ABSTRACT Aqueous dual‐ion batteries (DIBs) are becoming one of the most compelling choices for large‐scale stationary energy storage owing to the excellent safety performance, high power density, and cost‐effectiveness. However, their low output voltage leads to insufficient energy density. Here, we design a highly reversible pH‐neutral Ag↔Ag 2 SO 4 electrochemistry and construct a novel Zn‐based conversion‐type aqueous anion–cation shuttle DIB. A dendrite‐free Zn anode with functional graphite layer is prepared to improve cycle life. Benefitting from the synchronous effect of Zn 2+ /SO 4 2− dual charge carries and dendrite‐free anode, the DIB delivers a high output voltage of 1.41 V, volumetric energy density of 3295.4 Wh L −1 at 0.5 A g −1 , and 95.9% capacity retention over 300 cycles at 1 A g −1 , superior to most reported DIBs. As a proof of concept, we fabricate a quasi‐solid‐state aqueous DIB with remarkable mechanical strength, flexibility, and impressive temperature resistance. With working temperature decreasing from 20 to −10°C, it shows only a very low‐capacity loss (8.4%) and negligible polarization change (0.05 V). This work overcomes the bottleneck of low output voltage in aqueous DIBs and offers a promising pathway for the development of future aqueous batteries with high energy density.

ABSTRACT Aqueous Zn–S batteries (AZSBs) have garnered significant attention owing to their high energy density and low cost. However, their practical application is hindered by the limited electrochemical reversibility of sulfur cathode and the interfacial instability of zinc anode. Here, we developed a functionalized co‐solvent electrolyte incorporating aprotic polar tetramethylurea (TMU) and potassium iodide (KI) as synergistic additives, where TMU regulates the Zn 2+ coordination environment and cooperates with iodide species to construct an electrolyte‐derived, interface‐confined, and coordination‐mediated dynamic ion bridge pathway. This pathway couples TMU‐regulated Zn 2+ transport with I 3 − /I − ‐mediated charge transfer at the sulfur cathode interface, thereby reducing the kinetic barriers for Zn 2+ transport and ZnS conversion. Meanwhile, the TMU/KI‐regulated interfacial environment homogenizes Zn 2+ flux at the anode, promotes uniform Zn plating/stripping, and suppresses parasitic reactions. Through the synergistic regulation of the ion bridge, the AZSB delivers a high specific capacity of 759 mAh g −1 at 5 A g −1 and maintains over 71.2% capacity retention after 1000 cycles. This work proposes a promising electrolyte design strategy for energetic AZSBs via synergistic regulation, offering a promising route toward next‐generation sustainable energy storage systems.

Silicon (Si) has been widely accepted as a promising anode material owing to its high theoretical capacity (3590 mAh g-1) and abundance. Nevertheless, its practical application in next-generation batteries has long been hindered by several inherent challenges, including an unstable solid-electrolyte interphase (SEI), large volume changes, and low electrical conductivity. Herein, a facile and effective chemical route is proposed to construct a functional organic molecule that could constrain the framework and tune the interfacial properties of Si/C electrodes. Superior electrochemical performance with high anode material loading (similar to 8.0 mg cm-2) and high areal capacity (above 3.0 mAh cm-2) is achieved for the Si/C anode in terms of excellent cycling stability. A unique interfacial anchoring mechanism is found that plays a major role in effectively alleviating the huge volume expansion and maintaining the integrity of the Si/C electrode. Moreover, an investigation of the surface chemistry confirms that the constructed molecule can improve the stability of the SEI by promoting the formation of a LiF-rich interphase. Our findings provide deep insights into the design of high-performance Si/C anodes for practical applications in next-generation batteries.

In recent years, oxychloride‐based materials have emerged as a promising solid‐state electrolyte (SSE) candidate owing to its ultrahigh ionic conductivity and decent cathode compatibility. Although the fabrication of SSE coatings for cathode materials has been recognized as a promising strategy, a precise synthesis of oxychloride‐based SSE coating is still not realized due to the lack of appropriate preparation method. As a proof of concept, we propose a superior lithium‐ion conductive aluminum‐based oxychloride (LAOC) coating synthesized by atomic level fabrication strategy with unique self‐limiting reaction mechanism. The LAOC modified lithium cobalt oxide (LCO) cathode exhibits a high capacity retention of 86.4% after 500 cycles at 5 C and significantly improved high‐voltage cycling stability. The outstanding performance is ascribed to the high interfacial ionic conductivity and construction of robust cathode electrolyte interphase. The ionic conductivity of LCO increased from 1.785 × 10 −7 to 2.823 × 10 −6 S cm −1 after LAOC coating. Scanning transmission X‐ray microscopy and transmission electron microscopy reveal that the LAOC coating suppresses interfacial degradation and mitigates the structural collapse of LCO. This study offers great opportunity for the atomic level fabrication of superior ionic conductive oxychloride thin films to realize high performance lithium‐ion batteries.

Alloy-based anodes, particularly indium (In) are emerging as promising candidates for achieving long-cycle life in all-solid-state lithium batteries (ASSLBs), due to their dendrite-free characteristics and ability to stabilize the anode interface. However, their practical applications remain hindered by limitations in the failure of In anodes under high current densities and areal capacities, where the incomplete understanding of the underlying failure mechanism limits the optimization strategies. Herein, we employ advanced characterization techniques to systematically investigate the failure mechanisms of In anodes under high current densities and areal capacities. Our findings reveal that alloying and dealloying processes involve an electro-chemo-mechanical coupling failure mechanism and further exacerbate performance degradation. By elucidating these failure mechanisms, our work provides critical insights and rational surface protection strategies by ALD coating with Al2O3 layer for enhancing the interfacial stability and performance of alloy anodes in ASSLBs. The maximum cycling capacity of the Li/In asymmetric cell at 0.5 mA/cm2 was enhanced from 0.2 to 2 mAh/cm(2) (>200 cycles). This work paves the way for the development of durable, high-energy-density batteries.

Aqueous zinc-based dual-ion batteries, which utilize fast-diffusing anions as charge carriers, offer a promising route to overcome the sluggish kinetics of conventional Zn2' intercalation. Yet they are hindered by the limited capacity of intercalation cathodes and the severe structural degradation of conversion-type materials. Herein, a self-reduced silver (SR-Ag) cathode with a self-assembled porous architecture is designed to achieve high energy density and durability by eliminating the redundant mass and providing internal space to manage the structural instability common in conventional silver powder electrodes, thereby unlocking the full potential of AgCl/Ag conversion chemistry in zinc-based dual-ion batteries. The interconnected pores within this framework act as mechanical buffers to accommodate volume expansion while providing open channels for rapid electrolyte penetration into the entire electrode. This structural design ensures complete utilization of the active material and prevents structural failure during cycling, enabling high capacity and excellent reversibility. Consequently, the dual-ion battery system delivers an outstanding volumetric capacity of 1258.1 mAh cm-3 and maintains 93.8% capacity retention over 1500 cycles at a high rate of 20 C. The stability of the flexible pouch cells under deformation confirms the potential of this system as a high-density and safe power source for portable electronics. (c) 2026 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

High-energy-density lithium (Li)–air cells have been considered a promising energy-storage system, but the liquid electrolyte-related safety and side-reaction problems seriously hinder their development. To address these above issues, solid-state Li–air batteries have been widely developed. However, many commonly-used solid electrolytes generally face huge interface impedance in Li–air cells and also show poor stability towards ambient air/Li electrodes. Herein, we fabricate a differentiating surface-regulated ceramic-based composite electrolyte (DSCCE) by constructing disparately LiI-containing polymethyl methacrylate (PMMA) coating and Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) layer on both sides of Li1.5Al0.5Ge1.5(PO4)3 (LAGP). The cathode-friendly LiI/PMMA layer displays excellent stability towards O2- and also greatly reduces the decomposition voltage of discharge products in Li–air system. Additionally, the anode-friendly PVDF-HFP coating shows low-resistance properties towards anodes. Moreover, Li dendrite/passivation derived from liquid electrolyte-induced side reactions and air/I-attacking can be obviously suppressed by the uniform and compact composite framework. As a result, the DSCCE-based Li–air batteries possess high capacity/low voltage polarization (11836 mA h g-1/1.45 V under 500 mA g-1), good rate performance (capacity ratio under 1000 mA g-1/250 mA g-1 is 68.2 %) and long-term stable cell operation (300 cycles at 750 mA g-1 with 750 mAh g-1) in ambient air.

Halide solid-state electrolytes (SSEs) have become a new research focus for all-solid-state batteries because of their significant safety advantages, high ionic conductivity, high-voltage stability, and good ductility. Nonetheless, stability issues are a key barrier to their practical application. In past reports, the analysis of halide electrolyte stability and its enhancement methods lacked relevance, which limited the design and optimization of halide solid electrolytes. This review focus on stability issues from a chemical, electrochemical, and interfacial point of view, with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces. By focusing on innovative strategies to address the stability issue, this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes, paving the way for their wider application in the next generation of energy storage technologies.

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.

All-solid-state batteries require advanced cathode designs to realize their potential for high energy density and economic viability1-3. 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 stability4-14. Here we present Li1.3Fe1.2Cl4, a cost-effective halide material that overcomes these challenges. Leveraging reversible Fe2+/Fe3+ redox and rapid Li+/e- transport within its framework, Li1.3Fe1.2Cl4 achieves an electrode energy density of 529.3 Wh kg-1 versus Li+/Li. Critically, Li1.3Fe1.2Cl4 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 Li1.3Fe1.2Cl4 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.

All-solid-state lithium metal batteries (ASSLMBs) with solid-state electrolytes (SSEs) are regarded as nextgeneration energy storage technology due to their superior safety and exceptional energy density. However, soft breakdown-a prevalent failure mechanism in ASSLMBs-has hindered their development. In this study, we introduce Li/SSE/current collector (CC) asymmetric cells as a novel evaluation method to assess the susceptibility of various SSEs to soft breakdown. Our findings reveal that metal-contained SSEs (e.g., LGPS) exhibit a stronger resistance to soft breakdown compared to metal-free SSEs (e.g., LPSC) through phase characterization including ToF-SIMS and XPS. This enhanced stability is attributed to the formation of a metal-containing solid electrolyte interphase (SEI) at the interface. Moreover, the impact of practical cell configuration including current density, stack pressure, cutoff voltage on the occurrence of soft breakdown was also discussed. The insights gained from this work deepen the understanding of the soft breakdown phenomenon in SSEs and provide valuable guidance for the design of advanced solid-state electrolytes.

Solid‐state Na batteries (SSNBs) are among the most promising next‐generation energy storage devices due to their high energy density, enhanced safety, and cost‐efficiency. Achieving high‐performance SSNBs depends on the development of solid‐state electrolytes (SSEs) with excellent ionic conductivity, wide electrochemical windows, and robust mechanical properties. Sulfide and halide‐based Na SSEs have been widely studied in recent years with their respective strengths and limitations. Herein for the first time, a new family of Na‐Zr‐S‐Cl sulfide‐chloride Na SSEs with tailored anion compositions is explored. A high ionic conductivity of 4.89 × 10 −4 S cm −1 is realized with a Cl‐rich structure, attributed to the unique chloride bridging structure and low Na‐ion migration barrier. Furthermore, by tuning the ratio between sulfur and chloride anions, two different unique structures are obtained with different surface morphology, thermal stability, mechanical properties, and electrochemical stability. The Cl‐deficient structure of Na 2 S‐1.3ZrCl 4 SSEs demonstrates excellent stability for solid‐state Na‐ion batteries, maintaining a high reversible capacity of over 90 mAh g −1 after 600 cycles at 0.1 C. This study offers insights into the design of new Na SSEs, advancing the development of safer and high‐performance SSNBs.

In this study, we present a large-scale machine learning screening to discover promising candidate compounds for lithium-based solid-state electrolyte batteries. Key properties such as superionic conductivity and wide electrochemical stability are crucial for achieving high-performance solid-state batteries, which have great potential as the next generation of batteries with high energy density and relatively low cost. Our work employs high-throughput screening using multiple regression machine learning models on lithium-containing materials. Subsequently, ab initio molecular dynamics (AIMD) simulation and experimental validation were conducted exhibiting high ionic conductivity, namely Li4.5TiO3.25 and Li2VCl5. Furthermore, we applied a design methodology to increase the ionic conductivity at ambient temperature. These findings provide a comprehensive strategy for the development of room-temperature superionic conductors for high-performance solid-state batteries.

The evolution of inorganic solid electrolytes has revolutionized the field of sustainable organic cathode materials, particularly by addressing the dissolution problems in traditional liquid electrolytes. However, current sulfide-based all-solid-state lithium-organic batteries still face challenges such as high working temperatures, high costs, and low voltages. Here, we design an all-solid-state lithium battery based on a cost-effective organic cathode material phenanthrenequinone (PQ) and a halide solid electrolyte Li 2 ZrCl 6 . Thanks to the good compatibility between PQ and Li 2 ZrCl 6 , the PQ cathode achieved a high specific capacity of 248 mAh g −1 (96 % of the theoretical capacity), a high average discharge voltage of 2.74 V (vs. Li + /Li), and a good capacity retention of 95 % after 100 cycles at room temperature (25 °C). Furthermore, the interactions between the high-voltage carbonyl PQ cathode and both sulfide and halide solid electrolytes, as well as the redox mechanism of the PQ cathode in all-solid-state batteries, were carefully studied by a variety of advanced characterizations. We believe such a design and the corresponding investigations into the underlying chemistry give insights for the further development of practical all-solid-state lithium-organic batteries.

The all-solid-state lithium metal battery is considered the next-generation energy storage device with the potential to double the energy density of state-of-the-art Li-ion batteries and eliminate safety hazards. Achieving stable Li plating/stripping without dendrite propagation within the solid electrolyte is crucial for delivering the promised high energy density. In this study, through the comparison of various synthesis routes, a novel cube-shaped microstructure in the Li5.3PS4.3ClBr0.7 argyrodite electrolyte, synthesized using the high-speed mechanical milling followed by annealing method (BMAN-LPSCB) is identified. The uniform microstructure allows for the production of an electrolyte pellet with significantly reduced porosity through cold pressing. The removal of defects has significantly enhanced the electrolyte's ability to inhibit dendrite formation, with a critical current density reaching 3.8 mA cm-2. The lithium symmetric cell with BMAN-LPSCB electrolyte exhibits stable Li plating/stripping for over 150 h at a high current density and cutoff capacity of 3 mA cm-2 / 3 mAh cm-2. The all-solid-state Li/NCM battery utilizing the BMAN-LPSCB electrolyte also demonstrates excellent durability, with a capacity retention of 96% over 1000 cycles at a 1C rate. This study emphasizes that the microstructure of the sulfide electrolyte is a critical factor influencing mechanically-driven Li dendrite propagation in all-solid-state batteries. A novel cube-shaped microstructure in the Li5.3PS4.3ClBr0.7 argyrodite electrolyte is identified by synthesizing via high-speed mechanical milling followed by an annealing method (BMAN-LPSCB). The uniform microstructure allows to produce an electrolyte pellet with significantly reduced porosity through cold pressing. The removal of defects has significantly enhanced the electrolyte's ability to inhibit dendrite formation. image

Room-temperature (RT) solid-state sodium-sulfur batteries (SSNSBs) are one of the most promising next-generation energy storage systems because of their high energy density, enhanced safety, cost-efficiency, and non-toxicity. While most of the studies for SSNSBs focused on designing and developing sulfur cathodes, we carve out a new path to understanding and modulating the structures and properties of sulfide solid-state electrolytes (SSEs) for achieving high-performance SSNSBs. A novel cation and anion co-doped approach was developed to enhance the ionic conductivity and expand the electrochemical stability of sulfide SSEs, and eventually improve the electrochemical performance of SSNSBs. The crystal structure and local structure of the cation/anion co-doped sulfide SSEs have been studied in detail combined with the density functional theory (DFT) calculations for mechanism understanding. SSNSBs incorporating co-doped sulfide SSEs demonstrate high capacity and stable cycling performance, even at high rates, which is at the top of the reported performances in the literature. Our novel approach for cation and anion-tuned SSEs demonstrates excellent ionic conductivity and electrochemical stability, paving a new way for the next generation of solid-state sodium batteries.

Designing Na-ion solid electrolytes (SEs) of high ionic conductivity and excellent chemical/mechanical compatibility with cathode materials remains challenging for all -solid-state Na-ion batteries (ASSNIBs). In this study, we successfully design and synthesize a novel amorphous NaTaCl6 halide SE with unprecedented ionic conductivity of 4 x 10-3 S cm -1 at room temperature. The exceptional ionic conductivity arises from a unique reconstructed amorphous poly-(TaCl6) octahedra network with weakening Na-Cl interactions through high-energy mechanochemical reactions. Notably, the amorphous NaTaCl6 halide SE exhibits remarkable mechanical deformability, chemical/electrochemical stability, and outstanding electrochemical performance when coupled with the Na3V2(PO4)3 cathode in ASSNIBs, resulting in a remarkable initial Coulombic efficiency of 99.60%, excellent rate performance (85% capacity retention at 2 C), and stable long -cycling profiles (81%/95%/98% capacity retention after 4,000/600/1,500 cycles at 3/1/0.5 C). This discovery of superionic amorphous Na-ion halide SEs opens a promising avenue for advancing high-performance ASSNIBs.

The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na2O2–MCly, M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na2O2–MCly electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm−1, wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na2O2–HfCl4 electrolyte and a Na0.85Mn0.5Ni0.4Fe0.1O2 cathode exhibit a superior rate capability and long-term cycle stability, with 78

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm-2) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li3N SSE. This vacancy-rich β-Li3N SSE shows a high ionic conductivity of 2.14 × 10-3 S cm-1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li3N achieve breakthroughs in high critical current densities up to 45 mA cm-2 and high capacities up to 7.5 mAh cm-2, and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li3N is unveiled as intrinsic stability to lithium metal. In addition, β-Li3N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li3N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi0.83Co0.11Mn0.06O2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g-1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g-1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li3N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm-2 for the compact pellet-type cells and around 2.2 mAh cm-2 for the all-solid-state lithium metal pouch cells.