硅基电池日历老化性能劣化研究

周丰松; 陈涛; 肖翔鸣; 方娜; 尚进; 展新

doi:10.19799/j.cnki.2095-4239.2026.0801

您当前的位置：

首页 >

文章列表页 >

硅基电池日历老化性能劣化研究

XXXX | 更新时间：2026-10-31

- 硅基电池日历老化性能劣化研究
- Calendar Aging of Silicon-based Batteries: A Review of Performance Degradation, Failure Mechanisms, and Safety Assessment
- 储能科学与技术 2026年页码：1-20
- 作者机构：
  
  东风汽车集团有限公司研发总院，武汉 430058
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2026.0801
  中图分类号： TM 912
- 收稿：2026-09-11，
  
  修回：2026-10-28，
  
  网络首发：2026-10-31，
- 稿件说明：
移动端阅览
周丰松, 陈涛, 肖翔鸣, 等. 硅基电池日历老化性能劣化研究[J]. 储能科学与技术, XXXX, XX(XX): 1-20.

Zhou Fengsong, Chen Tao, Xiao Xiangming, et al. Calendar Aging of Silicon-based Batteries: A Review of Performance Degradation, Failure Mechanisms, and Safety Assessment[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-20.
周丰松, 陈涛, 肖翔鸣, 等. 硅基电池日历老化性能劣化研究[J]. 储能科学与技术, XXXX, XX(XX): 1-20. DOI： 10.19799/j.cnki.2095-4239.2026.0801.

Zhou Fengsong, Chen Tao, Xiao Xiangming, et al. Calendar Aging of Silicon-based Batteries: A Review of Performance Degradation, Failure Mechanisms, and Safety Assessment[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-20. DOI： 10.19799/j.cnki.2095-4239.2026.0801.

摘要

硅基电池的日历老化速度要比石墨体系快得多，是影响它商业化的关键所在。本文主要研究硅基电池存储老化过程中性能下降的情况，从容量、阻抗、产气、安全等方面来梳理它的衰减表现，并试图把失效机理同性能发展联系起来；产气毒性及可燃性部分，把典型的文献里的分数有效剂量（

FED

）、分数刺激性浓度（

FIC

）、Purser致死性模型（

FED

）和最大爆炸指数（

max

）这些评价模型综合起来。全文从材料的设计、制造工艺、系统的应用三个方面入手，用“策略原理—核心发现—表征方法—开放问题”为线索，重点放在SECM、可变OCV-RPT、超声扫描、高精度漏电流、FIB-EDS断层扫描等表征手段的定量分析上，同时整理出Ah级软包电池和商用18650电池的长期老化数据。就整体而言，采用SECM把硅SEI钝化退化分为全局化学溶解和局部机械开裂两种形式，其中化学退化占主要地位，用可变OCV-RPT协议把存储中的化学降解和循环引起的机械损伤分开统计，静置满一个月之后发现化学贡献大得多，LAM和LLI的相对贡献也会因为硅含量以及SOC的不同而改变，利用漏电流检测可以得到硅负极寄生反应速率和失衡电荷损失导致的容量衰减之间存在线性关系，超声成像可以观察到锂迁移、SEI破坏、副反应的循环过程，通过分析4年的老化数据可知长期衰减主要是由于电解液消耗造成的，不是HF侵蚀引起的。化成电位≤0.75V (vs. Li+/Li)、过锂化约20%、多价添加剂、30%-60% SOC存储等都有各自的适用范围。因此SEI钝化化学退化属于日历老化的一种推助因素，SiOx含量是决定老化速率的根本原因；但是精细机理大多来自于扣式电池、模型电极以及短期测试，对于Ah级商用电池的放大验证还很缺乏。建议在12个月或者更长时间内建立一个“过锂化、日历寿命、安全”三者之间的三角权衡框架，推进有关测试标准的一致性。

Abstract

Calendar aging proceeds markedly faster in silicon-based batteries than in graphite-based systems

and this gap has become a bottleneck to commercialization. Performance degradation of silicon-based batteries during storage aging is the focus of this review: decay is surveyed across capacity

impedance

gas generation

and safety

and an attempt is made to relate failure mechanisms to performance evolution

. For gas toxicity and flammability

quantitative assessments available in the literature—carried out with the fractional effective dose (

FED

)

fractional irritant concentration (

FIC

)

Purser lethality model (

FED

)

and maximum explosion index (

max

)—are integrated rather than reproduced. The discussion is organized at three levels

material design

manufacturing process

and system application

along the thread of "strategy rationale—key findings—characterization methods-open questions." Quantitative results from SECM

variable open-circuit voltage-reference performance test (OCV-RPT) protocols

ultrasonic scanning

high-precision leakage current measurements

and FIB-EDS tomography receive particular attention; long-term aging data of Ah-level pouch cells and commercial 18650 cells are also drawn upon. Taken together

SECM separates silicon SEI passivation degradation into global chemical dissolution and localized mechanical cracking

with chemical degradation dominating. The variable OCV-RPT protocol distinguishes storage-induced chemical degradation from cycle-induced mechanical damage; the chemical contribution grows once the cell has rested for a month or longer. The relative contributions of the loss of active material (LAM) and the loss of lithium inventory (LLI) shift with silicon content and SOC. Leakage current measurements link the parasitic reaction rate of silicon anodes linearly to capacity fade caused by imbalanced charge loss. Ultrasonic imaging records the cycle of "lithium migration-SEI destruction-side reactions." Four-year aging data attribute long-term decay mainly to electrolyte consumption rather than HF erosion. On the countermeasure side

formation potential ≤0.75 V (vs. Li

/Li)

overlithiation of about 20%

multivalent additives

and storage at 30—60% SOC each applies within its own boundary. In short

chemical degradation of SEI passivation is what promotes calendar aging

and SiOx cont

ent is an intrinsic determinant of the aging rate. Most fine mechanistic conclusions

however

derive from coin cells

model electrodes

and short-term tests; validation toward Ah-level commercial cells remains inadequate. A trilemma framework that weighs overlithiation

calendar life

and safety over periods of 12 months or longer is recommended

together with unified calendar aging test standards.

关键词

Keywords

references

McBrayer J D, Rodrigues M F, Schulze M C, et al. Calendar aging of silicon-containing batteries [J]. Nature Energy, 2021, 6(9): 866-872.. DOI: 10.1038/s41560-021-00883-w.

Obrovac M N, Chevrier V L. Alloy negative electrodes for Li-ion batteries [J]. Chemical Reviews, 2014, 114(23): 11444-11502.DOI:10.1021/cr500207g.

Keil P, Schuster S F, Wilhelm J, et al. Calendar aging of lithium-ion batteries: I. impact of the graphite anode on capacity fade [J]. Journal of the Electrochemical Society, 2016, 163(9): A1872-A1880. DOI:10.1149/2.0411609jes.

Peled E, Menkin S. Review: SEI: past, present and future [J]. Journal of the Electrochemical Society, 2017, 164(7): A1703-A1719. DOI: 10.1149/2.1441707jes

McBrayer J D, Schorr N B, Lam M N, et al. Scanning electrochemical microscopy reveals that model silicon anodes demonstrate global solid electrolyte interphase passivation degradation during calendar aging [J]. ACS Applied Materials & Interfaces, 2024, 16(15): 19663-19671.DOI: 10.1021/acsami.3c14361.

McBrayer J D, Harrison K L, Allcorn E, et al. Chemical contributions to silicon anode calendar aging are dominant over mechanical contributions [J]. Frontiers in Batteries and Electrochemistry, 2023, 2: 1308127.DOI: 10.3389/fbael.2023

Cai J Y, Zhou X W, Li T Y, et al. Critical contribution of imbalanced charge loss to performance deterioration of Si-based lithium-ion cells during calendar aging [J]. ACS Applied Materials & Interfaces, 2023, 15(41): 48085-48095.DOI: 10.1021/acsami.3c11280

Huang Z Y, Shao Y X, Zheng Q, et al. Calendar aging of silicon pouch cells: In-situ ultrasound analysis and polymer electrolyte interfacial engineering [J ] . Nano Research, 2026, 19(8): 94908634.DOI: 10.26599/NR.2026.94908634.

F Rodrigues M T, Yang Z Z, Trask S E, et al. Pouch cells with 15% silicon calendar-aged for 4 years [J]. Journal of Power Sources, 2023, 565: 232894. DOI: 10.1016/j.jpowsour.2023.232894.

Bischof K, Flügel M, Hölzle M, et al. Aging mechanism for calendar aging of Li-ion cells with Si/graphite anodes [J]. Journal of the Electrochemical Society, 2024, 171(1): 010510. DOI: 10.1149/1945-7111/ad1b7c

Zilberman I, Sturm J, Jossen A. Reversible self-discharge and calendar aging of 18650 nickel-rich, silicon-graphite lithium-ion cells [J]. Journal of Power Sources, 2019, 425: 217-226. DOI: 10.1016/j.jpowsour.2019.03.118.

胡晓艳. 高镍/硅碳锂离子电池高温条件下的产气研究 [J]. 电池工业, 2024, 28(5): 230-237. DOI: 10.19996/j.cnki.ChinBatInd.2024.05.002.

Zhang Y Y, Li X, Sivonxay E, et al. Silicon anodes with improved calendar life enabled by multivalent additives [J]. Advanced Energy Materials, 2021, 11(37): 2101820. DOI: 10.1002/aenm.202101820.

Wang X H, Li C H, Liu S Y, et al. Revealing the overlithiation effect on cycling and calendar aging of a silicon/graphite electrode for high-energy lithium-ion batteries [J]. Chemical Science, 2024, 15(43): 17979-17987.DOI: 10.1039/d4sc05632a.

Wan Z W, Weng A, Pannala S, et al. Managing silicon burn-out via onboard material diagnostics for durable high-energy density batteries [J ] . Joule, 2026: 102531. DOI: 10.1016/j.joule.2026.102531.

Kalaga K, Rodrigues M F, Trask S E, et al. Calendar-life versus cycle-life aging of lithium-ion cells with silicon-graphite composite electrodes [J]. Electrochimica Acta, 2018, 280: 221-228.DOI: 10.1016/j.electacta.2018.05.101.

Yin Y L, Arca E, Wang L N, et al. Nonpassivated silicon anode surface [J]. ACS Applied Materials & Interfaces, 2020, 12(23): 26593-26600. DOI: 10.1021/acsami.0c03799.

Sun K, Zhang Z J, Fu K, et al. Tracing the origins of calendar aging in Si-containing lithium-ion batteries [J]. Nano Letters, 2025, 25(3): 931-938.DOI: 10.1021/acs.nanolett.4c03530.

Majherova V, Fiamegkou E, Nakhanivej P, et al. Revealing how silicon oxide accelerates calendar ageing of commercial 21700 nickel-rich lithium-ion cells [J]. Journal of the Electrochemical Society, 2025, 172(9): 090505. DOI: 10.1149/1945-7111/adfe98.

Barua S, Mou R J, Yao K P C. Aging-driven in situ polymerization of FEC additive boosts the calendar-life of silicon anodes via surface passivation enhancement [J ] . Journal of Power Sources, 2026, 691: 240999.DOI:10.1149/MA2026-013406mtgabs.

Zülke A, Li Y, Keil P, et al. High-energy nickel-cobalt-aluminium oxide (NCA) cells on idle: anode- versus cathode-driven side reactions [J]. Batteries & Supercaps, 2021, 4(6): 934-947. DOI:10.1002/batt.202100046.

Gewald T, Lienkamp M, Lehmkuhl D, et al. Accelerated aging characterization of lithium-ion cells: limitation of Arrhenius dependency [C ] //2019 Fourteenth International Conference on Ecological Vehicles and Renewable Energies (EVER). May 8-10, 2019 , Monte-Carlo, Monaco. IEEE, 2019: 1-10. DOI: 10.1109/EVER.2019.8813589.

Kiran I, Azzam M, Endisch C, et al. Evaluation of calendar aging in cells with graphite: silicon anode using float current analysis under the influence of voltage hysteresis [J]. Journal of the Electrochemical Society, 2025, 172(10): 100529.DOI: 10.1149/1945-7111/ae0fe8

Quinn J, Badami P, Huang Q, et al. Quantifying silicon anode restructuring during calendar aging of lithium-ion batteries by plasma focused ion beam tomography and chemical mapping [J]. EES Batteries, 2025, 1(3): 598-608. DOI: 10.1039/d5eb00036j.

Frie F, Ditler H, Klick S, et al. An analysis of calendaric aging over 5 years of Ni-rich 18650-cells with Si/C anodes [J]. ChemElectroChem, 2024, 11(9): e202400020.DOI: 10.1002/celc.202400020.

方靖, 杨续来, 戴涛, 等. 锂离子电池硅负极用聚合物黏结剂研究进展 [J]. 储能科学与技术, 2024, 13(11): 3811-3825. DOI: 10.19799/j.cnki.2095-4239.2024.0467.

Xiang Y, Jiang B, Dai H F. Cerberus : a deep learning hybrid model for lithium-ion battery aging estimation and prediction based on relaxation voltage curves [PP/OL ] . V1. arXiv (2023-08-15)[2026-06-09 ] . https://doi.org/10.48550/arXiv.2308.07824.

Zhao Z Y, Chen F Q, Han J W, et al. Revival of microparticular silicon for superior lithium storage [J]. Advanced Energy Materials, 2023, 13(24): 2300367. DOI: 10.1002/aenm.202300367

Yang Y Z, Yang Z, Li Z L, et al. Rational electrolyte design for interfacial chemistry modulation to enable long-term cycling Si anode [J]. Advanced Energy Materials, 2023, 13(41): 2302068. DOI: 10.1002/aenm.202302068.

Zhang W J, Yang S M, Heng S, et al. Improved solid electrolyte interphase and Li-storage performance of Si/graphite anode with ethylene sulfate as electrolyte additive [J]. Functional Materials Letters, 2020, 13(7): 2051041. DOI: 10.1142/S1793604720510418.

Xie Y C, Feng X N, Wang Y L, et al. Thermochemical crosstalk in Si-C anodes: mechanism and stabilization via a polymerizable phosphorus-based additive [J ] . Advanced Energy Materials, 2026, 16(6): e04167.DOI: 10.1002/aenm.202670453.

Yan M Y, Liang J Y, Zhang X S, et al. An additive-assisted hydrolysis-blocking route enables thermally stable interfacial chemistry of silicon-based anode materials in a rechargeable lithium battery [J]. Advanced Energy Materials, 2025, 15(33): 2501637. DOI: 10.1002/aenm.202501637.

Peng Y, Yang L Z, Ju X Y, et al. A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO 4 cathode [J ] . Journal of Hazardous Materials, 2020, 381: 120916.DOI: 10.1016/j.jhazmat.2019.120916.

Qiu M M, Liu J H, Cong B H, et al. Research progress in thermal runaway vent gas characteristics of Li-ion battery [J]. Batteries, 2023, 9(8): 411.DOI: 10.3390/batteries9080411

Purser D A, McAllister J L. SFPE Handbook of Fire Protection Engineering [M]. 5th ed. Cham: Springer Nature Switzerland, 2026: 2271-2352.

Shao Y Y, University S M, Liu J H, et al. Toxicity and explosive hazards of thermal runaway gases in aged batteries under different states of charge [J]. ACS Chemical Health & Safety, 2026, 33(1): 60-72.DOI: 10.1021/acs.chas.5c00142.

Wang M, Wu S M, Chen Y, et al. Quantitative safety assessment of lithium-ion batteries: Integrating abuse risks and intrinsic safety [J]. Journal of Power Sources, 2025, 640: 236789. DOI: 10.1016/j.jpowsour.2025.236789

Quinn J, Kim J M, Yi R, et al. Fluoro-ethylene-carbonate plays a double-edged role on the stability of Si anode-based rechargeable batteries during cycling and calendar aging [J]. Advanced Materials, 2024, 36(30): 2402625.DOI: 10.1002/adma.202402625.

Lam S, et al. Surprising relationship between silicon anode calendar aging and electrolyte components in a localized high-concentration electrolyte system [J]. ACS Applied Materials & Interfaces, 2025, 17(30): 43020-43033. DOI: 10.1021/acsami.5c07869.

Verma A, Schulze M C, Colclasure A, et al. Significant improvements to Si calendar lifetime using rapid electrolyte screening via potentiostatic holds [J ] . Journal of the Electrochemical Society, 2024, 171(7): 070539.DOI: 10.1149/1945-7111/ad6376.

Verma A, Schulze M C, Colclasure A, et al. Assessing electrolyte fluorination impact on calendar aging of blended silicon-graphite lithium-ion cells using potentiostatic holds [J]. Journal of the Electrochemical Society, 2023, 170(7): 070516. DOI: 10.1149/1945-7111/ace65d

Kondracki Ł, Niemelä J P, Baster D, et al. Synergy of artificial SEI and electrolyte additive for improved performance of silicon electrodes in Li-ion batteries [J]. ACS Applied Energy Materials, 2024, 7(20): 9336-9348. DOI: 10.1021/acsaem.4c01862.

Wang X X, Wang K, Wan Z W, et al. Inorganic/organic composite binder with self-healing property for silicon anode in lithium-ion battery [J]. Materials Today Energy, 2024, 43: 101567. DOI: 10.1016/j.mtener.2024.101567.

He T Y, University N, Ding Y Y, et al. Self-healing SA@Borax binder for in situ tuning of the solid electrolyte interfaces for silicon anodes [J ] . ACS Sustainable Chemistry & Engineering, 2025, 13(10): 4093-4107. DOI: 10.1021/acssuschemeng.4c10154.

Attia E, Hassan F, Li M, et al. A robust bundled and wrapped structure design of ultrastable silicon anodes for antiaging lithium-ion batteries [J]. ACS Applied Energy Materials, 2022, 5(5): 5540-5550.DOI: 10.1021/acsaem.1c03469.

Luo H, Zhang X M, Xu C, et al. Constructing a yolk–shell structure SiO x /C@C composite for long-life lithium-ion batteries [J ] . ACS Applied Energy Materials, 2022, 5(7): 8982-8989.DOI: 10.1021/acsaem.2c01463.

Diaz M, Williams A, McBrayer J D, et al. Effects of silicon anode porosity on capacity retention during calendar aging [J]. Journal of the Electrochemical Society, 2026, 173(9): 090515. DOI: 10.1149/1945-7111/ae6622.

McBRAYER J D. Calendar life of lithium ion batteries containing silicon and the role of solid electrolyte interphase mechanics[D]. Boulder: University of Colorado Boulder, 2022.

Lu W Q, Zhang L H, Qin Y, et al. Calendar and cycle life of lithium-ion batteries containing silicon monoxide anode [J]. Journal of the Electrochemical Society, 2018, 165(10): A2179-A2183. DOI:10.1149/2.0631810jes.

Von Kolzenberg L, Latz A, Horstmann B. Solid–electrolyte interphase during battery cycling: theory of growth regimes [J]. ChemSusChem, 2020, 13(15): 3901-3910. DOI: 10.1002/cssc.202000867.

Philipp M C J, Köbbing L, Karger A, et al. Physics-based modeling of cyclic and calendar aging of LIBs with Si-Gr composite anodes [PP/OL]. V1. arXiv (2026-04-29)[2026-07-19]. https://doi.org/10.48550/arXiv.2604.26545.

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

锂离子电池安全改性策略研究进展

不同荷电状态钛酸锂电池高温日历老化研究

模拟仿真在锂离子电池热安全设计中的应用

锂离子电池长寿命石墨电极研究现状与展望

基于改进TD3算法的储能系统多目标优化调度策略研究