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Title: New Cost-Effective Halide Solid Electrolytes for All-Solid-State Batteries: Mechanochemically Prepared Fe3+-Substituted Li2ZrCl6

Journal Article · · Advanced Energy Materials
 [1];  [2];  [3];  [1];  [4];  [1];  [5];  [6];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Yonsei Univ., Seoul (Korea, Republic of); Hanyang Univ., Seoul (Korea, Republic of)
  2. Dongguk Univ., Seoul (Korea, Republic of)
  3. Daegu Gyeongbuk Inst. of Science and Technology (DGIST) (Korea, Republic of)
  4. Yonsei Univ., Seoul (Korea, Republic of)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  6. Hanyang Univ., Seoul (Korea, Republic of)
+ Show Author Affiliations

Abstract Owing to the combined advantages of sulfide and oxide solid electrolytes (SEs), that is, mechanical sinterability and excellent (electro)chemical stability, recently emerging halide SEs such as Li 3 YCl 6 are considered to be a game changer for the development of all‐solid‐state batteries. However, the use of expensive central metals hinders their practical applicability. Herein, a new halide superionic conductors are reported that are free of rare‐earth metals: hexagonal close‐packed (hcp) Li 2 ZrCl 6 and Fe 3+ ‐substituted Li 2 ZrCl 6 , derived via a mechanochemical method. Conventional heat treatment yields cubic close‐packed monoclinic Li 2 ZrCl 6 with a low Li + conductivity of 5.7 × 10 −6 S cm −1 at 30 °C. In contrast, hcp Li 2 ZrCl 6 with a high Li + conductivity of 4.0 × 10 −4 S cm −1 is derived via ball‐milling. More importantly, the aliovalent substitution of Li 2 ZrCl 6 with Fe 3+ , which is probed by complementary analyses using X‐ray diffraction, pair distribution function, X‐ray absorption spectroscopy, and Raman spectroscopy measurements, drastically enhances the Li + conductivity up to ≈1 mS cm −1 for Li 2.25 Zr 0.75 Fe 0.25 Cl 6 . The superior interfacial stability when using Li 2+ x Zr 1− x Fe x Cl 6 , as compared to that when using conventional Li 6 PS 5 Cl, is proved. Furthermore, an excellent electrochemical performance of the all‐solid‐state batteries is achieved via the combination of Li 2 ZrCl 6 and single‐crystalline LiNi 0.88 Co 0.11 Al 0.01 O 2 .

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF); Korean Ministry of Trade, Industry & Energy (MOTIE); USDOE
Grant/Contract Number:
SC0012704; 2017M1A2A2044501; 2018R1A2B6004996; 2017M1A2A2044502; 20007045
OSTI ID:
1766778
Alternate ID(s):
OSTI ID: 1804508
Report Number(s):
BNL-221043-2021-JAAM
Journal Information:
Advanced Energy Materials, Vol. 11, Issue 12; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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25 ENERGY STORAGE
solid-state batteries
halides
solid electrolytes
electrodes
ionic conductivities