Two-dimensional (2D) layered thiophosphates have garnered attention for advanced battery technology due to their open ionic diffusion channels, high capacity, and unique catalytic properties. However, their potential in energy storage applications remains largely unexplored. In this study, we report a 2D transition metal thiophosphate (Nb4P2S21) with high sulfur content, synthesized via chemical vapor transport (CVT). The bulk material, exhibiting a layered quasi-one-dimensional (quasi-1D) structure, can be exfoliated into high-quality nanoplates using glue-assisted grinding. Density functional theory (DFT) calculations reveal a direct bandgap of 1.64 eV (HSE06 method) for Nb4P2S21, aligning with its near-infrared (NIR) photoluminescence at 755 nm. Despite an initial discharge capacity of 1500 mA h g-1, the material shows low reversible capacity and rapid capacity decay at 0-2.6 V. In situ Raman confirms the formation of polysulfides during cycling. Given its high sulfur content, the material was evaluated at 0.5-2.6 V, 1.0-2.6 V, and 1.5-2.6 V to assess its sulfur-equivalent cathode performance. In carbonate-based electrolytes, electrochemical performance is hindered by polysulfide formation and side reactions, but switching to ether-based electrolytes improves initial reversible capacity and coulombic efficiency due to additional Li x S conversion above 2.2 V. EDS and TOF-SIMS analyses of cycled electrodes show a significant sulfur loss, worsening the polysulfide shuttle effect and leading to battery failure. Adapting strategies from lithium-sulfur batteries, such as polar host catalysts, could enhance the material's performance.

Chemistry and Physics of Materials University of Salzburg Jakob Haringer Strasse 2A 5020 Salzburg Austria

Department of Inorganic Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague Czech Republic

Department of Molecular Chemistry and Materials Science Weizmann Institute of Science Rehovot 7610001 Israel

Department of Organic Technology University of Chemistry and Technology Prague Technická 5 166 28 Prague Czech Republic

Department of Physical and Macromolecular Chemistry Faculty of Science Charles University Prague 12843 Czech Republic

Institute of Micro Nano Materials and Devices Ningbo University of Technology Ningbo 315211 P R China

School of Materials Science and Engineering Zhejiang Sci Tech University Hangzhou 310018 PR China

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