Antiperovskite Electrolytes for Solid-State Batteries

Abstract

Solid-state batteries have fascinated the research community over the past decade, largely due to their improved safety properties and potential for high-energy density. Searching for fast ion conductors with sufficient electrochemical and chemical stabilities is at the heart of solid-state battery research and applications. Recently, significant progress has been made in solid-state electrolyte development. Sulfide-, oxide-, and halide-based electrolytes have been able to achieve high ionic conductivities of more than 10 −3 S/cm at room temperature, which are comparable to liquid-based electrolytes. However, their stability toward Li metal anodes poses significant challenges for these electrolytes. The existence of non-Li cations that can be reduced by Li metal in these electrolytes hinders the application of Li anode and therefore poses an obstacle toward achieving high-energy density. The finding of antiperovskites as ionic conductors in recent years has demonstrated a new and exciting solution. These materials, mainly constructed from Li (or Na), O, and Cl (or Br), are lightweight and electrochemically stable toward metallic Li and possess promising ionic conductivity. Because of the structural flexibility and tunability, antiperovskite electrolytes are excellent candidates for solid-state battery applications, and researchers are still exploring the relationship between their structure and ion diffusion behavior. Herein, the recent progress of antiperovskites for solid-state batteries is reviewed, and the strategies to tune the ionic conductivity by structural manipulation are summarized. Major challenges and future directions are discussed to facilitate the development of antiperovskite-based solid-state batteries.

Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors

“…In Li 3 OCl (Figure 3, top), we find that the presence of GBs has a profound effect which is in good agreement with previous calculations that employed classical interatomic potentials. 10 This provides further confirmation as to why computational predictions from simulations on bulk tend to overestimate the conductivity of antiperovskite materials compared to experiments which report activation energies as large as 0.6 eV, 23,38 which is in better agreement with our GB simulations than with our bulk simulations. For Li 3 PS 4 (Fig-…”

Unravelling the alkali transport properties in nanocrystalline A3OX (A = Li, Na, X = Cl, Br) solid state electrolytes. A theoretical prediction

“…The search for affordable inorganic electrolytes for future all solid state alkali-ion batteries is one of the current hot topics due to the urgent need for high energy density materials and relevant safety issues. [1][2][3][4][5] Exploration and prediction of the properties of electrolytes are crucial for the improvement of performance and durability of the battery. [1][2][3][4][5][6][7] Of particular interest, the development of inorganic solid electrolyte faces critical issues, such as the lower electrical conductivity as compared to conventional liquid electrolytes, interfacial resistance with the electrodes, narrow electrochemical window that constrain its practical applications.…”

“…[1][2][3][4][5] Exploration and prediction of the properties of electrolytes are crucial for the improvement of performance and durability of the battery. [1][2][3][4][5][6][7] Of particular interest, the development of inorganic solid electrolyte faces critical issues, such as the lower electrical conductivity as compared to conventional liquid electrolytes, interfacial resistance with the electrodes, narrow electrochemical window that constrain its practical applications. [4][5][6][7] Of the compounds with special interest for inorganic solid electrolyte, the Li-rich anti-perovskite Li 3 OX (X ¼ Cl À , Br À ) has attracted large scientic interest due to the high Li ionic conductivity (z1 mS cm À1 ) and stability with the electrode, and low Li activation energy (z0.2 eV).…”

“…[1][2][3][4][5][6][7] Of particular interest, the development of inorganic solid electrolyte faces critical issues, such as the lower electrical conductivity as compared to conventional liquid electrolytes, interfacial resistance with the electrodes, narrow electrochemical window that constrain its practical applications. [4][5][6][7] Of the compounds with special interest for inorganic solid electrolyte, the Li-rich anti-perovskite Li 3 OX (X ¼ Cl À , Br À ) has attracted large scientic interest due to the high Li ionic conductivity (z1 mS cm À1 ) and stability with the electrode, and low Li activation energy (z0.2 eV). [8][9][10][11][12] Nevertheless, a higher activation energy (z0.6 eV) and a lower ionic conductivity for Li 3 OX have recently been reported experimentally.…”

Flexible Asymmetric Organic-Inorganic Composite Solid-State Electrolyte Based on PI Membrane for Ambient Temperature Solid-State Lithium Metal Batteries

“…The key component of solid-state batteries is a solid-state electrolyte (SSE). A perfect SSE should have high ionic conductivity, good interfacial stability and adhesion with the electrodes, a wide electrochemical window, good chemical stability, strong mechanical stability, nonvolatility, and nonflammability ( Quartarone and Mustarelli, 2011 ; Judez et al, 2019 ; Xia et al, 2022 ). A great deal of research has been devoted to the various SSE materials, which can be summarized into three kinds, inorganic (oxides/sulfide) solid electrolytes, solid polymer electrolytes (SPEs), and their hybrids.…”