Inorganic All‐Solid‐State Sodium Batteries: Electrolyte Designing and Interface Engineering

Abstract

Inorganic all‐solid‐state sodium batteries (IASSSBs) are emerged as promising candidates to replace commercial lithium‐ion batteries in large‐scale energy storage systems due to their potential advantages, such as abundant raw materials, robust safety, low price, high‐energy density, favorable reliability and stability. Inorganic sodium solid electrolytes (ISSEs) are an indispensable component of IASSSBs, gaining significant attention. Herein, this review begins by discussing the fundamentals of ISSEs, including their ionic conductivity, mechanical property, chemical and electrochemical stabilities. It then presents the crystal structures of advanced ISSEs (e.g., β/β′′‐alumina, NASICON, sulfides, complex hydride and halide electrolytes) and the related issues, along with corresponding modification strategies. The review also outlines effective approaches for forming intimate interfaces between ISSEs and working electrodes. Finally, current challenges and critical perspectives for the potential developments and possible directions to improve interfacial contacts for future practical applications of ISSEs are highlighted. This comprehensive review aims to advance the understanding and development of next‐generation rechargeable IASSSBs.This article is protected by copyright. All rights reserved

A hierarchical approach to designing a Na-rich phosphide solid-state electrolyte for Na-ion batteries

“…Strikingly, the calculated activation energy of Na diffusion in A-phase Na 7 TaP 4 is only 0.24 eV using ML-MD simulations, which is among the lowest known values for Na-ion SSEs. 7,76–78 This result manifests that crystal structure engineering has a significant impact on the Na diffusion properties. As this is the key finding of this work, we paid substantial efforts to check its accuracy by performing all-DFT MD simulations.…”

Y-Doped LiZr2(PO4)3 in a PVDF-HFP Composite Electrolyte for Solid-State Li-Metal Batteries

“…21 Although ceramic electrolytes have certain advantages (electrochemical stability, Li + conductivity, and mechanical strength), their brittle nature, high electrolyte−electrode interfacial resistance, and high processing costs limit their commercial applications. 22 SPEs are a combination of polymers, e.g., poly(ethylene oxide) (PEO), polyvinylidene fluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), poly(methyl methacrylate) (PMMA), poly(vinylpyrrolidone) (PVP), etc., and different Li-salts (LiTFSI, LiFSI, LiClO 4 ). 23,24 SPEs generally exhibit flexibility and good interfacial contact with the electrodes and can accommodate the volumetric expansion of electrodes during the charge−discharge cycle.…”

“…It has been reported that the substitution of Y 3+ at the Zr-site in LZP stabilizes the rhombohedral structure in the Li 1.15 Y 0.15 Zr 1.85 (PO 4 ) 3 phase with a total Li-ion conductivity of ∼3.5 × 10 –5 S cm –1 . Although ceramic electrolytes have certain advantages (electrochemical stability, Li + conductivity, and mechanical strength), their brittle nature, high electrolyte–electrode interfacial resistance, and high processing costs limit their commercial applications …”

Cation Configuration and Structural Degradation of Layered Transition Metal Oxides in Sodium-Ion Batteries

“…Achieving global carbon neutrality hinges on the continual advancement and widespread implementation of large-scale energy storage systems (ESSs). Lithium-ion batteries (LIBs), as one of the earliest commercialized ESSs, have already changed our life by their applications in electric vehicles and mobile electronics. − However, due to the shortage of lithium resources and the rising price of lithium salts, sodium-ion batteries (SIBs) present broad market prospects as the alternatives to complement LIBs in sustainable energy storage devices. − Besides, the physicochemical affinities between lithium and sodium afford the development of SIBs by drawing upon the extensive and successful research foundations established for LIBs. Given the cathode material’s significant influence on a battery’s cost and its electrochemical attributessuch as cycle stability, rate capability, and energy densitythe exploration of suitable cathode materials for SIBs becomes paramount. − The investigation of cathode materials for SIBs mainly includes primarily transition metal oxides, − polyanion compounds, , and Prussian blue analogues. , Statistics over the past five years reveal a consistent annual growth in papers related to these cathode materials as shown in Figure a, and the volume of articles on layered transition metal oxide (LTMO) cathode materials surpasses that of the other two cathode materials.…”