Lead-Free Solid-State Organic–Inorganic Halide Perovskite Electrolyte for Lithium-Ion Conduction

Abstract

Exploring new solid electrolytes (SEs) for lithium-ion conduction is significant for the development of rechargeable all-solid-state lithium batteries. Here, a lead-free organic–inorganic halide perovskite, MASr0.8Li0.4Cl3 (MA = methylammonium, CH3NH3 in formula), is reported as a new SE for Li-ion conduction due to its highly symmetric crystal structure, inherent soft lattice, and good tolerance for composition tunability. Via density functional theory calculations, we demonstrate that the hybrid perovskite framework can allow fast Li-ion migration without the collapse of the crystal structure. The influence of the lithium content in MASr1–x Li2x Cl3 (x = 0.1, 0.2, 0.3, or 0.4) on Li+ migration is systematically investigated. At the lithium content of x = 0.2, the MASr0.8Li0.4Cl3 achieves the room-temperature lithium ionic conductivity of 7.0 × 10–6 S cm–1 with a migration energy barrier of ∼0.47 eV. The lithium–tin alloy (Li–Sn) symmetric cell exhibits stable electrochemical lithium plating/stripping for nearly 100 cycles, indicating the alloy anode compatibility of the MASr0.8Li0.4Cl3 SE. This lead-free organic–inorganic halide perovskite SE will open a new avenue for exploring new SEs.

Potential electrolytes for solid state batteries and its electrochemical analysis—A review

“…Nano‐sized solid‐state electrolyte NASICON typed LATP was synthesized by evaporation‐induced self‐assembly for x = 0.4. The evaporation rate influences the particle size and when the concentration of aluminum increases in NATP then activation energy can decrease and the average grain size can increase, resulting in the improvement in total ionic conductivity 175 . The concentration of alkali salt may also influence the ionic conductivity of the synthesized material.…”

“…The evaporation rate influences the particle size and when the concentration of aluminum increases in NATP then activation energy can decrease and the average grain size can increase, resulting in the improvement in total ionic conductivity. 175 The concentration of alkali salt may also influence the ionic conductivity of the synthesized material. Therefore, the additional lithium salt may enhance the ionic conductivity of the material.…”

N‐Butyl Pyridinium Diiodido Argentate(I): A One‐Dimensional Ag‐I Network with Superior Solid‐State Ionic Conductivity at Room Temperature

“…Organic-inorganic metal halides are important materials for the next generation optoelectronic applications. [1][2][3] Whether the phase is perovskite or non-perovskite, these materials have been extensively used as light emitting solid state materials, [4][5][6][7][8] precursors are mixed in acetonitrile, heated to reflux, and then allowed to cool to room temperature. After a few hours, the crystalline product directly precipitates as yellow crystals that can directly be analyzed with single crystal X-ray diffraction.…”

“…A further advantage is that many solid ionic conductors can easily be patterned or shaped in device fabrication processes to match certain requirements. [5,13,16] Among all solid ionic conductors, silver halide based ionic conductors are arguably the most intensely researched compounds. [17,18] Among these, α-AgI is of particular interest because it shows superionic ionic conductivity as high as 1 S cm −1 .…”

Transitioning Towards Asymmetric Gel Polymer Electrolytes for Lithium Batteries: Progress and Prospects

“…Therefore, for highly safe solid-state polymer electrolytes, low conductivity, and unstable interfacial issues exist for battery operation at low temperatures. [4] Additionally, continuous consumption of additives during battery cycling does not entirely resolve flammability issues and reduces cell performance. [5] For such reasons, major modifications are still necessary for the progress and utilization of electrolytes.…”