Jiamin Fu

Halide solid electrolytes (SSEs) hold promise for next‐generation all‐solid‐state batteries (ASSBs), yet scalable fabrication of halide SSE films and ampere‐hour‐scale all‐solid‐state pouch cells (ASSPCs) via slurry coating has not been demonstrated. Here, we introduce a dual‐solvent supramolecular assembly strategy that precisely regulates the chain organization of a multiblock copolymer binder (SEEPS), enabling low‐binder, high‐viscosity slurries for uniform halide SSE film formation. Methylcyclohexane and decane are identified as chemically compatible solvents that diminish InCl ₃ surface precipitation in Li ₃ InCl ₆ , preserving ionic conductivity. The resulting Li ₃ InCl ₆ /Li _{6− x} PS _{5− x} Cl _{1+ x} bilayer SSE film exhibits high ionic conductivity (1.26 mS/cm), mechanical robustness, and electrochemical stability. ASSBs using NCM88 cathodes and micro‐silicon anodes retain 71.3% capacity after 600 cycles at 0.5 C, while the first ten‐layer ampere‐hour‐scale halide ASSPC delivers 1.45 Ah at 0.2 C with 95.1% capacity retention over 100 cycles. This approach establishes a practical and scalable pathway for fabricating halide ASSPCs, bridging laboratory innovations and commercial deployment.

UCl₃-based halide solid electrolytes have garnered increasing interest for application in all-solid-state batteries, yet their structural characteristics, chemical composition, and ion transport mechanisms remain under debate. These uncertainties hamper their rational design and broader application. Taking PrCl₃ as a model system, we present a comprehensive structural investigation and reveal that foreign cations (e.g., Ta⁵⁺, Zr⁴⁺ and In³⁺) preferentially reside in amorphous matrix rather than substituting for Pr³⁺ in crystalline PrCl₃, owing to substantial mismatches in both ionic radii and coordination numbers. Importantly, the dominant pathway for fast Li⁺ conduction lies within the amorphous phase, rather than the PrCl₃ nanocrystals or their interfacial regions. Guided by these insights, Li_0.5Pr_0.455Ta_0.179Zr_0.06Cl₃ is rationally designed, realizing high ionic conductivity (3.10 mS cm⁻¹) and a low activation energy (0.236 eV). These improved ion-conducting properties enables battery with a capacity retention of 71.7% at 20 mA g^-1 and -20 °C, and a prolonged cycle life of 1350 cycles at 100 or 200 mA g^-1 and -10 °C. These results underscore the critical role of amorphous phase engineering in halide electrolytes and the potential of UCl₃-type systems for low-temperature all-solid-state batteries.

Rechargeable zinc metal batteries are promising for large-scale energy storage due to their low cost and high safety, but their development is seriously hindered by the dendritic growth and side reactions of zinc metal anodes. To address this challenge, we report here that rational design of low-surface-tension electrolytes can enable dense nucleation and fine-grained growth of zinc. This low-surface-tension strategy leads to high stability of the solid-electrolyte interface, dendrite-free morphology and suppressed side reactions. Therefore, zinc metal anodes achieve a high average Coulombic efficiency of 99.72% over a lifespan of 8400 hours at 1 mA cm⁻²/1 mAh cm⁻². Even at harsh electrochemical conditions of 10 mA cm⁻²/10 mAh cm⁻², the lifespans of zinc metal anodes exceed 2200 and 300 hours at 17% and 85% depth of discharge, respectively—over 20-fold and 150-fold improvements compared with those using conventional electrolytes (2 mol kg⁻¹ zinc trifluoromethanesulfonate with 1.5 wt% zinc acetate dihydrate). A 1.27 Ah pouch cell is demonstrated to showcase the practicability of this strategy. This work uncovers the critical role of electrolyte’s surface tension for advanced zinc metal anodes, and offers a potentially cost-effective and sustainable pathway toward commercially viable rechargeable zinc metal batteries.

All-solid-state batteries frequently encounter mechanical instability due to the inherent brittleness and low elasticity of inorganic ceramic electrolytes, such as sulfides, oxides, and halides. These electrolytes struggle to accommodate the volumetric fluctuations of positive electrode materials during cycling, potentially leading to performance degradation and premature failure. To address this challenge, we propose a defect-based toughening approach for resilient halide solid electrolytes. By meticulously controlling the cooling rate during synthesis, we successfully increase the defect density within the electrolyte, enhancing its mechanical properties and mitigating the risk of mechanical failure. Mechanical property testing, high-resolution transmission electron microscopy characterization, and synchrotron radiation diffraction analysis reveal that the quenched material exhibit not only a higher Young’s modulus, rendering it less susceptible to deformation under stress and a higher capacity for energy absorption before plastic deformation or fracture due to its increased dispersed defect density. Consequently, it demonstrates better adaptability to the volumetric changes associated with the positive electrode material during battery cycling, effectively mitigating strain-induced material behavior. Here we show the effectiveness of defect-enhanced toughening strategies in optimizing the mechanical properties and microstructure of electrolyte materials, thereby enhancing the overall integrity of solid-state batteries without requiring modifications to their chemical composition.

Lithium sulfide (Li₂S), a key cathode material for all-solid-state lithium-sulfur (Li-S) batteries, faces challenges such as low electronic and ionic conductivities and limited active material utilization during cycling. In this study, we developed a new cathode featuring nanosized Li₂S embedded in an amorphous LiFeS₂ matrix (92Li₂S@8LiFeS₂). Benefiting from the mixed electronic and ionic conductivities of LiFeS₂ along with its catalytic effect and the nanosized Li₂S that shortens electron and ion transport distances, this 92Li₂S@8LiFeS₂ cathode exhibits long-term cycling stability with a capacity retention of over 99% after 320 cycles. With an active material content of 48% and a mass loading of 19.1 mg/cm², the cathode achieves an areal capacity of 13.2 mAh/cm². This work presents a facile and novel approach to designing Li₂S-based cathodes for high-performance, all-solid-state Li-S batteries.

Organic electrode materials offer a versatile, sustainable approach for next-generation lithium-ion batteries but are limited by low working voltages and poor cycling stability. Here we report a solid-solvation-structure design strategy to improve both the voltage and stability of organic electrode materials in all-solid-state batteries. As a proof of concept, we incorporate halide electrolytes as solid solutes and tetrachloro-o-benzoquinone as a solid solvent to form homogeneous solid cathode solutions. Systematic optimization of the inner solvation configuration enables tetrachloro-o-benzoquinone to achieve a high working voltage (3.6 V vs. Li⁺/Li) at room temperature within an asymmetric solid solvation sheath. Moreover, the equilibrium redox pathway and electrostatically driven self-healing interfaces revealed rapid redox kinetics and stable performance over 7,500 cycles in all-solid-state batteries under low stack pressures. This work demonstrates that organic electrode materials can serve as viable, durable and cost-effective alternatives to transition metal oxides in all-solid-state batteries.

All-solid-state batteries require advanced cathode designs to realize their potential for high energy density and economic viability^1,2,3. Integrated all-in-one cathodes, which eliminate inactive conductive additives and heterogeneous interfaces, hold promise for substantial energy and stability gains but are hindered by materials lacking sufficient Li⁺/e⁻ conductivity, mechanical robustness and structural stability^{4,5,6,7,8,9,10,11,12,13,14}. Here we present Li_1.3Fe_1.2Cl₄, a cost-effective halide material that overcomes these challenges. Leveraging reversible Fe²⁺/Fe³⁺ redox and rapid Li⁺/e⁻ transport within its framework, Li_1.3Fe_1.2Cl₄ achieves an electrode energy density of 529.3 Wh kg⁻¹ versus Li⁺/Li. Critically, Li_1.3Fe_1.2Cl₄ shows unique dynamic properties during cycling, including reversible local Fe migration and a brittle-to-ductile transition that confers self-healing behaviour. This enables exceptional cycling stability, maintaining 90% capacity retention for 3,000 cycles at a rate of 5 C. Integration of Li_1.3Fe_1.2Cl₄ with a nickel-rich layered oxide further increases the energy density to 725.6 Wh kg⁻¹. By harnessing the advantageous dynamic mechanical and diffusion properties of all-in-one halides, this work establishes all-in-one halides as an avenue for energy-dense, durable cathodes in next-generation all-solid-state batteries.

Halide solid‐state electrolytes (SSEs) are promising superionic conductors with high oxidative stability and ionic conductivity, making them attractive for all‐solid‐state lithium‐ion batteries. However, most studies have focused on ion‐stacking structures, overlooking the role of bond characteristics in ionic transport. Here, we investigate bond dynamics and the superionic transition (SIT) in bromide electrolyte, Li ₃ InBr ₆ , using synchrotron X‐ray techniques and ab initio molecular dynamics (AIMD) simulations. We demonstrate that the SIT in halide SSEs is driven by a thermally induced transition in bonding character (ionic to covalent) rather than a change in crystal phase. AIMD simulations further reveal enhanced Li⁺ diffusion and collective anion motion at elevated temperatures. Expanding our study to Li ₃ LnBr ₆ (Ln = Gd, Tb, Ho, Tm, and Lu), we confirm the widespread occurrence of SIT in this material class, with Li ₃ GdBr ₆ exhibiting the highest ionic conductivity (5.2 mS cm ⁻¹ at 298 K). More importantly, the ionic‐covalent transition is highly tunable through electrolyte modifications, such as cation/anion substitution and synthesis methods. Our findings provide a new perspective on ionic transport, highlighting the critical role of chemical bond characteristics in halide SSEs.