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Three-step thermodynamic vs. two-step kinetics-limited sulfur reactions in all-solid-state sodium batteries

Journal Article · · Energy & Environmental Science
DOI:https://doi.org/10.1039/d4ee03160a· OSTI ID:2479949
 [1];  [2];  [3];  [4];  [5];  [1];  [1];  [5];  [6];  [1]
  1. Northeastern Univ., Boston, MA (United States)
  2. Rochester Inst. of Technology, NY (United States)
  3. Univ. of Western Ontario, London, ON (Canada)
  4. Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  5. Boston College, Chestnut Hill, MA (United States)
  6. Xiamen Univ. (China)
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The investigation of all-solid-state sodium–sulfur batteries (ASSSBs) is still in its early stage, where the intermediates and mechanism of the complex 16-electron conversion reaction of the sulfur cathode remain unclear. Herein, this study presents a comprehensive investigation of the sulfur reaction mechanism in ASSSBs by combining electrochemical measurements, ex situ synchrotron X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and first-principles calculations. This work, for the first time, proved that the sulfur cathode undergoes an intrinsic three-step solid–solid redox reaction following the thermodynamic principle under the extreme low rate (C-rates ≤ C/100) or at high temperature (≥ 90 °C), where S8 is first reduced to long-chain polysulfides (Na2S5 and Na2S4), then to Na2S2, and finally to Na2S, resulting in a three-plateau voltage profile. However, under conventional battery test conditions, i.e., temperatures ≤60 °C and C-rates ≥C/20, the Na2S2 phase is bypassed due to kinetic limitations, leading to a direct conversion from Na2S4 to Na2S, resulting in the commonly observed two-plateau voltage profile. First-principles calculations reveal that the formation energy of Na2S2 is only 4 meV per atom lower than the two-phase equilibrium of Na2S4 and Na2S, explaining its absence under kinetics-limited conditions. This work clarified the thermodynamic and kinetics-limited pathways of the 16-electron conversion reaction of the sulfur cathode in ASSSBs, providing valuable insights into the solid-state sodium–sulfur reaction mechanisms.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); USDOE
Grant/Contract Number:
SC0012704; CBET-ES-1924534
OSTI ID:
2479949
Alternate ID(s):
OSTI ID: 2475214; OSTI ID: 2507153
Report Number(s):
BNL-227527-2025-JAAM
Journal Information:
Energy & Environmental Science, Vol. 17, Issue 23; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
All-solid-state batteries
Na-S batteries
Reaction mechanism
X-ray absorption spectroscopy
In-situ Raman spectroscopy
First-principles calculations