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Stabilizing LiCoO2 at 4.6 V by regulating anti-oxidative solvents

Journal Article · · Energy & Environmental Science
DOI:https://doi.org/10.1039/d4ee02049a· OSTI ID:2583976
 [1];  [2];  [3];  [1];  [1];  [1];  [1];  [1];  [4];  [5];  [4];  [1];  [3];  [1];  [1]
  1. Peking University, Shenzhen (China)
  2. Peking University, Shenzhen (China); Tsinghua University, Shenzhen (China)
  3. Tsinghua University, Shenzhen (China)
  4. Argonne National Laboratory (ANL), Argonne, IL (United States)
  5. Peking University, Shenzhen (China); Qiantu battery Technology Co., Ltd, Dongguan (China)
+ Show Author Affiliations
For LiCoO2 (LCO) operating at high voltages (>4.5 V vs. Li/Li+), the intensive side reactions between LCO and traditional ethylene carbonate (EC)-based electrolytes with LiPF6 salts can produce plenty of corrosive species (such as HF and HPO2F2), causing severe surface degradation. Herein, anti-oxidative fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC) were selected as co-solvents to reduce the generation of corrosive species. Besides, PF6− anions enrich the Helmholtz plane of the LCO/electrolyte interface and promote the formation of a robust cathode/electrolyte interphase (CEI) featuring LiF/LixPOyFz/Li3PO4 inorganics and P-containing organics under the synergy of fluorinated solvents, which significantly inhibits the catalysis of highly oxidative Co4+/On− (0 < n < 2). Benefiting from the reduced corrosive species and reinforced CEI, the layered structure of the LCO surface is well preserved during long-term cycling, with a highly reversible O3/H1-3 phase transition. Consequently, a LCO||graphite pouch cell exhibits a remarkable capacity retention of 85.7% after 500 cycles in 3.0–4.55 V. Furthermore, this work provides a new insight into developing advanced functional electrolytes for high-voltage lithium-ion batteries.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China; Soft Science Research Project of Guangdong Province; Basic and Applied Basic Research Foundation of Guangdong Province; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2583976
Alternate ID(s):
OSTI ID: 2447499
Journal Information:
Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 20 Vol. 17; ISSN 1754-5706; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

Co/O loss
cathode/electrolyte interphase
corrosive species
high-voltage LiCoO2
solvation structure