accepted:2023-07-14 Published:2023-07-31
Contact: Email: huixing@nwpu.edu.cn (Hui Xing)geng.zhang@kaust.edu.sa (Geng Zhang)sqshi@shu.edu.cn (Siqi Shi)
Supported by:
the National Natural Science Foundation of China(52102280); the National Natural Science Foundation of China(U2030206); the National Key Research and Development Program of China(2021YFB3802104); the Shanghai Municipal Science and Technology Commission(19DZ2252600); the Shanghai Pujiang Program(2019PJD016); the Scientific Research Project of Zhejiang Laboratory(2021PE0AC02)

1. 附件.pdf(1678KB)

摘要/Abstract

摘要：

电池内部不可控的枝晶生长问题严重地影响着电池的循环性能和安全性能，这对于锂金属电池的实际应用是一个严峻的挑战。尽管已有较多的实验和理论研究工作聚焦于电极间锂离子各向异性输运特性对枝晶形貌的影响，但仍有一些开放性的问题有待进一步研究，例如，如何将枝晶生长的动态演变与电解液性质、电势分布或隔膜多孔结构诱导的锂离子各向异性输运关联起来。我们通过将锂离子在电解液中的扩散系数(D_L)表示为二阶张量的形式并进行相场模拟，发现D_yy : D_xx比值的增加，以及电势诱导的电极/电解液界面锂离子快速扩散层均可以降低界面处锂离子浓度梯度和电势梯度，从而减弱枝晶生长的驱动力。我们还发现隔膜基体与y方向之间夹角的增大也会显著促进电解液中的锂离子各向异性输运特性，以利于抑制枝晶生长。籍此本文提出设计D_yy : D_xx = 10 : 1的电解液和基体倾斜角为arctan(0.5)的隔膜用于锂金属电池。该相场研究有望为设计具有抑制枝晶能力的电解液或隔膜提供指导。

关键词: 锂枝晶, 相场模拟, 电解液, 隔膜, 锂离子扩散系数

Abstract:

Lithium metal is a promising anode candidate for high-energy-density secondary batteries due to its high theoretical capacity and low electrochemical potential, while the uncontrolled dendrite growth causing poor cycling performance and safety concerns poses serious challenges for the practical application of lithium metal batteries. During the electrodeposition process, the lithium-ion (Li⁺) diffusion process is directly related to the electrode/electrolyte interfacial Li⁺ concentration gradient as well as the dendritic morphology. Regulating the anisotropic Li⁺ diffusion property is a convenient way to reshape its transfer behavior without introducing any external fields (e.g., temperature field, magnetic field, acoustic field, etc.) or increasing the weight of batteries. Despite the large amount of experimental and theoretical work on the effect of the anisotropic Li⁺ diffusion behavior on the dendritic morphology, some open questions remain to be deliberated, e.g., correlating the dynamic evolution of dendrite growth with the anisotropic Li⁺ diffusion induced by the electrolyte property, electric potential, and separator structure. In this paper, an electrochemical phase-field model is applied to explore the influences of electrolyte inherent anisotropic Li⁺ diffusion, electric potential-induced anisotropic Li⁺ diffusion, and separator-structure-induced anisotropic Li⁺ migration on dendrite growth via a homemade MATLAB code. Instead of a fixed numerical value, the modified Li⁺ diffusivity in the electrolyte (D_L) is expressed as a second-order tensor by decomposing into two components along the x (D_xx) and y (D_yy) directions, which is not only able to explore the electrolyte inherent anisotropic Li⁺ diffusion but also easy to describe the electric potential-induced fluctuations of D_L and the corresponding Li⁺ concentration distribution. Predicted results indicate that with the increase of D_yy : D_xx, the interfacial Li⁺ concentration gradient is alleviated due to the accelerated longitudinal Li⁺ replenishment and decelerated transversal "entrainment" phenomenon, thus decreasing the driving force of dendrite growth. Besides, the electric potential-induced interfacial Li⁺ fast diffusion layer can also reduce the electric potential gradients surrounding the dendrite tips and then uniform the dendrite morphologies. Surprisingly, separators with higher matrix tilt angles are demonstrated to achieve effective anisotropic Li⁺ diffusion in electrolyte, which can not only reduce the dendrite-growth velocity, but also extend the dendrite-growth pathway and prolong the battery short circuit time. Following this, electrolyte with the D_yy : D_xx = 10 : 1 and separator with the matrix tilt angle of arctan(0.5) are evaluated as promising materials for lithium metal batteries. This study provides a rational guidance for designing electrolytes or separators with dendrite-inhibiting capability.

Key words: Lithium dendrite, Phase-field simulation, Electrolyte, Separator, Lithium-ion diffusivity

李亚捷, 陈斌, 王依平, 邢辉, 赵伟, 张更, 施思齐. 定制电解液或隔膜实现锂离子各向异性输运从而抑制枝晶生长：相场模拟研究[J]. 物理化学学报, 2024, 40(3), 2305053. doi: 10.3866/PKU.WHXB202305053

Yajie Li, Bin Chen, Yiping Wang, Hui Xing, Wei Zhao, Geng Zhang, Siqi Shi. Inhibiting Dendrite Growth by Customizing Electrolyte or Separator to Achieve Anisotropic Lithium-Ion Transport: A Phase-Field Study[J]. Acta Phys. -Chim. Sin. 2024, 40(3), 2305053. doi: 10.3866/PKU.WHXB202305053

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202305053

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I3/2305053

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Parameter	Symbol	Value	Ref.
Interfacial mobility of ξ	L_ξ	2.5 × 10⁻⁶ m³∙J⁻¹∙s⁻¹	30
Interfacial mobility of φ	L_φ	5 × 10⁻⁸ m³∙J⁻¹∙s⁻¹	40
Kinetic coefficient	L_η	1 s⁻¹	30
Barrier height	W	1.334 × 10⁻⁷ J∙m⁻³
Gradient energy coefficient 1	κ₀	4.17 × 10⁻⁵ J∙m⁻¹
Gradient energy coefficient 2	κ_φ	8.34 × 10⁻⁵ J∙m⁻¹
Anisotropic mode	ω	4	30
Anisotropic strength	r	0.05	30
Charge transfer coefficient	α	0.5	30
Conductivity in electrolyte	σ_L	2.67 S∙m⁻¹	41
Conductivity in electrode	σ_S	1.0 × 10⁻⁷ S∙m⁻¹	30
Scalar Li⁺ diffusivity in the electrode	D_S	3.68 × 10⁻¹³ m²∙s⁻¹	41
Scalar Li⁺ diffusivity in the electrolyte	D_L	3.68 × 10⁻¹⁰ m²∙s⁻¹	41
Faraday constant	F	9.6485 × 10⁴ C∙mol⁻¹
Transferred number of electrons	z⁺	1

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定制电解液或隔膜实现锂离子各向异性输运从而抑制枝晶生长：相场模拟研究

Inhibiting Dendrite Growth by Customizing Electrolyte or Separator to Achieve Anisotropic Lithium-Ion Transport: A Phase-Field Study

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