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Thermal-overdischarge coupling induced aging mechanisms in LiFePO4 batteries: insights from multi-scale electrochemical and material diagnostics

Author

Listed:
  • Tang, Rui
  • Xu, Yuelei
  • Dong, Jinyang
  • Shi, Qi
  • Yan, Kang
  • Guan, Yibiao
  • Lu, Yun
  • Su, Yu
  • Liu, Jinzhong
  • Zhao, Fangze
  • Jin, Yi
  • Li, Ning
  • Su, Yuefeng
  • Wu, Feng
  • Chen, Lai

Abstract

This study deciphers aging mechanisms in lithium iron phosphate (LiFePO4) batteries under coupled thermal-electrochemical stresses using a multi-scale approach. Industrial-grade LiFePO4/graphite pouch cells underwent accelerated aging across orthogonal temperature (25/45/65 °C) and discharge cut-off voltage (2.5/1.0/0.5 V) conditions. Integrating electrochemical diagnostics (DCIR, EIS, IC/DV) with post-mortem characterization (SEM/TEM/XRD/ToF-SIMS/μXRF) reveals that: (1) Elevated temperatures amplify lithium loss and SEI instability; (2) Deep over-discharge (≤1.0 V) triggers anode degradation via graphite structural collapse, copper dissolution, and SEI rupture; (3) Coupled stresses induce synergistic failure—manifested by DCIR transitions from linear to exponential growth—correlated microscopically with dead lithium accumulation, metal deposition percolation, and interfacial collapse; (4) Extreme conditions (65 °C/0.5 V) provoke atypical mechanisms including cathode FePO4 segregation and copper migration. The work establishes DCIR inflection as a non-destructive marker for failure-stage transition and provides fundamental insights into stress-coupled degradation pathways, advancing predictive models for LiFePO4 battery durability in energy storage systems.

Suggested Citation

  • Tang, Rui & Xu, Yuelei & Dong, Jinyang & Shi, Qi & Yan, Kang & Guan, Yibiao & Lu, Yun & Su, Yu & Liu, Jinzhong & Zhao, Fangze & Jin, Yi & Li, Ning & Su, Yuefeng & Wu, Feng & Chen, Lai, 2025. "Thermal-overdischarge coupling induced aging mechanisms in LiFePO4 batteries: insights from multi-scale electrochemical and material diagnostics," Applied Energy, Elsevier, vol. 401(PC).
    • Handle: RePEc:eee:appene:v:401:y:2025:i:pc:s0306261925016009
    DOI: 10.1016/j.apenergy.2025.126870
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