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New synthesis strategies to improve Co-Free LiNi0.5Mn0.5O2 cathodes: Early transition metal d0 dopants and manganese pyrophosphate coating

Journal Article · · Journal of Power Sources
 [1];  [2];  [3];  [3];  [2];  [4];  [4];  [4];  [2];  [5];  [2];  [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Tennessee Technological Univ., Cookeville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Tennessee Technological Univ., Cookeville, TN (United States)
+ Show Author Affiliations
Here in this work, we report solution-based doping and coating strategies to improve the electrochemical performance of the Co-free layered oxide cathode LiNi0.5Mn0.5O2 (NM-50/50). Small amounts of d0 dopants (e.g., Mo6+and Ti4+, 0.5–1 at. %) increase the cathode's specific capacity, cycling stability, and rate capability. For example, a Mo-doped cathode with the nominal composition LiNi0.495Mn0.495Mo0.01O2 exhibits a high reversible capacity of 180 mA h/g at 20 mA/g compared to only 156 mA h/g for undoped NM-50/50. Effects of 1 at.% Mo dopant on the cathode structure were studied using a suite of characterization tools including X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. These measurements demonstrate that Mo6+ dopant is enriched near the particle surface and improves the electrochemical performance of LiNi0.5Mn0.5O2 by: (i) reducing Li+/Ni2+ cation mixing which facilitates Li+ transport, (ii) mitigating undesirable phase transformations near the cathode surface, and (iii) altering the cathode/electrolyte interfacial chemistry. This work also reports the use of an inorganic Mn2P2O7 coating which enhances the cycling stability of Mo-doped NM-50/50, presumably through formation of a stable cathode electrolyte interphase (CEI) layer. Overall, the synthesis approaches reported herein are quite general and can potentially be expanded to other high voltage Li-ion battery cathodes.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1770664
Alternate ID(s):
OSTI ID: 1809598
OSTI ID: 1776715
OSTI ID: 1673415
Journal Information:
Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 479; ISSN 0378-7753
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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