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Evolution of the Electrode–Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress

Journal Article · · Chemistry of Materials
 [1];  [1];  [2];  [2];  [2];  [3];  [1];  [4];  [5];  [6];  [3];  [2];  [1]
  1. Binghamton Univ., NY (United States)
  2. Rutgers Univ., New Brunswick, NJ (United States)
  3. Univ. of Cambridge (United Kingdom)
  4. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.; Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  5. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
+ Show Author Affiliations
For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode–electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li2CO3, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques in our work, we study the evolution of these CEI species as a function of electrochemical and thermal stress for LiNi0.8Co0.15Al0.05O2 (NCA) particle electrodes using a LiPF6 ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li2CO3 and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF6 breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Grant/Contract Number:
AC02-05CH11231; SC0001294; SC0012583
OSTI ID:
1470192
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 3 Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes. journalarticle January 2019
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies journal December 2019
Effects of Charge Cutoff Potential on an Electrolyte Additive for LiNi 0.6 Co 0.2 Mn 0.2 O 2 –Mesocarbon Microbead Full Cells journal March 2019
Fluoroethylene carbonate as an electrolyte additive for improving interfacial stability of high-voltage LiNi0.6Co0.2Mn0.2O2 cathode journal July 2018
Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems journal January 2019
Anodic decomposition of surface films on high voltage spinel surfaces—Density function theory and experimental study journal December 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge transport
defects
energy storage (including batteries and capacitors)
materials and chemistry by design
synthesis (novel materials)