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Title: Electrolyte-induced surface transformation and transition-metal dissolution of fully delithiated LiNi0.8Co0.15Al0.05O2

Journal Article · · Langmuir
ORCiD logo [1];  [2];  [3];  [2];  [1];  [1];  [1];  [4];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Rutgers Univ., North Brunswick, NJ (United States)
  2. Binghamton Univ., Binghamton, NY (United States)
  3. Rutgers Univ., Piscataway, NJ (United States)
  4. Univ. of California, Berkeley, CA (United States)
+ Show Author Affiliations

Enabling practical utilization of layered R3m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[0.8Co0.15Al0.05]O2(NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li2CO3 content on the magnitude and character of the dissolution reaction was studied.

Research Organization:
Rutgers Univ., New Brunswick, NJ (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012583; AC02-05CH11231
OSTI ID:
1364759
Alternate ID(s):
OSTI ID: 1476541
Journal Information:
Langmuir, Vol. 33, Issue 37; ISSN 0743-7463
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 62 works
Citation information provided by
Web of Science

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Multifunctional NiTiO 3 nanocoating fabrication based on the dual-Kirkendall effect enabling a stable cathode/electrolyte interface for nickel-rich layered oxides journal January 2018
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies journal December 2019

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