Abstract The performance of all‐solid‐state batteries (ASSBs) relies on the Li+transport and stability characteristics of solid electrolytes (SEs). Li3PS4is notable for its stability against lithium metal, yet its ionic conductivity remains a limiting factor. This study leverages local structural disorder via O substitution to achieve an ionic conductivity of 1.38 mS cm−1with an activation energy of 0.34 eV for Li3PS4−xOx(x = 0.31). Optimal O substitution transforms Li+transport from 2D to 3D pathways with increased ion mobility. Li3PS3.69O0.31exhibits improvements in the critical current density and stability against Li metal and retains its electrochemical stability window compared with Li3PS4. The practical implementation of Li3PS3.69O0.31in ASSBs half‐cells, particularly when coupled with TiS2as the cathode active material, demonstrates substantially enhanced capacity and rate performance. This work elucidates the utility of introducing local structural disorder to ameliorate SE properties and highlights the benefits of strategically combining the inherent strengths of sulfides and oxides via creating oxysulfide SEs.
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Critical Role of Structural Water for Enhanced Li + Insertion Kinetics in Crystalline Tungsten Oxides
Electrochemical ion insertion into transition metal oxides forms the foundation of several energy technologies. Transition metal oxides can exhibit sluggish ion transport and/or phase-transformation kinetics during ion insertion that can limit their performance at high rates (<10 min). In this study, we investigate the role of structural water in transition metal oxides during Li + insertion using staircase potentiostatic electrochemical impedance spectroscopy (SPEIS) and electrochemical quartz crystal microbalance (EQCM) analysis of WO 3 ·H 2 O and WO 3 thin-film electrodes. Overall, the presence of structural water in WO 3 ·H 2 O improves Li + insertion kinetics compared to WO 3 and leads to a less potential-dependent insertion process. Operando electrogravimetry and 3D Bode impedance analyses of nanostructured films reveal that the presence of structural water promotes charge accommodation without significant co-insertion of solvent, leading to our hypothesis that the electrochemically induced structural transitions of WO 3 hinder the electrode response at faster timescales (<10 min). Designing layered materials with confined fluids that exhibit less structural transitions may lead to more versatile ion-insertion hosts for next-generation electrochemical technologies.
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- Award ID(s):
- 1653827
- PAR ID:
- 10342197
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 169
- Issue:
- 3
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- 030534
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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