Controllable synthesis of a Na-enriched Na4V2(PO4)3 cathode for high-energy sodium-ion batteries: a redox-potential-matched chemical sodiation approach† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3sc03498d
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ABSTRACT:
SUBMITTER: Xu M
PROVIDER: S-EPMC10646896 | biostudies-literature | 2023 Oct
REPOSITORIES: biostudies-literature
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Project description:Recently, all-solid-state sodium batteries (Na-ASSBs) have received increased interest owing to their high safety and potential of high energy density. The potential of Na-ASSBs based on sodium superionic conductor (NASICON)-structured Na3 V2 (PO4 )3 (Na3 VP) cathodes have been proven by their high capacity and a long cycling stability closely related to the microstructural evolution. However, the detailed kinetics of the electrochemical processes in the cathodes is still unclear. In this work, the sodiation/desodiation process of Na3 VP is first investigated using in situ high-resolution transmission electron microscopy (HRTEM). The intermediate Na2 V2 (PO4 )3 (Na2 VP) phase with the P21 /c space group, which would be inhibited by constant electron beam irradiation, is observed at the atomic scale. With the calculated volume change and the electrode-electrolyte interface after cycling, it can be concluded that the Na2 VP phase reduces the lattice mismatch between Na3 VP and NaV2 (PO4 )3 (NaVP), preventing structural collapse. Based on the density functional theory calculation (DFT), the Na+ ion migrates more rapidly in the Na2 VP structure, which facilitates the desodiation and sodiation processes. The formation of Na2 VP phase lowers the formation energy of NaVP. This study demonstrates the dynamic evolution of the Na3 VP structure, paving the way for an in-depth understanding of electrode materials for energy-storage applications.
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Project description:Solid electrolytes hold promise in safely enabling high-energy metallic sodium (Na) anodes. However, the poor Na‖solid electrolyte interfacial contact can induce Na dendrite growth and limit Na utilization, plaguing the rate performance and energy density of current solid-state Na-metal batteries (SSSMBs). Herein, a simple and scalable Pb/C interlayer strategy is introduced to regulate the surface chemistry and improve Na wettability of Na3Zr2Si2PO12 (NZSP) solid electrolyte. The resulting NZSP exhibits a perfect Na wettability (0° contact angle) at a record-low temperature of 120 °C, a negligible room-temperature Na‖NZSP interfacial resistance of 1.5 Ω cm2, along with an ultralong cycle life of over 1800 h under 0.5 mA cm-2/0.5 mA h cm-2 symmetric cell cycling at 55 °C. Furthermore, we unprecedentedly demonstrate in situ fabrication of weight-controlled Na anodes and explore the effect of the negative/positive capacity (N/P) ratio on the cyclability of SSSMBs. Both solid-state Na3V2(PO4)3 and S full cells show superior electrochemical performance at an optimal N/P ratio of 40.0. The Pb/C interlayer modification demonstrates dual functions of stabilizing the anode interface and improving Na utilization, making it a general strategy for implementing Na metal anodes in practical SSSMBs.
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