Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study

Liu, Qi; Liu, Yadong; Yang, Fan; He, Hao; Xiao, Xianghui; Ren, Yang; Lu, Wenquan; Stach, Eric; Xie, Jian

doi:10.1021/acsami.7b13060

Capacity Fading Mechanism of the Commercial 18650 LiFePO₄-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study

Journal Article · Mon Jan 08 00:00:00 EST 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b13060· OSTI ID:1461322

Liu, Qi ^[1]; Liu, Yadong ^[2]; Yang, Fan ^[1]; He, Hao ^[2]; Xiao, Xianghui ^[3]; Ren, Yang ^[3]; Lu, Wenquan ^[4]; ^[5]; ^[2]

Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), IN (United States). Dept. of Mechanical and Energy Engineering. Purdue School of Engineering and Technology; Purdue Univ., West Lafayette, IN (United States). School of Mechanical Engineering
Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), IN (United States). Dept. of Mechanical and Energy Engineering. Purdue School of Engineering and Technology
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division. Advanced Photon Source
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Science and Engineering Division
Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science and Engineering. School of Engineering and Applied Science

In this paper, in situ high-energy synchrotron XRD studies were carried out on commercial 18650 LiFePO₄ cells at different cycles to track and investigate the dynamic, chemical, and structural changes in the course of long-term cycling to elucidate the capacity fading mechanism. The results indicate that the crystalline structural deterioration of the LiFePO₄ cathode and the graphite anode is unlikely to happen before capacity fades below 80% of the initial capacity. Rather, the loss of the active lithium source is the primary cause for the capacity fade, which leads to the appearance of inactive FePO₄ that is proportional to the absence of the lithium source. Our in situ HESXRD studies further show that the lithium-ion insertion and deinsertion behavior of LiFePO₄ continuously changed with cycling. For a fresh cell, the LiFePO₄ experienced a dual-phase solid-solution behavior, whereas with increasing cycle numbers, the dynamic change, which is characteristic of the continuous decay of solid solution behavior, is obvious. Finally, the unpredicted dynamic change may result from the morphology evolution of LiFePO₄ particles and the loss of the lithium source, which may be the cause of the decreased rate capability of LiFePO₄ cells after long-term cycling.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461322

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 5 Vol. 10; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

18650 cell
25 ENERGY STORAGE
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capacity fade mechanism
in situ study
synchrotron XRD