Revisiting the Role of Hydrogen in Lithium‐Rich Antiperovskite Solid Electrolytes: New Insight in Lithium Ion and Hydrogen Dynamics

Li2OHX (X = Cl or Br) with an antiperovskite structure possess the advantages of low melting point, low cost, and ease of scaling‐up, which show great promise for applications in all‐solid‐state Li metal batteries (ASSLMBs). However, Li‐ion transport mechanisms in Li2OHX are still debated and the influence of H on the electrochemical performance of Li2OHX is yet to be explored. Herein, combining the theoretical calculations and experimental measurements, it is found that H affects Li‐ion transport, crystal stability, electrochemical stability, and electronic conductivity of Li2OHX. Compared with H‐free Li3OCl, although H helps to generate vacancy‐like defects, the electrostatic repulsive force between H and Li‐ion leads to an increase in both the activation energy and the diffusion length (space compensation effect), resulting in special Li ion transport trajectories along the Li‐O plane. Decreasing H content reduces the electronic conductivity and enhances the reduction‐resistant ability of Li2OHX, promoting the cycling stability and rate performance of Li∣Li2OHX∣Li symmetric cells and the ASSLMBs. This work delivers a new insight into the role of H in antiperovskite Li2OHX and can serve as guidance for solid electrolyte design.

[1]  G. Cui,et al.  A polymer electrolyte with a thermally induced interfacial ion-blocking function enables safety-enhanced lithium metal batteries , 2022, eScience.

[2]  Yang Zhao,et al.  Antiperovskite Electrolytes for Solid-State Batteries. , 2022, Chemical reviews.

[3]  Shiwei Chen,et al.  Ultrathin salt-free polymer-in-ceramic electrolyte for solid-state sodium batteries , 2021, eScience.

[4]  Huimin Yuan,et al.  Li-Rich Antiperovskite/Nitrile Butadiene Rubber Composite Electrolyte for Sheet-Type Solid-State Lithium Metal Battery , 2021, Frontiers in Chemistry.

[5]  Jinlong Zhu,et al.  Regulating the lithium metal growth by Li3BO3/Li2OHCl solid-state electrolyte for long-lasting lithium metal stripping-plating , 2021 .

[6]  L. Ci,et al.  A novel coral-like garnet for high-performance PEO-based all solid-state batteries , 2021, Science China Materials.

[7]  Shuai Li,et al.  Stabilization of NASICON-Type Electrolyte against Li Anode via an Ionic Conductive MOF-Incorporated Adhesive Interlayer , 2021, ACS Energy Letters.

[8]  Z. Deng,et al.  Lithium-Rich Anti-perovskite Li2OHBr-Based Polymer Electrolytes Enabling an Improved Interfacial Stability with a Three-Dimensional-Structured Lithium Metal Anode in All-Solid-State Batteries. , 2021, ACS Applied Materials and Interfaces.

[9]  S. Shi,et al.  Computational insights into the ionic transport mechanism and interfacial stability of the Li2OHCl solid-state electrolyte , 2021 .

[10]  M. Islam,et al.  Atomistic Insights into the Effects of Doping and Vacancy Clustering on Li-Ion Conduction in the Li3OCl Antiperovskite Solid Electrolyte , 2021 .

[11]  Z. Wen,et al.  In situ fabricated ceramic/polymer hybrid electrolyte with vertically aligned structure for solid-state lithium batteries , 2021 .

[12]  J. Tu,et al.  Porous Polyamide Skeleton-Reinforced Solid-State Electrolyte: Enhanced Flexibility, Safety, and Electrochemical Performance. , 2021, ACS applied materials & interfaces.

[13]  Chen‐Zi Zhao,et al.  Critical Current Density in Solid‐State Lithium Metal Batteries: Mechanism, Influences, and Strategies , 2021, Advanced Functional Materials.

[14]  Cheng Ma,et al.  Interplay between Li3YX6 (X = Cl or Br) solid electrolytes and the Li metal anode , 2021, Science China Materials.

[15]  R. Li,et al.  A flexible electron-blocking interfacial shield for dendrite-free solid lithium metal batteries , 2020, Nature communications.

[16]  Shuai Li,et al.  Local Structural Changes and Inductive Effects on Ion Conduction in Antiperovskite Solid Electrolytes , 2020 .

[17]  Craig M. Brown,et al.  Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li2OHCl , 2020 .

[18]  X. Lü,et al.  Antiperovskites with Exceptional Functionalities , 2019, Advanced materials.

[19]  Liquan Chen,et al.  Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces. , 2019, Chemical reviews.

[20]  Xiulin Fan,et al.  High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes , 2019, Nature Energy.

[21]  C. Liang,et al.  Aligning academia and industry for unified battery performance metrics , 2018, Nature Communications.

[22]  Chunsheng Wang,et al.  Suppressing Li Dendrite Formation in Li2S‐P2S5 Solid Electrolyte by LiI Incorporation , 2018 .

[23]  Yaxiang Lu,et al.  Drawing a Soft Interface: An Effective Interfacial Modification Strategy for Garnet-Type Solid-State Li Batteries , 2018 .

[24]  Wei Luo,et al.  Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries , 2018, Advanced materials.

[25]  Christian Masquelier,et al.  Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries. , 2018, Journal of the American Chemical Society.

[26]  O. Borodin,et al.  Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups , 2018 .

[27]  G. Ceder,et al.  Role of Point Defects in Spinel Mg Chalcogenide Conductors , 2017, 1710.10443.

[28]  P. Jena,et al.  Li-rich antiperovskite superionic conductors based on cluster ions , 2017, Proceedings of the National Academy of Sciences.

[29]  Yizhou Zhu,et al.  Origin of fast ion diffusion in super-ionic conductors , 2017, Nature Communications.

[30]  Shaofei Wang,et al.  Solid-State Lithium Metal Batteries Promoted by Nanotechnology: Progress and Prospects , 2017 .

[31]  Ruiqin Q. Zhang,et al.  C=C π Bond Modified Graphitic Carbon Nitride Films for Enhanced Photoelectrochemical Cell Performance. , 2017, Chemistry, an Asian journal.

[32]  Zachary D. Hood,et al.  Li2OHCl Crystalline Electrolyte for Stable Metallic Lithium Anodes. , 2016, Journal of the American Chemical Society.

[33]  L. Daemen,et al.  Superionic conductivity in lithium-rich anti-perovskites. , 2012, Journal of the American Chemical Society.

[34]  M. Jansen,et al.  High lithium ionic conductivity in the lithium halide hydrates Li3-n(OHn)Cl (0.83 < or = n < or = 2) and Li3-n(OHn)Br (1 < or = n < or = 2) at ambient temperatures. , 2003, Chemphyschem : a European journal of chemical physics and physical chemistry.

[35]  Potential Solid-State Electrolytes with Good Balance between Ionic Conductivity and Electrochemical Stability: Li5xM1xMxO4 (M = Al and Ga and M = Si and Ge) , 2022 .