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Origin of structural degradation in Li-rich layered oxide cathode

Journal Article · · Nature (London)
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  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Peking Univ., Shenzhen (China)
  3. Univ. College London (United Kingdom)
  4. City Univ. of Hong Kong, Kowloon (Hong Kong); Argonne National Lab. (ANL), Lemont, IL (United States)
  5. Univ. College London (United Kingdom); Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Argonne National Lab. (ANL), Lemont, IL (United States); Mohammed VI Polytechnic University, Benguerir (Morocco); Stanford Univ., CA (United States)
+ Show Author Affiliations
Li- and Mn-rich (LMR) cathode materials that utilize both cation and anion redox can yield substantial increases in battery energy density1,2,3. However, although voltage decay issues cause continuous energy loss and impede commercialization, the prerequisite driving force for this phenomenon remains a mystery3,4,5,6 In this work, with in situ nanoscale sensitive coherent X-ray diffraction imaging techniques, we reveal that nanostrain and lattice displacement accumulate continuously during operation of the cell. Evidence shows that this effect is the driving force for both structure degradation and oxygen loss, which trigger the well-known rapid voltage decay in LMR cathodes. By carrying out micro- to macro-length characterizations that span atomic structure, the primary particle, multiparticle and electrode levels, we demonstrate that the heterogeneous nature of LMR cathodes inevitably causes pernicious phase displacement/strain, which cannot be eliminated by conventional doping or coating methods. We therefore propose mesostructural design as a strategy to mitigate lattice displacement and inhomogeneous electrochemical/structural evolutions, thereby achieving stable voltage and capacity profiles. These findings highlight the significance of lattice strain/displacement in causing voltage decay and will inspire a wave of efforts to unlock the potential of the broad-scale commercialization of LMR cathode materials.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
National Key Research and Development Program of China; Shenzhen Science and Technology Research; Soft Science Research Project of Guangdong Province; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357; SC0012704
OSTI ID:
1873170
Alternate ID(s):
OSTI ID: 1969284
Report Number(s):
BNL-223092-2022-JAAM
Journal Information:
Nature (London), Journal Name: Nature (London) Journal Issue: 7913 Vol. 606; ISSN 0028-0836
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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25 ENERGY STORAGE
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SUPERCONDUCTIVITY AND SUPERFLUIDITY
batteries