ABSTRACT Lithium‐ion batteries have permeated every aspect of modern production and daily life due to their outstanding performance. However, in the face of continuously rising performance demands and emerging application scenarios, existing commercial lithium‐ion batteries can no longer meet current demands. As a novel battery system, lithium metal batteries demonstrate higher energy density compared to traditional lithium‐ion batteries, yet still face challenges such as lithium dendrite growth, unstable SEI formation, electrolyte consumption, and high safety risks. Although strategies like electrolyte modification, artificial solid electrolyte interphase (SEI) formation, and current collector modification have improved the performance of Li‐ion and Li metal batteries, they still struggle to balance characteristics like energy density, rate capability, cycle life, wide temperature range, and safety. In recent years, the high‐entropy concept has been introduced into liquid electrolyte‐based lithium‐ion and lithium metal batteries, achieving preliminary progress. This mini‐review focuses on the application of high‐entropy effects in liquid electrolytes for lithium‐ion and lithium metal batteries. In this review, we summarize methods for modulating electrolyte mixing entropy and configuration entropy. Furthermore, the structure‐property relationships between entropy‐driven lithium‐ion solvation environments and battery performances such as high rate capability, wide voltage window, and temperature range adaptability are discussed. Through a series of characterization studies and theoretical simulations, the regulatory mechanisms are elucidated. Finally, based on existing researches, this review proposes perspectives for future studies and practical development of liquid high‐entropy electrolytes, aiming to accelerate technological iteration in novel lithium‐ion batteries and high‐energy‐density lithium metal batteries.

All-solid-state supercapacitors are promising candidates for energy storage in flexible electronics and multifunctional structural components. However, when solid polymer electrolytes (SPEs) replace liquid electrolytes, capacitance drops dramatically, limiting the achievable energy density of these devices. Prior research has largely focused on enhancing ionic conductivity, while the role of the electrode-electrolyte interface remains underexplored and may represent the dominant performance bottleneck. We investigated PEO, PLA, and PMMA-based SPEs (each with 20 wt % lithium salt) under identical controlled thermal histories to assess the impact of morphology and interfacial contact on electrochemical performance. Temperature-dependent ionic conductivity measurements show that PLA exhibits the lowest conductivity, PEO the highest, and PMMA intermediate, following Arrhenius-type behavior. Despite its lower conductivity relative to PEO, PMMA maintains a smooth, amorphous interface, resulting in stable interfacial capacitance, whereas crystalline PEO and PLA undergo crystallization, producing ordered structure and capacitance decay. All as-cast films showed rough surfaces and poor contact with gold electrodes (<1 μF/cm2), but thermal melting followed by rapid cooling enabled replication of the electrode's smooth morphology, sharply increasing capacitance up to ∼35 μF/cm2. Slow cooling induced crystallization in PEO and PLA electrolytes, reducing interfacial conformity and driving capacitance back toward initial values, while PMMA remained amorphous, preserving stable capacitance (∼10.2-10.4 μF/cm2), highlighting the advantage of amorphous polymers for achieving durable electrode-electrolyte contact. These findings confirm that interfacial capacitance stability correlates with morphological stability rather than bulk ionic conductivity, emphasizing the critical role of phase behavior and interfacial engineering as a critical pathway to designing durable, high-performance next-generation SPE-based energy storage devices.

ABSTRACT The transition from liquid to solid electrolytes is driven by the need for enhanced safety and higher energy density in advanced batteries. Solid‐state electrolytes (SSEs) eliminate flammability and leakage risks but suffer from low ionic conductivity at ambient conditions due to lattice constraints and high migration barriers. Breakthroughs in SSEs materials such as Li 10 GeP 2 S 12 (LGPS), Li 7 La 3 Zr 2 O 12 (LLZO), and Argyrodite‐type Li 6 PS 5 Cl reveal a unique phenomenon: lithium ions exhibit “floating” behavior within a stable anionic framework, enabling quasi‐fluid migration through interconnected channels. This work explores the physicochemical nature of “floating Li,” emphasizing weak interactions, multi‐path coupling, and framework flexibility as key factors reducing migration barriers. We further propose an electronic‐density‐based approach using the interaction region indicator (IRI) to extract characteristic descriptors for high‐conductivity SSEs. Comparative analysis of IRI maps across different electrolytes demonstrates distinct patterns associated with low‐electron‐density migration channels. These insights establish a paradigm shift from single‐path models to networked migration behavior and suggest that integrating chemical bonding theory, lattice dynamics, and data‐driven screening can accelerate the rational design of next‐generation solid electrolytes.

The growing demand for energy storage systems makes it crucial to develop high-performance anode materials for sodium-ion batteries. This study proposes an innovative strategy for constructing a porous CuO@ fluorinated graphdiyne (F-GDY) composite anode guided by a F-GDY coating. The synergistic effect of Cu(OH)2 core contraction and F-GDY shell confinement led to the formation of a porous CuO structure while preserving the well-defined linear array morphology. The interfacial charge transfer between F-GDY and CuO modulates the electronic structure of CuO, significantly enhancing electron transport efficiency and sodium ion adsorption capacity. The porous structure effectively accommodates volume fluctuations during sodium-ion insertion/extraction, thereby facilitating the formation of a stable solid electrolyte interphase. Electrochemical tests demonstrate that the composite anode exhibits high reversible capacity (681 mAh g-1 after 100 cycles at 50mA g-1) and excellent long-term cycling stability (maintaining 278 mAh g-1 after 1250 cycles at 2000mA g-1). Mechanistic analysis further confirms that the sodium storage process is predominantly capacitive and possesses a high ionic diffusion coefficient. This study provides a new perspective for developing high-stability anode materials for SIBs that can accommodate volume changes.

2D transition metal carbides and nitrides (MXenes) are promising electrode materials for next-generation energy storage devices. However, their charge-storage mechanisms in solid-state systems remain poorly understood, hindering further performance optimization. Here, Li-ion intercalation and conversion reactions in Ti3C2Tx are directly visualized in sulfide-based solid-state Li batteries using operando scanning transmission electron microscopy combined with electron energy-loss spectroscopy. The real-time observations reveal three distinct reaction pathways: (i) Li (de)intercalation within the interlayer spacings of Ti3C2Tx accompanied by Ti redox reactions; (ii) partially reversible formation and decomposition of Li2O on the Ti3C2Tx surface; and (iii) electrochemical decomposition of the sulfide solid electrolyte. The Li-intercalation behavior is strongly governed by the surface terminations of Ti3C2Tx: O-terminated MXenes enable efficient Li accommodation and redox activity at room temperature, whereas F- and Cl-terminated MXenes require elevated temperatures for sufficient Li penetration. These findings provide direct nanoscale evidence of intercalation and conversion processes and highlight surface-termination engineering as an effective strategy to enhance Li accommodation and improve their redox utilization in all-solid-state battery systems.

Rechargeable aqueous zinc-iodine (Zn-I2) batteries face severe challenges, primarily stemming from the interfacial incompatibility between the Zn anode and electrolyte, complex side reactions, and the aggravated polyiodide shuttle effect induced by sluggish charge-transfer kinetics. To mitigate these issues, this work introduces copper hexadecafluorophthalocyanine (FCP) as a novel electrolyte additive to in situ construct a mechanically robust, Zn3N2-rich inorganic-organic hybrid solid electrolyte interphase (SEI). This unique SEI, featuring highly ion-conductive Zn3N2, not only accelerates Zn2+ migration but also leverages the macrocyclic conjugated structure of FCP to generate a delocalized electric field, facilitating the desolvation of hydrated Zn2+. Additionally, the planar π-conjugated backbone promotes in-plane electron transport, further optimizing interfacial kinetics. Furthermore, FCP molecules preferentially adsorb onto the Zn surface, guiding uniform Zn deposition and improving interfacial stability. As a result, the assembled symmetric cells achieve ultrastable cycling for over 6000 cycles at ultrahigh current densities (20 and 50mA cm-2), while the Zn anode exhibits an ultrahigh Coulombic efficiency of 98.7% and exceptional reversibility in plating/stripping. A Zn-I2 full battery also delivers outstanding long-term cycling stability, retaining 80.9% capacity after 65000 cycles at an ultrahigh rate of 50 C.

The reversible K-intercalation chemistry in graphite anode plays a critical role in advancing the development of potassium-ion batteries (PIBs) for large-scale energy storage systems. However, the poor stability of natural solid electrolyte interface (SEI) on graphite anode as well as the co-intercalation of K+-solvent into graphite has caused poor cycling stability and sluggish reaction kinetics. Herein, a mechanochemical-induced radical reaction between graphite and open-shell Spiro-O8 radicals has been discovered and applied to construct a uniform organic layer on graphite, in which the phenoxy radicals can efficiently facilitate the decomposition of KFSI salt to generate outer inorganic-rich layer when the graphite was evaluated as anode for PIBs. The outer inorganic film can enhance K+ transport kinetics and inhibit the co-intercalation of K+-solvent, while the inner Spiro-O8 film can effectively accommodate the volume change during the cycling process. As a result, the highly ion-conductive Spiro-O8 modified graphite exhibited reversible capacity of 241.0 mAh g-1 at 100 mA g-1, high-rate capability (147.2 mAh g-1 at 1 A g-1) and stable cycles more than 600 cycles with a capacity retention of 89.4 %. The interfacial radical reaction in our work provides a new avenue to solve the interface problems of graphite anode for high-performance PIBs.

Mesoporous carbon materials represent promising anodes for advanced lithium-ion batteries, but their performance is still limited by poor structural stability and unstable electrochemical interface. To overcome this, we design a rigid and flexible multi-dimensional architecture, in which mesoporous carbon spheres were uniformly encapsulated by 2D Ti3C2Tx MXene nanosheets, followed by the in situ growth of 1D carbon nanotubes (CNTs). This rational multi-dimensional design preserves the intrinsic merits of mesoporous carbon, while leveraging the rich surface chemistry and mechanical flexibility of MXene to enhance interfacial stability. The interwoven CNTs network further improves the electronic conductivity and mechanical integrity. As a result, the MC@MXene-CNT electrode delivers a high reversible capacity of 671.9 mAh g-1 after 150 cycles at 100mA g-1, and 593.6 mAh g-1 after 600 cycles at 1000mA g-1. In situ electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy depth profiling further reveal that the enhanced performance mainly stems from the formation of a stable, inorganic-rich solid electrolyte interphase. Furthermore, electrochemical kinetics analysis and theoretical calculations demonstrate markedly improved charge transfer kinetics and strengthened lithium-ion adsorption. This work highlights the efficacy of multi-dimensional integration in designing anode materials with rapid transport dynamics and stable electrochemical interface.

ABSTRACT All‐solid‐state lithium‐sulfur batteries (ASSLSBs) offer exceptional promise for next‐generation energy storage due to their high energy density and intrinsic safety. However, their practical application is hindered by sluggish sulfur redox kinetics and severe interfacial degradation. Here, we report a sulfur|carbon and sulfur|solid electrolytes (SEs) interfaces‐dominant cathode structure that concurrently enhances sulfur redox kinetics and interfacial stability. Conventional sulfur cathodes rely on randomly mixed sulfur|carbon, sulfur|SEs, and carbon|SEs three‐phase boundaries, which hinder efficient sulfur redox. This work presents an interfacial architecture that is realized through carbon host nanostructure engineering, where tailored surface area and porosity favor the spontaneous formation of sulfur|carbon and sulfur|SEs dual interfaces, thereby establishing complementary Li + and e − pathways and reinforcing electrochemical performance. At the same time, this strategy alleviates the formation of carbon|SEs interfaces, thereby blocking the initiators of electrolyte decomposition. As a result, ASSLSBs employing the dual‐interface‐dominant architecture achieve a high initial capacity of 1111 mAh g −1 at 0.2 C with a sulfur loading of 5 mg cm −2 , and exhibit long‐term cycling stability, retaining 1234 mAh g −1 (93.3%) over 100 cycles at a 0.1 C rate. This work highlights the critical role of rational carbon host engineering in constructing well‐defined interfaces for high‐performance ASSLSBs.

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here we discover that heterogeneous Ag+ doping dramatically affects lithium intrusion into Li6.6La3Zr1.6Ta0.4O12 (LLZO), a brittle solid electrolyte. Nanoscale Ag+ doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag-Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag+ incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag+-doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag+-doped LLZO surface exhibits improved lithium plating at >250 mA cm-2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

Solid electrolyte interphase (SEI) dissolution in sodium-ion batteries (NIBs) triggers electrolyte decomposition and gas evolution, resulting in capacity decay and safety issues. Lowering the solvation power of electrolyte mitigates SEI dissolution but decreases ionic conductivity. Here, we report a recessive solvent activation strategy, where the recessive solvent 1,2-epoxy-3,3,3-trifluoropropane (TFPO) alone dissolves NaFSI only sparingly, but its solubility is greatly enhanced by the addition of an activating solvent, diethylene glycol diethyl ether (DEE). By harnessing the tunable solvation behavior of the DEE-TFPO system, we designed a weakly solvating electrolyte (WSE) containing 24 vol% DEE, far below the bulk-solvent fractions typical of WSEs, and a high anion-to-DEE ratio. This low DEE content mitigates solvent-induced SEI dissolution, while the high anion-to-DEE ratio promotes anion-dominated solvation structure, forming a robust inorganic-rich SEI. These effects preserve high ionic conductivity while overcome the challenge of SEI dissolution. The optimized electrolyte enabled hard carbon || NaMn0.33Fe0.33Ni0.33O2 full cells to retain 80.0% capacity after 500 cycles and 99.5% capacity in 1.0 Ah pouch cells after 230 cycles with suppressed gas release.

Silicon oxide/graphite (SiOx/Gr) anodes are promising candidates for high energy-density lithium-ion batteries. However, their complex multiphysics degradation mechanisms pose challenges for accurately interpreting and predicting capacity fade behavior. In particular, existing multiphysics models typically treat gas generation and solid electrolyte interphase (SEI) growth as independent or unidirectionally coupled processes, neglecting their bidirectional interactions. Here, we develop an electro–thermal–mechanical–gaseous coupled model to capture the dominant degradation processes in SiOx/Gr anodes, including SEI growth, gas generation, SEI formation on cracks, and particle fracture. Model validation shows that the proposed framework can accurately reproduce voltage responses under various currents and temperatures, as well as capacity fade under different thermal and mechanical conditions. Based on this validated model, a mechanistic analysis reveals two key findings: (1) Gas generation and SEI growth are bidirectionally coupled. SEI growth induces gas release, while accumulated gas in turn regulates subsequent SEI evolution by promoting SEI formation through hindered mass transfer and suppressing it through reduced active surface area. (2) Crack propagation within particles is jointly governed by the magnitude and duration of stress. High-rate discharges produce large but transient stresses that restrict crack growth, while prolonged stresses at low rates promote crack propagation and more severe structural degradation. This study provides new insights into the coupled degradation mechanisms of SiOx/Gr anodes, offering guidance for performance optimization and structural design to extend battery cycle life.

Fluoride solid electrolytes (SEs), despite their extremely low ionic conductivities, offer a promising pathway for enabling 5 V-class chemistries in all-solid-state batteries (ASSBs) owing to their exceptional oxidative stability. Herein, we report a new amorphous oxyfluoride SE, Li1+xTaOxF6-x (x = 0.0-1.0), which exhibits over 3 orders of magnitude higher Li+ conductivity than crystalline LiTaF6, reaching 1.08 × 10-6 S cm-1 at 30 °C (x = 1.0). Pair distribution function analysis, Raman spectroscopy, and X-ray absorption spectroscopy reveal an extended, corner-sharing chain of Ta(O/F)6/7 polyhedra framework. Melt-quenching ab initio molecular dynamics simulations further demonstrate that this interconnected structure broadens Li+ diffusion pathways. Leveraging high oxidative stability (>5 V) and improved Li+ conductivity, Li2TaOF5 was implemented as a shielding layer for 5 V-class LiNi0.5Mn1.5O4 cathodes, enabling exceptional cycling performance with 85.8% capacity retention after 1000 cycles at 1.0C and 30 °C. Even under high-mass-loading (49.3 mg cm-2) or low-temperature (-20 °C) conditions, the modified LNMO electrodes with Li2TaOF5 exhibited promising performance, achieving >5.9 mAh cm-2 with 94% retention. These findings underscore the efficacy of amorphization in advancing fluoride SEs and provide key design insights for advanced halide SEs in high-voltage ASSBs.

Solid electrolytes are promising candidates for safe, high-energy battery systems. Composite solid electrolytes, in particular, hold the potential to combine high ionic conductivity with stable electrode interfaces. However, a fundamental trade-off often exists between ion conduction and mechanical properties. Here we present a composite solid electrolyte design that decouples ion conduction from mechanical flexibility, achieving a high ionic conductivity of 10.2 mS cm-1 at 25 °C while maintaining close mechanical contact with the electrode. The composite architecture consists of alternating layers of perpendicularly aligned (PA) Li0.3Cd0.85PS3 nanosheets, to establish continuous superionic conduction pathways, and Li-containing polyethylene oxide (PEO) layers, to ensure flexibility and interfacial compatibility. At 25 °C, this PA-Li0.3Cd0.85PS3/PEO electrolyte enables Li||LiNi0.8Co0.1Mn0.1O2 coin cells (stack pressure during assembly <0.5 MPa) to retain 92% discharge capacity after 600 cycles at 0.2 mA cm-2, with an average cycling Coulombic efficiency of 99.9%, and also facilitates practical use of pressure-less (stack pressure <0.1 MPa) Li||LiFePO4 pouch cells. This composite design strategy is further validated by substituting Cd with Mn in the inorganic sulfide nanosheets to produce a PA-Li0.46Mn0.77PS3/PEO electrolyte, exhibiting an ionic conductivity of 6.1 mS cm-1 at 25 °C and good mechanical flexibility.

Enhancement of room-temperature performance in solid-state batteries by succinonitrile-based composite solid electrolyte ion channels.

A dual-mode electrochromic and thermochromic smart window utilizing a polyzwitterionic hydrogel.

Lithiophilic NiB embedded hollow carbon nanorods as multifunctional interlayer for dendrite-free and stable lithium metal batteries.

Multifunctional carbon layers design enabling high-performance micro-sized silicon anodes for advanced lithium-ion batteries.

1,3,2-Dioxathiolane 2,2-dioxide additive in carbonate-based gel polymer electrolyte enables dual-Interface stabilization for high-performance long-cycling sodium metal batteries.

In situ integrated design of composite SEI-gel electrolytes boosting high-safety and wide-temperature lithium metal batteries.