Ionic Conductivity Research Articles

Enhancing performance and sustainability of lithium manganese oxide cathodes with a poly(ionic liquid) binder and ionic liquid electrolyte

Current battery production involves various energy intensive processes and the use of volatile, flammable and/or toxic chemicals. This study explores the potential for using a water-soluble and functional binder, poly(diallyldimethylammonium) (PDADMA) with diethyl phosphate (DEP) as a counter anion, for lithium manganese oxide (LMO) cathodes. By replacing the traditional polyvinylidene fluoride (PVDF) binder and its associated toxic N-methyl-2-pyrrolidone (NMP) solvent, PDADMA-DEP offers a more sustainable and cost-effective solution. Notably, PDADMA-DEP electrodes do not require high-temperature calendaring to achieve high performance unlike PVDF electrodes. X-ray Photoelectron Spectroscopy (XPS) indicated significant interactions between the binder and LMO that enhance stability and ion conduction. The PDADMA-DEP binder demonstrated excellent electrochemical rate capability up to 10C with the conventional organic liquid electrolyte (LP30), outperforming PVDF electrodes. The performance of both binders using a safer and non-volatile ionic liquid electrolyte, specifically 50 mol% LiFSI in N-trimethyl-N-propylammonium bis(fluorosulfonyl)imide, was also investigated to enhance the overall safety and environmental impact of the battery system. IL-based cells utilizing a PDADMA-DEP cathode binder demonstrated a 58 % capacity retention over 500 cycles at 0.5C when cycled at room temperature.

Charge Separation Induced by Asymmetric Surface Charge Effects in Quasi‐Solid State Electrolyte for Sustainable Anion Storage

AbstractCompared with conventional lithium‐ion battery systems, anion‐intercalation in graphite cathodes opens avenues for the development of batteries with groundbreaking power density. This study explores the enhancement of dual‐ion batteries (DIBs) by gel polymer electrolyte (GPE) enhanced with surface‐charged nanoclays, focusing on overcoming traditional challenges such as electrolyte decomposition, anion‐solvent co‐intercalation, and interfacial instability at the graphite cathode. Three nanoclays including montmorillonite, kaolinite, and halloysite are compared by incorporating them into GPE and evaluating their effect on the electrochemical properties, ion conduction, and mechanical integrity of DIBs. Particular attention is paid to the halloysite because of its differential internal and external surface charges, which generate charge separation, facilitate optimal lithium‐ion transport, and mitigate undesirable anion‐solvent interactions. These results indicate that halloysite‐incorporated GPE (HS‐G) significantly improves DIB performance, as demonstrated by extended cycle life, robust capacity retention at fast charge/discharge rates of 20 C, and operational stability over a wide temperature range (0–60 °C). These improvements are attributed to the unique structural advantages of HS‐G, including effective charge separation, enhanced anion diffusion, and reduced solvent co‐intercalation, which provide an environmentally friendly and cost‐effective approach to advanced DIB applications.

Porous Organic Cage-Based Quasi-Solid-State Electrolyte with Cavity-Induced Anion-Trapping Effect for Long-Life Lithium Metal Batteries

Porous organic cages (POCs) with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior, yet their feasibility as solid-state electrolytes has never been testified in a practical battery. Herein, we design and fabricate a quasi-solid-state electrolyte (QSSE) based on a POC to enable the stable operation of Li-metal batteries (LMBs). Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC, the resulting POC-based QSSE exhibits a high Li+ transference number of 0.67 and a high ionic conductivity of 1.25 × 10−4 S cm−1 with a low activation energy of 0.17 eV. These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h. As a proof of concept, the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85% capacity retention after 1000 cycles. Therefore, our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems, such as Na and K batteries.

Water as Dual-Function Plasticizer and Cosolvent in Gel Electrolytes for Dye-Sensitized Solar Cells.

This study presents a novel approach to developing eco-friendly dye-sensitized solar cells (DSSCs) using natural and renewable materials for gel polymer electrolytes (GPEs), reducing reliance on unsustainable solvents. Water is added to polar aprotic solvents, specifically ethylene carbonate/propylene carbonate (EC/PC), across various mass fractions (0:100 to 100:0). An amphiphilic hydroxypropyl cellulose (HPC) natural polymer is employed to formulate GPEs within this water-EC/PC cosolvent system, achieving successful gelation up to 50:50 mass fractions. Incorporating water reduced the gel strength and viscosity of the GPEs. Water acted as a plasticizer, enhancing the polymer chains mobility, and creating a more flexible and permeable structure. This increased ion diffusion coefficients and ion mobility, resulting in a maximum ionic conductivity of 18.17 mS cm-1. The highest efficiency achieved in DSSCs using these GPEs is 5.81%, with elevated short-circuit current density and reduced recombination losses. However, some compositions experienced syneresis, affecting their stability. The GPE with a 40:60 mass fraction exhibited superior long-term stability because it is free from syneresis, though it achieved a lower efficiency (4.83%), making it the best-performing sample. This work demonstrates the feasibility and benefits of using gel polymer electrolytes in an aqueous system, improving DSSC efficiency and sustainability.

ZnO Nanoparticle Assisted Liquid Metal for Dendrite-Free Zn Metal Anodes.

Dendrite growth and interfacial side reactions on Zn anode seriously affect the safety and service life of Zn ions batteries. Interface engineering is an effective way to solve these problems. Here, a liquid metal-ZnO composite coating with high ionic conductivity is creatively designed, which not only reduces the Zn2+ diffusion barrier but also increases the hydrogen evolution overpotential, thereby eliminating dendrite growth behavior and corrosion on the modified Zn anode. Moreover, its unique structure induces Zn deposition into the inner of coating, which can effectively avoid the volume expansion in the deposit layer of Zn anode. Therefore, it can cycle for 3000 h at an ultra-small polarization of 28 mV at 1 mA cm-2, and the microbattery assembled in combination with the MnO2 cathode also maintains 2000 cycles with high Coulomb efficiency, providing a general idea for the development of the next generation of rechargeable metal batteries.

In Situ Alloying Enabled by Active Liquid Metal Filler for Self‐Healing Composite Polymer Electrolytes

AbstractSolid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self‐healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li‐ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li‐LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid‐state Li/LiFePO4 battery achieves promising full‐cell functionality with notable rate performance and stable cycle life. This active filler‐mediated self‐healing approach could bring new insights into the battery design in versatile solid‐state systems.

In Situ Alloying Enabled by Active Liquid Metal Filler for Self-Healing Composite Polymer Electrolytes.

Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self-healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li-ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li-LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid-state Li/LiFePO4 battery achieves promising full-cell functionality with notable rate performance and stable cycle life. This active filler-mediated self-healing approach could bring new insights into the battery design in versatile solid-state systems.

Janus-Architectured Lithium Replenishment Separators Boosting Longevity of Anode-Free Lithium Metal Batteries.

Addressing the issue of inactive dead lithium deposition on the anode side remains a significant challenge for anode-free lithium metal batteries. While lithium compensation techniques can mitigate lithium depletion, directly introducing lithium compounds into the cathode material may degrade the electrode structure. Here the design and fabrication of a novel lithium replenishment separator (LRS) using a lithium compensation agent of Li2C4O4 is reported. The electrospun LRS demonstrates excellent ionic conductivity of 1.82 mS cm-1 and a high Li+ transference number of 0.51. Such a functionalized LRS not only provides additional active lithium for anode-free lithium metal batteries but also promotes uniform deposition of lithium metal. Compared with conventional polyolefin-based separators, the LRS effectively boosts LiFePO4||Cu anode-free batteries with enhanced cyclability. These results suggest this LRS strategy can find promising applications in next-generation anode-free batteries with high energy densities.

Synergistic Dual Electrolyte System of LATP and In‐ Situ Solod‐State PDOL System and its Improvement on the Performance of NCM811 Batteries

Abstract1,3‐Dioxolane (DOL) can undergo in‐situ polymerization in batteries to form solid‐state organic electrolyte PDOL. When applied to NCM811||Li battery system, PDOL electrolyte helps optimize the contact and interface stability between electrolyte and electrodes. This study explores the effects of PDOL with PE separators coated with Li1.3Al0.3Ti1.7(PO4)3(LATP) on the performance of NCM811||Li batteries. 2,2,2‐trifluoroethyl phosphite (DETFPi), was mixed with DOL at a 1 : 35 mass ratio. Then, LiBF4 was used to initiate in‐situ polymerization and thereby obtained DETFPi‐PDOL electrolyte after 24 h at room temperature. The composite electrolyte exhibits enhanced ion conductivity (1.59×10−4 S cm−1), high lithium ion transference number (0.78), wide electrochemical stability window (4.53 V), and high critical current density (2.2 mA cm−2). Li||PDOL@LATP||Li battery shows extremely low overpotential (35 mV) after a constant current stable cycle of 500 h at 1.0 mA cm−2. After 500 cycles at 1 C, the remaining capacity is 153.9 mAh g−1 with a capacity retention of 82.1 % in NCM811||PDOL@LATP||Li batteries. This indicates that the LATP coating on the surface of the PE separator plays an important role in optimizing the performance of DETFPI‐PDOL electrolyte batteries. LATP and DETFPI‐PDOL are effective in improving the cycling stability, rate performance, and interface state of NCM811 batteries.

Boosting Li-Ion Conductivity of Fluoride Solid Electrolyte by Low-Temperature Molten Salt Ablation and Particle Boundary Doping.

Halide solid electrolytes (SEs) are attracting great attention, owing to their high ionic conductivity and excellent high-voltage compatibility. However, severe moisture sensitivity, poor thermal stability, and instability at the lithium metal anode interface with chloride and bromide SEs retard their applications in solid-state lithium metal batteries. Fluoride SEs are expected to solve these problems, but they are now plagued by inadequate room-temperature (RT) ionic conductivity. Herein, a low-temperature molten salt (LiCl+1.33AlCl3) ablation method is proposed to enhance the ionic conductivity of monoclinic Li3GaF6 by particle boundary doping. The RT ionic conductivity of Li3GaF6 is correspondingly increased by 2 orders of magnitude, and the conductivity reaches 10-4 S cm-1 at 60 °C. The improved ionic conductivity benefits from the enhancement of interfacial ion transport, with the formation of more conductive chlorine-doped Li3GaF6-xClx and in situ binder LiAlCl4 to cement surrounding nanoparticles. The as-synthesized Li3GaF6 demonstrates outstanding humidity tolerance without conductivity degradation after exposure to a relative humidity of up to 35%. It also exhibits the widest electrochemical stability window experimentally (close to 6 V) compared with other state-of-the-art SEs. The solid-state Li/Li3GaF6/LiFePO4 cell with a stable Li+-conductive polymer interface is successfully driven for at least 200 cycles at 0.5C. Our study provides a solution to various chemical and electrochemical stability issues encountered by the halide SE family.

Organic-Inorganic Dual-Network Composite Separators for Lithium Metal Batteries.

The suboptimal ionic conductivity of commercial polyolefin separators exacerbates uncontrolled lithium dendrite formation, deteriorating lithium metal battery performance and posing safety hazards. To address this challenge, a novel organic-inorganic composite separator designed is prepared to enhance ion transport and effectively suppress dendrite growth. This separator features a thermally stable, highly porous poly(m-phenylene isophthalamide) (PMIA) electrospun membrane, coated with ultralong hydroxyapatite (HAP) nanowires that promote "ion flow redistribution." The synergistic effects of the nitrogen atoms in PMIA and the hydroxyl groups in HAP hinder anion transport while facilitating efficient Li+ conduction. Meanwhile, the optimized unilateral pore structure ensures uniform ion transport. These results show that the 19µm-thick HAP/PMIA composite separator achieves remarkable ionic conductivity (0.68mS cm-1) and a high lithium-ion transference number (0.51). Lithium symmetric cells using HAP/PMIA separators exhibit a lifespan exceeding 1000h with low polarization, significantly outperforming commercial polypropylene separators. Furthermore, this separator enables LiFePO4||Li cells to achieve an enhanced retention of 97.3% after 200 cycles at 1C and demonstrates impressive rate capability with a discharge capacity of 72.7mAh g-1 at 15C.

AdvancedEutectogel Electrolyte for High‐Performance and Wide‐Temperature Flexible Zinc‐Air Batteries

Despite ongoing challenges, achieving further breakthroughs in the development of gel polymer electrolytes with a wide temperature range, excellent liquid retention capability and enhanced anode compatibility in flexible zinc‐air batteries (FZABs) remains a significant objective. This study presents a significant advancement in the development of choline chloride/ethylene glycol‐polyvinyl alcohol (ChCl/EG‐PVA) eutectogel electrolyte, tailored for high‐performance operation across a wide temperature range. Systematic in‐situ and ex‐situ characterizations and theoretical simulations confirm the formation of robust hydrogen bonding and denser polymer cross‐linked networks within the prepared eutectogel, leading to enhanced liquid retention ability (93.7% after 96 h exposure to air) and the ion transport capacity (ionic conductivity of 171.3 mS cm‐1). Additionally, the zincophilicity nature of the choline cation in eutectogel effectively suppresses dendrites growth. The assembled FZAB utilizing this eutectogel electrolyte achieves a peak power density of 109.3 mW cm‐2 and a cycle life of 90 h. Notably, the power density of FZAB is maintained as high as 38.2 mW cm‐2 at ‐40 oC and 63.2 mW cm‐2 at 50 oC, demonstrating its prominent suitability for applications in extreme temperature conditions. The design of eutectogel provides a novel way to achieve the high‐performance FZAB.

AdvancedEutectogel Electrolyte for High-Performance and Wide-Temperature Flexible Zinc-Air Batteries.

Despite ongoing challenges, achieving further breakthroughs in the development of gel polymer electrolytes with a wide temperature range, excellent liquid retention capability and enhanced anode compatibility in flexible zinc-air batteries (FZABs) remains a significant objective. This study presents a significant advancement in the development of choline chloride/ethylene glycol-polyvinyl alcohol (ChCl/EG-PVA) eutectogel electrolyte, tailored for high-performance operation across a wide temperature range. Systematic in-situ and ex-situ characterizations and theoretical simulations confirm the formation of robust hydrogen bonding and denser polymer cross-linked networks within the prepared eutectogel, leading to enhanced liquid retention ability (93.7% after 96 h exposure to air) and the ion transport capacity (ionic conductivity of 171.3 mS cm-1). Additionally, the zincophilicity nature of the choline cation in eutectogel effectively suppresses dendrites growth. The assembled FZAB utilizing this eutectogel electrolyte achieves a peak power density of 109.3 mW cm-2 and a cycle life of 90 h. Notably, the power density of FZAB is maintained as high as 38.2 mW cm-2 at -40 oC and 63.2 mW cm-2 at 50 oC, demonstrating its prominent suitability for applications in extreme temperature conditions. The design of eutectogel provides a novel way to achieve the high-performance FZAB.

Ionic Covalent Organic Frameworks Consisting of Tetraborate Nodes and Flexible Linkers.

Covalent organic frameworks (COFs) have emerged as versatile materials with many applications, such as carbon capture, molecular separation, catalysis, and energy storage. Traditionally, flexible building blocks have been avoided due to their potential to disrupt ordered structures. Recent studies have demonstrated the intriguing properties and enhanced structural diversity achievable with flexible components by judicious selection of building blocks. This study presents a novel series of ionic COFs (ICOFs) consisting of tetraborate nodes and flexible linkers. These ICOFs use borohydrides to irreversibly deprotonate the alcohol monomers to achieve a high degree of polymerization. Structural analysis confirms the dia topologies. Reticulation is explored using various monomers and metal counterions. Also, these frameworks exhibit excellent stability in alcohols and coordinating solvents. The materials have been tested as single-ion conductive solid-state electrolytes. ICOF-203-Li displays one of the lowest activation energies reported for ion conduction. This tetraborate chemistry is anticipated to facilitate further structural diversity and functionality in crystalline polymers.

Hydrogel Electrolyte with Regulated Water Activity and Hydrogen Bond Network for Ultra‐Stable Zinc Electrode

AbstractQuasi‐solid‐state zinc‐ion batteries (QZIBs) have attracted wide attention due to their excellent dimensional stability and high safety. However, poor ion conduction capabilities, severe dendrite growth, and rampant side reactions still hinder their commercialization. The regulation of the solvation structure of Zn2+ is considered to be an effective method to address these issues. Herein, a hydrogel electrolyte with a regulated solvation structure (HE‐RS) is designed via the combination of tetramethyl urea (TMU) additive and polyvinyl alcohol (PVA) matrix. The hydrophilic ─C═O group of TMU exhibits strong affinity with the PVA chains, improving the mechanical strength of the PVA matrix. The ─N(CH3)2 groups at both ends of TMU exhibit strong hydrophobic characteristics, which leads to local hydrophobicity and decreased water activity. Additionally, abundant oxygen‐containing (electronegative) groups on both PVA and TUM can adsorb Zn2+ and provide sites for Zn2+ transference. Benefiting from these merits, Zn2+ solvation structure and deposition behavior are regulated. Consequently, the Zn||Zn symmetric cell with HE‐RS exhibits a stable cycling life exceeding 2000 h. Moreover, the HE‐RS‐based Zn||NH4V4O10 cell exhibits a capacity retention of 96.4% after 1000 cycles at 2 A g−1.

Synthesis, Structure, and Electrochemistry of Crystallized Layered Chlorides, LiMCl6 (M = Ta/Nb)

AbstractA suitable solid electrolyte can turn the long‐standing dream of a safe commercial all‐solid‐statebattery into reality in the same way as appropriate liquid electrolytes kickstarted the first commercial lithium‐ion battery. Presently, halide‐based electrolytes despite their reactivity with lithium metal are extensively studied as they offer better processability, malleability, oxidative stability, and safety over sulfide‐based electrolytes. Particularly, LiMCl6 (M = Ta/Nb) chloride‐based amorphous electrolytes are generating widespread interest with their high conductivities, comparable to liquid electrolytes. In this context, with synchrotron X‐ray and neutron powder diffraction techniques, well‐crystallized triclinic layered LiMCl6 (M = Ta/Nb) chlorides with an hcp AB‐type stacking of chloride ions is reported. The hexagonally ordered NbCl6 octahedra share edges with LiCl6 octahedra forming a honeycomb pattern, whereas Li+ is intermixed with M5+ for M = Ta. Furthermore, it is found that crystalline LiTaCl6 has an ionic conductivity of ≈10−5 mS cm−1, six orders of magnitude lower than that reported for superionic amorphous LiTaCl6. Nevertheless, crystalline LiTaCl6 is utilized as an intercalation compound in an all‐solid‐state‐battery, uncovering a solid‐solution/two‐phase/conversion pathway for lithium‐insertion during the three distinct redox plateaus below 3 V versus Li+/Li°. Broadly, the findings give insights into the structure, ionic conduction, and intercalation in a new family of layered halides.

Synthesis, characterization, electrochemical impedance spectroscopy performance and photodegradation of methylene blue: Mesoporous PEG/TiO2 by sol-gel electrospinning

Sol-gel and electrospinning methods successfully prepared porous TiO2 fibers. The samples were calcined at temperatures of 450 °C and 550 °C and characterized using different techniques. XRD analysis also revealed crystalline anatase and rutile phases of mp-TiO2 observed at calcining temperatures of 450 °C and 550 °C, whereas as-prepared showed an amorphous-like structure. Relatively higher surface area and photocatalytic efficiency were increased with a decrease in crystallite size. All samples absorb UV region. The Rs value of TiO2 calcined at 550 °C was 16.6 Ω, which is much lower than those of the 450 °C calcined TiO2 powder electrode (52.7 Ω) and as-prepared TiO2 electrode (95.3 Ω). In addition, the Rp resistance of TiO2 calcined at 550 °C electrode (5.85 kΩ) was also lower than those of 450 °C calcined TiO2 powder (39.0 kΩ) and as-prepared TiO2 electrode (68.9 kΩ), revealing better electronic and ionic conduction of TiO2 calcined at 550 °C electrode.

Si3N4-Assisted Densification Sintering of Na3Zr2Si2PO12 Ceramic Electrolyte toward Solid-State Sodium Metal Batteries

The solid-state metal battery with solid-state electrolytes has been considered the next generation of energy storage technology owing to its superior safety and high energy density. But, unfavorable ionic conductivity and interfacial problems make it difficult to widely use in practice. In this work, Si3N4 was rationally introduced into the NASICON matrix as a sintering aid, and the influence of Si3N4 on the crystal phase, microstructure, electrochemical and electrical performance of Na3Zr2Si2PO12 (NZSP) ceramic was systematically studied. The results demonstrate that the introduction of Si3N4 can effectively lower the densification sintering temperature of Na3Zr2Si2PO12 electrolyte and enhance the room temperature ionic conductivity of the NZSP to 3.82 × 10−4 S cm−1. In addition, since Si3N4 has a high thermal conductivity and can inhibit the transmission of electrons between the grains of the electrolyte matrix, it will effectively hinder the generation of sodium metal dendrites and relieve the concentration of the heat source. Moreover, owing to the desirable interface compatibility of the Na and NZSP-Si3N4 electrolyte, the Na/NZSP-1150-1%Si3N4/Na symmetric battery exhibits excellent stability, and the electrode/electrolyte interface still maintains good integrity even after long-term cycling. The assembled Na/NZSP-1150-1%Si3N4/Na3.5V0.5Mn0.5Fe0.5Ti0.5(PO4)3 cell manifests an initial specific capacity of 152.5 mA h g−1, together with an initial Coulombic efficiency of 99.8%. Furthermore, after 200 cycles, the battery displays a capacity retention rate of 82%.

Novel Amorphous Nitride‐Halide Solid Electrolytes with Enhanced Performance for All‐Solid‐State Batteries

Solid electrolytes (SEs) in all‐solid‐state batteries (ASSBs) are garnering considerable attention for their potential applications in next‐generation energy storage systems. Amorphous SEs with dual‐anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride‐halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7.34 mS cm‒1 at 30 °C. The amorphous properties and local structures are investigated using powder X‐ray diffraction, cryogenic transmission electron microscopy, and atomic pair distribution function analysis. Impressively, ASSBs employing amorphous Li3xTaCl5Nx have demonstrated good performance at high rates and charging voltages, as well as at low temperature.

Novel Amorphous Nitride-Halide Solid Electrolytes with Enhanced Performance for All-Solid-State Batteries.

Solid electrolytes (SEs) in all-solid-state batteries (ASSBs) are garnering considerable attention for their potential applications in next-generation energy storage systems. Amorphous SEs with dual-anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride-halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7.34 mS cm‒1 at 30 °C. The amorphous properties and local structures are investigated using powder X-ray diffraction, cryogenic transmission electron microscopy, and atomic pair distribution function analysis. Impressively, ASSBs employing amorphous Li3xTaCl5Nx have demonstrated good performance at high rates and charging voltages, as well as at low temperature.