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Title: Quantifying Reaction and Rate Heterogeneity in Battery Electrodes in 3D through Operando X-ray Diffraction Computed Tomography

Journal Article · · ACS Applied Materials and Interfaces
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [4];  [3];  [2]; ORCiD logo [5];  [6]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Binghamton Univ., Binghamton, NY (United States)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. ESRF—The European Synchrotron, Grenoble (France)
  5. Argonne National Lab. (ANL), Argonne, IL (United States); Stony Brook Univ., Stony Brook, NY (United States)
  6. Stony Brook Univ., Stony Brook, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations

In composite battery electrode architectures, local limitations in ionic and electronic transport can result in nonuniform energy storage reactions. Understanding such reaction heterogeneity is important to optimizing battery performance, including rate capability and mitigating degradation and failure. Here, we use spatially resolved X-ray diffraction computed tomography to map the reaction in a composite electrode based on the LiFePO4 active material as it undergoes charge and discharge. Accelerated reactions at the electrode faces in contact with either the separator or the current collector demonstrate that both ionic and electronic transport limit the reaction progress. The data quantify how nonuniformity of the electrode reaction leads to variability in the charge/discharge rate, both as a function of time and position within the electrode architecture. Importantly, this local variation in the reaction rate means that the maximum rate that individual cathode particles experience can be substantially higher than the average, control charge/discharge rate, by a factor of at least 2–5 times. This rate heterogeneity may accelerate rate-dependent degradation pathways in regions of the composite electrode experiencing faster-than-average reaction and has important implications for understanding and optimizing rate-dependent battery performance. Benchmarking multiscale continuum model parameters against the observed reaction heterogeneity permits extension of these models to other electrode geometries.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Argonne National Lab. (ANL), Argonne, IL (United States); Binghamton Univ., NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0012583
OSTI ID:
1532531
Alternate ID(s):
OSTI ID: 1597020
Journal Information:
ACS Applied Materials and Interfaces, Vol. 11, Issue 20; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

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  • Hardy, Emilee; Clement, Derek; Vogel, John
  • 44TH ANNUAL REVIEW OF PROGRESS IN QUANTITATIVE NONDESTRUCTIVE EVALUATION, VOLUME 37, AIP Conference Proceedings https://doi.org/10.1063/1.5031536
conference January 2018

Cited By (2)

TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++ journal February 2018
Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes journal January 2020

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25 ENERGY STORAGE
Li-ion batteries
LiFePO4
X-ray diffraction computed tomography
operando
reaction heterogeneity
thick electrode