Influence of Chloride Ion Substitution on Lithium-Ion Conductivity and Electrochemical Stability in a Dual-Halogen Solid-State Electrolyte

Umeshbabu, Ediga; Satyanarayana, M.; Hu, Yang; Fichtner, Maximilian; Reddy, M. Anji

doi:10.1021/acsami.2c04160

Cited by 22 publications

(28 citation statements)

References 58 publications

(107 reference statements)

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“…Changing trivalent metal cations at the M site leads to halide SSEs with different reduction potentials ( 17 , 65 ). Altering halogen anions at the X site can adjust the oxidation stability of halide SSEs (F − > Cl − > Br − > I − ) ( 66 ). To better understand the structure-to-performance relationship, we summarize the ionic conductivity of various halide SSEs according to their anion sublattice and space groups ( Fig.…”

Section: Current Advances and Cost-effectiveness Of Halide Ssesmentioning

confidence: 99%

Prospects of halide-based all-solid-state batteries: From material design to practical application

et al. 2022

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The safety of lithium-ion batteries has caused notable concerns about their widespread adoption in electric vehicles. A nascent but promising approach to enhancing battery safety is using solid-state electrolytes (SSEs) to develop all-solid-state batteries, which exhibit unrivaled safety and superior energy density. A new family of SSEs based on halogen chemistry has recently gained renewed interest because of their high ionic conductivity, high-voltage stability, good deformability, and cost-effective and scalable synthesis routes. Here, we provide a comprehensive review of halide SSEs concerning their crystal structures, ion transport kinetics, and viability for mass production. Furthermore, their moisture sensitivity and interfacial challenges are summarized with corresponding effective strategies. Last, halide-based all-solid-state Li-ion and Li-S pouch cells with energy density targets of 400 and 500 Wh kg −1 are projected to guide future endeavors. This work serves as a comprehensive guideline for developing halide SSEs from material design to practical application.

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Section: Current Advances and Cost-effectiveness Of Halide Ssesmentioning

confidence: 99%

Prospects of halide-based all-solid-state batteries: From material design to practical application

et al. 2022

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“…[ 20 ] Furthermore, based on the investigation on Cl − ‐substituted Li 2 ZrF 6 , the Li + conductivity of Li 2 ZrF 5 Cl is improved by ∼5 orders of magnitude. [ 54 ] We can conclude that isovalent anion substitution could be an effective strategy to enhance the ionic conductivity of fluorides, and it is critical for fluorides to be used as electrolytes for LMSBs. More attention should be given in terms of improving the Li + conductivity of fluoride‐based SEs.…”

Section: Structure Features and Ionic Conductivity Of Halide‐based So...mentioning

confidence: 99%

Halide‐based solid electrolytes: The history, progress, and challenges

Nie

2023

Interdisciplinary Materials

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Lithium metal solid‐state batteries (LMSBs) have attracted extensive attention over the past decades, due to their fascinating advantages of safety and potential for high energy density. Solid‐state electrolytes (SEs) with fast ionic transport and excellent stability are indispensable components in LMSBs. Heretofore, a series of inorganic SEs have been extensively explored, such as sulfide‐ and oxide‐based electrolytes. Unfortunately, they both have difficulty in achieving a satisfactory balance of conductivity and stability, and oxides suffer from a high impedance of grain boundaries, while sulfides encounter poor stability. Halide‐based solid electrolytes are gradually emerging as one of the most promising candidates for LMSBs due to their advantages of decent room temperature ionic conductivity (>10−3 S cm−1), good compatibility with oxide cathode materials, good chemical stability, and scalability. Herein, research and development of the widely studied metal halide SEs including fluorides, chlorides, bromides, and iodides are reviewed, mainly focusing on the structures and ionic conductivities as well as preparation methods and electrochemical/chemical stabilities. And then, based on typical metal halide solid electrolytes, we emphasize the interface issues (grain boundaries, cathode−electrolyte and electrolyte–anode interfaces) that exist in the corresponding LMSBs and summarize the related work on understanding and engineering these interfaces. Furthermore, the typical (or in situ) characterization tools widely used for solid‐state interfaces are reviewed. Finally, a perspective on the future direction for developing high‐performance LMSBs based on the halide electrolyte family is put out.

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“…To realize ASSBs, several efforts have been devoted to developing solid-state electrolytes, such as oxides, sulfides, solid polymer electrolytes, halide electrolytes, and their hybrids, which are required to have high ionic conductivity, low electronic conductivity, and high mechanical and chemical stability. − Among these, sulfide-based solid electrolytes (SSEs) are considered more promising than commercially available oxides due to their high room-temperature ionic conductivity, moderate synthesis conditions, and low grain boundary resistance . One of the most explored SSEs for sodium metal batteries is sodium thiophosphate (Na 3 PS 4 ).…”

Section: Introductionmentioning

confidence: 99%

Microwave-Assisted Synthesis of Sulfide Solid Electrolytes for All-Solid-State Sodium Batteries

Aswathy

Suriyakumar

Kumar

et al. 2022

ACS Appl. Energy Mater.

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Sulfide-based solid electrolytes are one of the potential candidates for all-solid-state batteries due to their high ionic conductivity and low synthesis temperature compared to their oxide counterparts. However, the preparation methods involve the requirement of an inert atmosphere for ball milling, heating, and quenching facilities that severely limit their implementation, which necessitates a resurgence of interest in alternate synthesis approaches. Herein, a simple, accelerated, and energy-efficient method for the synthesis of highly crystalline cubic sodium thiophosphate solid electrolyte (Na 3 PS 4 ) is developed using the microwaveassisted irradiation technique. Along with impedance studies, 23 Na solid-state NMR spin-lattice relaxation experiments are performed to obtain insights into Na-ion mobility in Na 3 PS 4 solid electrolytes. The electrochemical properties and the interfacial stability of the electrolyte with the metallic sodium anode are thoroughly investigated and presented in this work. Further, a prototype full-cell constructed using a Na 3 V 2 (PO 4 ) 3 cathode, a Na 3 PS 4 solid electrolyte, and a modified sodium anode showed promising electrochemical properties. Although numerous studies focus on solid electrolyte interface modification and design, the simple and energy-efficient approach for sodium-ion solid electrolyte synthesis presented here will provide a meaningful advance to the accelerated synthesis of sulfide electrolyte-based all-solid-state batteries.

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Influence of Chloride Ion Substitution on Lithium-Ion Conductivity and Electrochemical Stability in a Dual-Halogen Solid-State Electrolyte

Cited by 22 publications

References 58 publications

Prospects of halide-based all-solid-state batteries: From material design to practical application

Prospects of halide-based all-solid-state batteries: From material design to practical application

Halide‐based solid electrolytes: The history, progress, and challenges

Microwave-Assisted Synthesis of Sulfide Solid Electrolytes for All-Solid-State Sodium Batteries

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