基于P2D-SEI改进模型的LiPF<sub>6</sub>三元电解液延缓老化研究

林孜翰; 杨廷方; 苏泓锭; 欧龙翔; 肖恩荣

doi:10.19799/j.cnki.2095-4239.2026.0844

您当前的位置：

首页 >

文章列表页 >

基于P2D-SEI改进模型的LiPF₆三元电解液延缓老化研究

XXXX | 更新时间：2026-10-31

- 基于P2D-SEI改进模型的LiPF₆三元电解液延缓老化研究
- Aging Characteristics and Composition Optimization of LiPF6/EC-EMC-DMC Ternary Electrolytes Based on an Improved P2D-SEI Model
- 储能科学与技术 2026年页码：1-14
- 作者机构：
  
  长沙理工大学湖南长沙 410114
- 作者简介：
  
  林孜翰（2003—），男，湖南人，硕士生，主要从事锂电池老化研究（E-mail：1309452798@qq.com.）
  杨廷方（1972—），男，湖南人，副教授，博士，硕导，主要从事高电压研究（E-mal：2630544839@qq.com.
- 基金信息：
  
  湖南省自然科学基金（面上项目）(2022JJ30043)
- DOI：10.19799/j.cnki.2095-4239.2026.0844
  中图分类号： TM 912
- 收稿：2026-09-24，
  
  修回：2026-10-22，
  
  网络首发：2026-10-31，
- 稿件说明：
移动端阅览
林孜翰, 杨廷方, 苏泓锭, 等. 基于P2D-SEI改进模型的LiPF₆三元电解液延缓老化研究[J]. 储能科学与技术, XXXX, XX(XX): 1-14. DOI: 10.19799/j.cnki.2095-4239.2026.0844.

Lin Kris, Yang Tingfang, Su Hongding, et al. Aging Characteristics and Composition Optimization of LiPF6/EC-EMC-DMC Ternary Electrolytes Based on an Improved P2D-SEI Model[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-14.
林孜翰, 杨廷方, 苏泓锭, 等. 基于P2D-SEI改进模型的LiPF₆三元电解液延缓老化研究[J]. 储能科学与技术, XXXX, XX(XX): 1-14. DOI: 10.19799/j.cnki.2095-4239.2026.0844. DOI：

Lin Kris, Yang Tingfang, Su Hongding, et al. Aging Characteristics and Composition Optimization of LiPF6/EC-EMC-DMC Ternary Electrolytes Based on an Improved P2D-SEI Model[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-14. DOI： 10.19799/j.cnki.2095-4239.2026.0844.

摘要

针对传统P2D-SEI模型对三元电解液组分演化及液相传输描述不足的问题，本文以LiPF

/EC-EMC-DMC体系为研究对象，在P2D-SEI耦合老化模型基础上引入三元组分演化关系和DMC相关液相传输修正，并比较候选溶剂配比及LiPF

浓度的模型响应。溶剂配比比较中，EC:EMC:DMC=10:20:70在模型输出平均SEI膜厚度、诊断极化及盐浓度分布方面表现出较为协调的变化趋势。固定该配比后，五种LiPF

浓度下各指标的极值并不重合：模型关联式估算的初始电导率在1.4 mol·L

¹附近最高，且与1.6 mol·L

¹基本持平；1.0 mol·L

¹的q=0.1～0.9平均总极化及q=0.9极化最低；1.6 mol·L

¹的相对盐浓度差最低。综合传输与诊断响应，1.4 mol·L

¹可作为当前候选范围内的折中浓度，但并非所有单项指标的最优值。SOH校准曲线用于实验对照，不等同于独立验证；其他结论为当前模型与所考察工况范围内的预测结果，可为配方筛选和后续实验验证提供参考。

Abstract

This study examines LiPF

/EC-EMC-DMC electrolytes using a coupled P2D-SEI aging model that incorporates ternary-solvent composition evolution and DMC-related liquid-phase transport corrections. Candidate solvent ratios and LiPF

concentrations are evaluated through model outputs. Within the investigated solvent range

EC:EMC:DMC = 10:20:70 shows a relatively balanced response in model-predicted average SEI thickness

diagnostic polarization

and electrolyte salt distribution. At this fixed solvent ratio

he performance extrema occur at different concentrations: the model-estimated initial conductivity is highest near 1.4 mol·L

¹ and is nearly unchanged at 1.6 mol·L

¹; 1.0 mol·L

¹ gives the lowest average absolute polarization over q=0.1–0.9 and the lowest polarization at q=0.9; and 1.6 mol·L

¹ yields the smallest relative salt-concentration difference. Considering the transport and diagnostic responses together

1.4 mol·L

¹ is a compromise candidate within the investigated range

not the optimum for every individual metric. The SOH calibration curve is used for comparison with experimental data and does not constitute independent validation; the remaining conclusions are model predictions limited to the investigated formulations and conditions.

关键词

Keywords

references

PELED E.The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems—The solid electrolyte interphase model[J].Journal of The Electrochemical Society,1979,126(12):2047-2051.

周思飞, 李骏, 王小飞, 张道明, 薛浩亮. 锂电池电解液电导率模型研究进展[J]. 储能科学与技术, 2022, 11(11): 3688-3698. DOI:10.19799/j.cnki.2095-4239.2022.0344.

XU K.Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J].Chemical Reviews,2004,104(10):4303-4417.

邢丽丹,谢启明,李伟善.电解液及其界面电化学性质的机理研究进展[J].物理学报,2020,69(22):228205.

VERMA P,MAIRE P,NOVÁK P.A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries[J].Electrochimica Acta,2010,55(22):6332-6341.

张慧敏, 王京, 王一博, 郑家新, 邱景义, 曹高萍, 张浩. 锂离子电池SEI多尺度建模研究展望[J]. 储能科学与技术, 2023, 12(2): 366-382.

VETTER J,NOVÁK P,WAGNER M R,et al.Ageing mechanisms in lithium-ion batteries[J].Journal of Power Sources,2005,147(1-2):269-281.

祝庆伟, 俞小莉, 吴启超, 徐一丹, 陈芬放, 黄瑞. 高能量密度锂离子电池老化半经验模型[J]. 储能科学与技术, 2022, 11(7): 2324-2331. DOI:10.19799/j.cnki.2095-4239.2021.0725.

AURBACH D,LEVI M D,LEVI E,et al.Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides[J].Journal of The Electrochemical Society,1998,145(9):3024-3034.

XU K.Electrolytes and interphases in Li-ion batteries and beyond[J].Chemical Reviews,2014,114(23):11503-11618.

昝文达, 张睿, 丁飞. 锂离子电池电化学模型发展与应用[J]. 储能科学与技术, 2023, 12(7): 2302-2318. DOI:10.19799/j.cnki.2095-4239.2023.0296.

ZHANG S S,JOW T R,AMINE K,HENRIKSEN G L.LiPF6-EC-EMC electrolyte for Li-ion battery[J].Journal of Power Sources,2002,107(1):18-23.

GRÜTZKE M,KRAFT V,HOFFMANN B,et al.Aging investigations of a lithium-ion battery electrolyte from a field-tested hybrid electric vehicle[J].Journal of Power Sources,2015,273:83-88.

KLETT M,GILBERT J A,PUPEK K Z,et al.Layered oxide,graphite and silicon-graphite electrodes for lithium-ion cells:Effect of electrolyte composition and cycling windows[J].Journal of The Electrochemical Society,2017,164(1):A6095-A6102.

WU X,LIU T,BAI Y,et al.Effects of solvent formulations in electrolytes on fast charging of Li-ion cells[J].Electrochimica Acta,2020,353:136453.

UCHIDA S, KIYOBAYASHI T. How does the solvent composition influence the transport properties of electrolyte solutions? LiPF6 and LiFSA in EC and DMC binary solvent[J]. Physical Chemistry Chemical Physics, 2021, 23(18): 10875-10887. DOI: 10.1039/D1CP00967B.

IDE Y,TODOROV Y M,DEGUCHI M,ABE K.DMC-rich,low-EC,moderately concentrated electrolytes for lithium-ion batteries:Roles of solvent composition and salt concentration[J].Journal of Power Sources,2026,681:240242.

SPOTTE-SMITH E W C,BLAU S M,XIE X,et al.Elementary decomposition mechanisms of lithium hexafluorophosphate in battery electrolytes and interphases[J].ACS Energy Letters,2023,8(1):347-355.

DOYLE M,FULLER T F,NEWMAN J.Modeling of galvanostatic charge and discharge of the lithium/polymer/insertion cell[J].Journal of The Electrochemical Society,1993,140(6):1526-1533.

FULLER T F,DOYLE M,NEWMAN J.Simulation and optimization of the dual lithium ion insertion cell[J].Journal of The Electrochemical Society,1994,141(1):1-10.

PLOEHN H J,RAMADASS P,WHITE R E.Solvent diffusion model for aging of lithium-ion battery cells[J].Journal of The Electrochemical Society,2004,151(3):A456-A462.

RAMADASS P,HARAN B,GOMADAM P M,WHITE R,POPOV B N.Development of first principles capacity fade model for Li-ion cells[J].Journal of The Electrochemical Society,2004,151(2):A196-A203.

KIRKALDY N, SAMIEIAN M A, OFFER G J, et al. Lithium-ion battery degradation: Comprehensive cycle ageing data and analysis for commercial 21700 cells[J]. Journal of Power Sources, 2024, 603: 234185.

KIRKALDY N, SAMIEIAN M A, OFFER G, et al. Data from: "Lithium-ion battery degradation: comprehensive cycle ageing data and analysis for commercial 21700 cells"[DS/OL]. Version 1. Zenodo, 2024.

KREMER L S, DANNER T, HEIN S, et al. Influence of the electrolyte salt concentration on the rate capability of ultra-thick NCM 622 electrodes[J]. Batteries & Supercaps, 2020, 3(11): 1172-1182. DOI:10.1002/batt.202000098.

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

FEC添加剂提升预锂化石墨负极的循环稳定性

热泵储电中双级压缩与梯度储热协同作用的分析

锂硫电池用硫化聚丙烯腈正极的结构，反应机理及研究进展

石墨和电解液界面研究进展：现状，挑战，未来

大型熔盐储罐动力特性及抗震分析方法研究

基于P2D-SEI改进模型的LiPF6三元电解液延缓老化研究

Aging Characteristics and Composition Optimization of LiPF6/EC-EMC-DMC Ternary Electrolytes Based on an Improved P2D-SEI Model

DOI：10.19799/j.cnki.2095-4239.2026.0844

摘要

Abstract

关键词

Keywords

references

基于P2D-SEI改进模型的LiPF₆三元电解液延缓老化研究