Anti‐perovskite materials for energy storage batteries

Abstract

Anti-perovskites X 3 BA, as the electrically inverted derivatives of perovskites ABX 3 , have attracted tremendous attention for their good performances in multiple disciplines, especially in energy storage batteries. The Li/Na-rich antiperovskite (LiRAP/NaRAP) solid-state electrolytes (SSEs) typically show high ionic conductivities and high chemical/electrochemical stability toward the Li-metal anode, illustrating their great potential for applications in the Limetal batteries (LMBs) using nonaqueous liquid electrolyte or all-solid-state electrolyte. The antiperovskites have been studied as artificial solid electrolyte interphase for Li-metal anode protection, film SSEs for thin-film batteries, and low melting temperature solid electrolyte enabling melt-infiltration for the manufacture of all-solid-state lithium batteries. Transition metal-doped LiRAPs as cathodes have demonstrated a high discharge specific capacity and good rate capability in the Li-ion batteries (LIBs). Additionally, the underlying scientific principles in antiperovskites with flexible structural features have also been extensively studied. In this review, we comprehensively summarize the development, structural design, ionic conductivity and ion transportation mechanism, chemical/electrochemical stability, and applications of some antiperovskite materials in energy storage batteries. The perspective for enhancing the performance of the antiperovskites is also provided as a guide for future development and applications in energy storage. K E Y W O R D S antiperovskite, chemical and electrochemical stability, energy storage, solid-state electrolyte Zhi Deng and Dixing Ni contributed equally to this work.

Bilayer Halide Electrolytes for All-Inorganic Solid-State Lithium-Metal Batteries with Excellent Interfacial Compatibility

“…It has been attracting more and more research attention since Zhao et al designed and synthesized Li 3 OCl and Li 3 OCl 0.5 Br 0.5 with a high ionic conductivity of 10 –3 S cm –1 in 2012. Antiperovskite halide ISSEs were investigated deeply for the application in solid-state batteries, − and reported to be stable against a lithium-metal anode by different studies. − Another type of halide ISSEs has a rock-salt phase with a chemical formula of Li a MX b (M = In, Y, Sc; X = Cl, Br). , It shows a high ionic conductivity of 10 –3 S cm –1 , good oxidation stability over 4 V vs Li/Li + , and excellent electrochemical compatibility with cathode materials. Nevertheless, the reduction stability of rock-salt halides ISSEs is usually poor .…”

Optimized Interfaces in Anti-Perovskite Electrolyte-Based Solid-State Lithium Metal Batteries for Enhanced Performance

“…Recently, a new type of oxyhalide electrolytes (Li 3 OX, X = Cl, Br) with interesting anti-perovskite structures have been developed and displayed intrinsic stability toward the lithium metal anode and high ionic conductivity (10 −3 S/cm level at room temperature) ( Zhao and Daemen, 2012 ; Lu et al, 2020 ; Deng et al, 2021 ). Later, the proton-rich derivatives Li 2 OHX (X = Cl, Br, I) have also been synthesized and showed higher purity and milder synthesis process ( Hood et al, 2016 ; Li et al, 2016 ; Xiao et al, 2021 ).…”

“…Later, the proton-rich derivatives Li 2 OHX (X = Cl, Br, I) have also been synthesized and showed higher purity and milder synthesis process ( Hood et al, 2016 ; Li et al, 2016 ; Xiao et al, 2021 ). The Li 2 OHX (X = Cl, Br, I) electrolytes possess high lithium content and a similar crystal structure to Li 3 OX but with higher phase stability and can be prepared from low-price starting materials ( Hood et al, 2016 ; Li et al, 2016 ; Koedtruad et al, 2020 ; Lu et al, 2020 ; Deng et al, 2021 ; Guo et al, 2021 ). They have also displayed remarkable chemical and electrochemical stabilities toward lithium metals even at elevated temperatures ( Guo et al, 2021 ; Lai et al, 2021 ).…”

Rational Design of an Artificial SEI: Alloy/Solid Electrolyte Hybrid Layer for a Highly Reversible Na and K Metal Anode

“…38 As a class of conductive solidstate electrolyte (SSE), anti-perovskite materials (i.e., Na 3 OCl, Na 3 OBr) possess favorable mechanical behavior, negligible electronic conductivity, and chemical stability as well as conduction of Na ions. 39,40 Nevertheless, the harsh synthesis conditions hinder its applications in metal anode protection. 41,42 Furthermore, alkali alloy (Na-Sn, Na/K-Bi) SEI protection layers have received widespread attention due to their low ionic diffusion barrier and high adsorption energy toward Na/K, which are expected to further lower the nucleation barrier for sodium metals.…”

“…To address these issues, various strategies have been proposed to regulate uniform metal deposition, including surface engineering on Na/K metal, , optimizing the electrolyte to construct a stable SEI, , and embedding Na/K metal into a 3D conductive matrix. ,, Among them, construction of a stable SEI layer on the surface of Na/K metal has been demonstrated as one facile and efficient strategy. , Many studies have used halogen molecules to form an alkali halide (i.e., NaF and NaBr) layer on the metal anode, owing to the high Young’s modulus, electron insulation, and chemical stability of the alkali halide. , However, an ideal SEI film should also possess sodiophilicity and fast ion transport in addition to the above features . As a class of conductive solid-state electrolyte (SSE), anti-perovskite materials (i.e., Na 3 OCl, Na 3 OBr) possess favorable mechanical behavior, negligible electronic conductivity, and chemical stability as well as conduction of Na ions. , Nevertheless, the harsh synthesis conditions hinder its applications in metal anode protection. , Furthermore, alkali alloy (Na-Sn, Na/K-Bi) SEI protection layers have received widespread attention due to their low ionic diffusion barrier and high adsorption energy toward Na/K, which are expected to further lower the nucleation barrier for sodium metals. , One can expect that constructing an alloy/solid electrolyte hybrid layer for an alkali metal battery by a simple and convenient method would be an effective solution for the inhibition of dendrite growth.…”