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Structural and Electrochemical Impacts of Mg/Mn Dual Dopants on the LiNiO2 Cathode in Li-Metal Batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [1];  [1];  [3];  [3];  [4];  [5];  [4];  [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Spallation Neutron Source Science Center, Dalang, (China); Australian Nuclear Science and Technology Organization (ANSTO), Lucas Heights, NSW (Australia)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. Australian Nuclear Science and Technology Organization (ANSTO), Lucas Heights, NSW (Australia); Univ. of Sydney, NSW (Australia)
+ Show Author Affiliations
Doping chemistry has been regarded as an efficient strategy to overcome some fundamental challenges facing the “no-cobalt” LiNiO2 cathode materials. By utilizing the doping chemistry, we evaluate the battery performance and structural/chemical reversibility of a new no-cobalt cathode material (Mg/Mn-LiNiO2). The unique dual dopants drive Mg and Mn to occupy the Li site and Ni site, respectively. We report the Mg/Mn-LiNiO2 cathode delivers smooth voltage profiles, enhanced structural stability, elevated self-discharge resistance, and inhibited nickel dissolution. As a result, the Mg/Mn-LiNiO2 cathode enables improved cycling stability in lithium metal batteries with the conventional carbonate electrolyte: 80% capacity retention after 350 cycles at C/3, and 67% capacity retention after 500 cycles at 2C (22 °C). We then take the Mg/Mn-LiNiO2 as the platform to investigate the local structural and chemical reversibility, where we identify that the irreversibility takes place starting from the very first cycle. The highly reactive surface induces the surface oxygen loss, metal reduction reaching the subsurface, and metal dissolution. Our data demonstrate that the dual dopants can, to some degree, mitigate the irreversibility and improve the cycling stability of LiNiO2, but more efforts are needed to eliminate the key challenges of these materials for battery operation in the conventional carbonate electrolyte.
Research Organization:
SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NSFC); Natural Science Foundation of Guangdong Province; Australian Centre for Neutron Scattering (ACNS)
Grant/Contract Number:
AC02-76SF00515; EE0008444; AC02-06CH11357
OSTI ID:
1617005
Alternate ID(s):
OSTI ID: 1633056
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 11 Vol. 12; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
cathode
dual doping
lithium battery
metal dissolution
no cobalt