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Reaction Heterogeneity in LiFePO4 Agglomerates and the Role of Intercalation-Induced Stress

Journal Article · · ACS Energy Letters
 [1];  [1];  [2];  [3];  [2];  [2];  [2];  [4];  [1]
  1. Rice University, Houston, TX (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Harbin Institute of Technology (China)
  4. Shanghai Jiao Tong Univ. (China)
+ Show Author Affiliations
As an important battery cathode material, reaction distribution in lithium iron phosphate (LiFePO4) has been extensively studied in dispersed particle systems, but remains poorly understood for mesoscopic agglomerates (or secondary particles) that are used in most commercial batteries. Herein, we apply three-dimensional X-ray spectroscopic imaging to characterize the two-phase structure in LiFePO4 secondary particles during electrochemical cycling. (De)lithiated domains are found to not form the commonly assumed core-shell structure but develop highly anisotropic filamentary morphology that is rate independent and symmetric between charging and discharging. Phase-field simulations elucidate that the observed 1D phase growth behavior is not caused by the 1D lithium diffusivity of LiFePO4 but the elastic interaction between primary particles, which gives rise to stronger reaction heterogeneity than dispersed nanoparticles. As a result, uniform lithium (de)intercalation does not occur on the secondary particle surface even at high cycling rates.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; AC02-98CH10886; SC0012704; SC0019111
OSTI ID:
1887530
Report Number(s):
BNL-223294-2022-JAAM
Journal Information:
ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 5 Vol. 7; ISSN 2380-8195
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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