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Realizing continuous cation order-to-disorder tuning in a class of high-energy spinel-type Li-ion cathodes

Journal Article · · Matter (Online)
 [1];  [2];  [3];  [4];  [1];  [5];  [6];  [7];  [7];  [8];  [1];  [9];  [1];  [1];  [1];  [9];  [10];  [11];  [3];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division; Univ. of Utah, Salt Lake City, UT (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  5. Univ. of California, Berkeley, CA (United States)
  6. Columbia Univ., New York, NY (United States)
  7. Univ. of California, Santa Barbara, CA (United States)
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  9. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division; Univ. of California, Berkeley, CA (United States)
  10. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  11. Univ. of California, Santa Barbara, CA (United States
+ Show Author Affiliations

Conventional Li-ion cathode materials are dominated by well-ordered structures, in which Li and transition metals occupy distinct crystallographic sites. Here, we show in this paper that profoundly new degrees of freedom for the optimization of electrochemical properties may be accessed if controllable cation disorder is introduced. In a class of high-capacity spinel-type cathode materials, we identify cation to anion ratio in synthesis as a key parameter for tuning the structure continuously from a well-ordered spinel, through a partially ordered spinel, to rocksalt. We find that the varying degree of cation disorder modifies the voltage profile, rate capability, and charge-compensation mechanism in a rational and predictable way. Our results indicate that spinel-type order is most beneficial for achieving high-rate performance as long as the cooperative 8a to 16c phase transition is suppressed, while more rocksalt-like disorder facilitates O redox, which can increase capacity. Our findings reveal an important tuning handle for achieving high energy and power in the vast space of partially ordered cathode materials.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF); Ministry of Education of the People's Republic of China; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1854556
Alternate ID(s):
OSTI ID: 1924024
Journal Information:
Matter (Online), Journal Name: Matter (Online) Journal Issue: 12 Vol. 4; ISSN 2590-2385
Publisher:
Cell Press/ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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