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Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c07343· OSTI ID:2476596
 [1];  [1];  [2];  [2];  [3];  [4];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [5];  [6];  [7];  [8]
  1. Western University, London, ON (Canada)
  2. National Synchrotron Radiation Research Centre, Hsinchu (Taiwan)
  3. Southern University of Science and Technology, Shenzhen, P. R. (China)
  4. Dongguan University of Technology (China)
  5. Eastern Institute of Technology, Ningbo, Zhejiang, P. R. (China)
  6. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  7. Canadian Light Source Inc., Saskatoon (Canada)
  8. Western University, London, ON (Canada); Eastern Institute of Technology, Ningbo, Zhejiang, P. R. (China)
+ Show Author Affiliations

The recently surged halide-based solid electrolytes (SEs) are great candidates for high-performance all-solid-state batteries (ASSBs), due to their decent ionic conductivity, wide electrochemical stability window, and good compatibility with high-voltage oxide cathodes. In contrast to the crystalline phases in halide SEs, amorphous components are rarely understood but play an important role in Li-ion conduction. Here, we reveal that the presence of amorphous component is common in halide-based SEs that are prepared via mechanochemical method. The fast Li-ion migration is found to be associated with the local chemistry of the amorphous proportion. Taking Zr-based halide SEs as an example, the amorphization process can be regulated by incorporating O, resulting in the formation of corner-sharing Zr–O/Cl polyhedrons. This structural configuration has been confirmed through X-ray absorption spectroscopy, pair distribution function analyses, and Reverse Monte Carlo modeling. The unique structure significantly reduces the energy barriers for Li-ion transport. As a result, an enhanced ionic conductivity of (1.35 ± 0.07) × 10–3 S cm–1 at 25 °C can be achieved for amorphous Li3ZrCl4O1.5. In addition to the improved ionic conductivity, amorphization of Zr-based halide SEs via incorporation of O leads to good mechanical deformability and promising electrochemical performance. In conclusion, these findings provide deep insights into the rational design of desirable halide SEs for high-performance ASSBs.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Basic Research Foundation of Guangdong Province
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
2476596
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 5 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Halogens
Heat transfer
Inorganic compounds
Ionic conductivity
Thermodynamic modeling