Lithium metal batteries (LMBs), operating at high voltage (>4.2 V), exhibit unprecedented energy density (>400 Wh kg-1), but are restricted by uncontrollable Li dendrites, enigmatic interfacial chemistries, and unstable solid electrolyte interfaces (SEIs). Fluorine, with its high stability, non-flammability, and low cost, is playing an increasingly vital role in high-voltage LMBs and is expected to resolve the above obstacles. Unfortunately, there are few reviews that comprehensively summarise the exquisite design of fluorine engineering in high-voltage LMBs, especially in-depth analysis of its action mechanism in LMBs. In this review, we start with the fundamentals of SEI formation and Li nucleation and deposition, systematically dissecting the exquisite engineering of fluorine chemistry in high-voltage LMBs, including fluorinated electrolyte systems (salts, solvents, additives, etc.), fluorinated polymer-based SEIs, fluorinated collectors and separators. Meanwhile, several targeted and sophisticated cases are handpicked to be portrayed in conjunction with the proposed ideas, aiming to clarify the functionality of fluorine engineering in inhibiting dendrite growth, stabilising SEIs, and minimising safety hazards. Additionally, we highlight the obstacles faced by fluorine chemistry in LMBs and point out its future perspectives. This review provides guidance for the engineering of fluorine chemistry in high-voltage LMBs.

ABSTRACT Extracting lithium from seawater offers an additional Li source but is hindered by corrosion of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) and weak adhesion of conventional coating layers. Here we propose a permeation growth strategy to construct an intergrowth TiO 2 protection layer on a LAGP membrane (LAGP membrane with intergrowth layer) for long‐term stable lithium extraction from seawater. An acidic TiO 2 sol is spin‐coated onto a polished LAGP membrane and sintered, during which acid etching and Ti 4+ /Ge 4+ ion exchange generate a lattice‐matched Li 1+x Al x Ti 2‐x (PO 4 ) 3 /LAGP interfacial phase beneath a dense TiO 2 intergrowth layer. This intergrowth‐structure eliminates interfacial gaps, enhances peel strength and hardness, and provides continuous Li + transport pathways, delivering an ionic conductivity of 2.40 × 10 −4 S cm −1 at room temperature and excellent chemical stability in seawater. Applied in a lithium extraction device using natural seawater as anolyte and an organic electrolyte as catholyte, the LAGP membrane with intergrowth layer maintains integrity, Li + /Na + selectivity, and stable operation for 650 h, achieving a Coulombic efficiency of 97.4% and an energy consumption of 17.4 kWh kg −1 Li . This permeation growth strategy offers a general route to construct intergrowth‐structure Li ion‐sieve membranes with chemical stability and Li + transport for seawater lithium extraction.

This review identifies the key interfacial challenges in solid-state sodium batteries and highlights materials design, interface engineering, characterization, and modeling strategies to enable stable, high-performance, and commercially viable SSSBs.

Li-rich layered oxide cathodes enable ultrahigh energy density through oxygen redox chemistry but suffer from severe structural degradation and thermal instability caused by irreversible oxygen loss and transition-metal migration. Here, a bond-level regulation strategy is proposed by introducing lithium manganese iron phosphate as a surface buffer layer to induce a bond crosstalk between P-O and transition-metal-O bonds. This crosstalk effectively suppresses oxygen release, restrains transition-metal migration, and stabilizes the layered framework during cycling. As a result, the modified cathode delivers outstanding voltage retention of 87.35% after 500 cycles with an ultralow voltage decay. Moreover, the P-O and TM-O bonds interaction markedly enhances thermal robustness, leading to delayed thermal runaway and excellent high-temperature cycling stability (81.7% capacity retention after 200 cycles at 50 degrees C). This work establishes bond crosstalk engineering as an effective strategy for simultaneously improving the durability and safety of Li-rich cathodes.

The practical application of sodium-carbon dioxide (Na-CO2) batteries is impeded by persistent challenges, including high charging overpotential and inadequate cycling stability, which originate from the insulating nature of the discharge product (Na2CO3) and detrimental electrolyte decomposition at elevated voltages. Although substantial research has focused on cathode catalysts, the charging voltage typically remains above 4 V, resulting in irreversible side reactions and limited cycle life. In this study, we introduce a nitrate-based molten-salt electrolyte strategy to address these issues fundamentally. The NaNO3-KNO3-CsNO3 eutectic electrolyte exhibits a high ionic conductivity of 96 mS cm-1 and a broad electrochemical window, enabling a Na-CO2 battery with a Super P cathode to operate at a low charge plateau of 3.2 V and deliver a high discharge capacity of 4852 mAh g-1 over 150 cycles. Moreover, by incorporating a RuO2 catalyst supported on Super P, the charge voltage is further reduced to 3.0 V, and the cycle life exceeds 300 cycles. This work underscores the synergistic effect of molten-salt electrolytes and heterogeneous catalysts in overcoming kinetic and stability limitations, providing a viable pathway toward practical, high-performance Na-CO2 batteries.

Solid-state electrolytes with superionic conductivity and high compatibility with lithium-metal anode are essential for high specific energy all-solid-state batteries. Here, we develop an argyrodite-type solid-state electrolyte that enables fast Li+ transport and excellent interfacial compatibility with Li metal through a cooperative anion-cation modulation strategy. A robust anodic interface is spontaneously formed via the in situ reaction between Li metal and the tailored electrolyte. The cation Mo introduced into the electrolyte can be reduced to form a lithiophilic Li-Mo alloy, while the anion N is capable of forming highly Li-compatible Li3N. These interfacial products promote uniform Li stripping/plating and suppress parasitic reactions at the anodic interface. Meanwhile, Mo incorporation weakens the strong N─Li electrostatic interaction, ensuring rapid Li+ migration within the electrolyte. The modulated electrolyte exhibits high dynamic stability and Li reversibility at the anodic side, enabling Li//Li symmetric cells to cycle stably for over 3100 h at 0.5 mA cm-2. The Li//LiNi0.8Co0.1Mn0.1O2 batteries demonstrate an ultra-stable long cycle life with 75% capacity retention over 1500 cycles at 4C (3.0 mA cm-2), accompanied by an outstanding average coulombic efficiency of 99.99%. This work highlights an anion-cation cooperative modulation strategy for designing electrolytes that enable high-performance all-solid-state lithium-metal batteries.

The practical deployment of propylene carbonate (PC)-based electrolytes in low-temperature lithium-ion batteries is severely constrained by the spontaneous co-intercalation of PC molecules into graphite anodes, which leads to electrode exfoliation and rapid capacity fade. Here, we introduce a hybrid solid–liquid configuration comprising a 3 Å zeolite membrane placed on the graphite electrode to circumvent this issue. Unlike conventional strategies that rely on high-salt concentrations or sacrificial additives, this zeolite-mediated approach actively restructures the electrolyte solvation environment without altering the bulk composition. In a dilute 1.5 M LiFSI-PC/EMC (3:7, v/v) electrolyte, the zeolite membrane dramatically reduces the population of free PC molecules and solvent-separated ion pairs while promoting the formation of contact ion pairs and ionic aggregates. Consequently, the solvation sheath becomes anion-rich, fostering an inorganic, anion-derived solid electrolyte interphase that effectively blocks PC co-intercalation. The resulting graphite anode delivers an initial Coulombic efficiency of ∼89% and sustains over 1000 stable cycles without any film-forming additives. Furthermore, leveraging the wide liquidus range of the PC-based system, the battery retains reliable discharge capability down to −50 °C. This work establishes a new paradigm for enabling PC-compatible graphite anodes through interfacial solvation regulation, offering a low-cost and scalable route toward wide-temperature lithium-ion batteries.

Phase-transition kinetics is an important concern in the wide application of Li-ion batteries, while its in-depth understanding is still limited by the complexity of real electrode systems. As a derivative phenomenon, electrochemical oscillation is closely coupled with the underlying phase-transition kinetics, providing a direct and sensitive probe to track kinetic variations. Herein, a valence-engineering strategy is presented to modulate the phase-transition kinetics of Mn-doped Li4Ti5O12 (LMTO), which can be directly manifested through the characteristic evolution of electrochemical oscillation behaviour. Actually, LMTO-Ar (sintering under Ar) exhibits enhanced oscillatory amplitude during de-lithiation, whereas LMTO-O2 (sintering under O2) triggers oscillation at the onset of lithiation, which can be interpreted using the split overpotentials of nucleation and phase transition, owing to the high overpotential of the nucleation step and the hysteresis of the phase-transition step in LMTO. Additionally, the electrochemical oscillation is quantitatively reproduced with a million-particle electrode through tailoring the nucleation and phase-transition kinetics. Therefore, this investigation provides profound insights into the origin of electrochemical oscillation and establishes a generalizable kinetics-oscillation correlation framework for advancing the rational design of phase-transition electrode materials.

Electrolyte design for advanced lithium-metal batteries faces a persistent challenge: reconciling physicochemical performance, economic viability, and environmental sustainability within a single molecular framework. Here, we introduce an AI-guided protocol that integrates molecular and electronic descriptors to rapidly screen over 1000 solvent candidates. Our design principle centers on introducing asymmetric alkyl or alkoxy substituents along the ether backbone, creating an electronic and steric environment that simultaneously modulates dipole moment distribution, liquid range, and electrochemical potential window. Experimental and computational results demonstrate that extending the ether chain length enhances oxidative stability and volatility resistance through multidentate coordination, eliminating the need for conventional fluorination. Concurrently, molecular asymmetry introduces electronic inequivalence among the coordinating oxygen atoms, generating a solvation environment that preserves the thermodynamic stability of multidentate binding while kinetically facilitating desolvation via a weakened coordination site. The optimized fluorine-free asymmetric ether electrolyte enables Li || LiCoO2 (LCO) coin cells to retain 81.2% of room-temperature capacity at -40 °C and maintain 91.3% capacity after 300 cycles. A 301 Wh kg-1 (1 Ah) pouch cell retains 71.9% capacity at -35 °C, and a 475 Wh kg-1 (5 Ah) pouch cell operates under lean electrolyte conditions (1 g Ah-1). This molecular asymmetry strategy within fluorine-free ether frameworks represents a paradigm shift, uniquely unifying high-voltage stability, volatility resistance, and reliable ultralow-temperature operation. The methodology integrates data-driven high-throughput screening with rational molecular engineering, offering an efficient route toward high-performance, cost-effective, and environmentally benign electrolytes for extreme-condition batteries.

The advancement of all-solid-state sodium-oxygen (Na-O2) batteries is fundamentally constrained by the formidable chemo-mechanical and kinetic barriers at solid-solid interfaces. Herein, we report a high-performance, room-temperature all-solid-state Na-O2 battery enabled by a monolithic bilayer β-Al2O3 architecture that redefines interfacial charge transfer through a dual-interface integration strategy. By constructing an integrated porous-dense scaffold, we eliminated the macroscopic physical boundaries between the electrolyte and cathode, establishing a seamless, low-resistance ionic conduction continuum. Specifically, a conformal, 30 nm thick graphitic carbon layer was deposited within the cathodic framework via plasma-enhanced chemical vapor deposition, creating a high-fidelity electronic network that maximizes active site utilization. On the anode side, we introduced a reactive wetting mechanism mediated by Bi2O3 nanosheets. The in situ chemical reconfiguration and alloying reaction at the interface generate a gradient Na-Bi-O mixed-conducting interphase, effectively fusing the sodium metal to the ceramic electrolyte and ensuring stable long-term cycling (>14,000 h for symmetric cells). Consequently, the battery delivers an unprecedented discharge capacity of 4012 mA h g-1 at room temperature with an exceptional reversibility. Operando Raman spectroscopy and differential electrochemical mass spectrometry reveal that the solid-state environment provides a unique kinetic stabilization for the metastable NaO2 phase, suppressing the parasitic disproportionation pathways common to liquid systems. This work provides a universal blueprint for engineering chemically integrated interfaces in complex multiphase all-solid-state energy chemistry.

The undesirable Zn-dendrite growth seriously impedes the development of aqueous zinc metal batteries. Compared to thermodynamic improvements reported in most strategies, kinetic manipulation is neglected, limiting the deep research on metal plating process and narrowing the solution design for dendrite-free anode. In this work, a dynamic match regulation strategy is proposed to build dendrite-free zinc anode inspired by the close association between dendrite formation and dynamic mismatch. The dynamic transition is proved to reflect the morphology change from block deposits to dendrite growth. Then, imidazolidinyl urea, is developed as interfacial regulator to restrict the kinetic gap between charge transfer and interfacial diffusion and ensure consistent dynamic model during continuous plating, contributing to uniform deposition layer without dendrite generation under a high capacity of 10 mAh cm-2. The Zn anode also delivers both high CE of over 99.70% and extended lifetime of 1700 h under 20%DOD. This work not only proves the effectiveness of kinetic regulation in dendrite suppression, but also provides a new dimension of interfacial dynamic design for metal anode stabilization.

All-solid-state lithium-iodine batteries (ASSLIBs) are constrained by low energy density and sluggish kinetics due to excessive solid-state electrolytes. Here, a synergistic N/S codoped Ketjen Black (NSKB) host is engineered to resolve the loading-kinetics trade-off. By modulating surface charge, NSKB achieves a remarkable I2/carbon mass ratio of 3.78, increasing the iodine cathode proportion to 53.6 wt %. Sulfur codoping significantly boosts nitrogen content and promotes graphitic nitrogen formation, providing abundant active sites for rapid redox conversion. Consequently, NSKB-based ASSLIBs demonstrate a high initial Coulombic efficiency of 92.8% and a 82.4% capacity retention over 1000 cycles. Even at a high areal loading of 3.26 mAh cm-2, excellent stability is maintained. Distribution of relaxation times (DRT) analysis confirms that NSKB reduces solid-state diffusion impedance and accelerates iodine conversion kinetics. This strategy offers insights for designing high-energy-density solid-state conversion chemistries.

ABSTRACT Zinc (Zn)‐based aqueous electrochemical systems promise low‐cost, high safety, and simplicity, yet they struggle with poor rechargeability due to dendritic Zn growth. The root cause of dendrite formation and poor utilization of Zn electrodes is identified as the competitive hydrogen evolution reaction (HER) and its co‐deposition of insulating side‐products, the latter deteriorating both the nucleation and growth of Zn electrodeposition. By investigating the effect of substrate materials, we classified the thermodynamic and kinetic effects of both HER and Zn reduction and their influence on Zn reversibility. Benefitting from this guideline, we developed a multifunctional graphite‐coated copper current collector that significantly suppresses HER while maintaining good affinity with Zn deposition. The substrate design enhances Zn reversibility to 99.95% with 1‐time excessive Zn design, and endows an aqueous Zn//AC supercapacitor with over 400 000 cycles and a high‐areal‐capacity Zn‐MnO 2 battery with a low N/P ratio.

Lattice-oxygen redox in layered oxides can enhance energy density, but its limited reversibility causes structural instability during deep cycling. Here we develop an iron-mediated strategy to regulate lattice-oxygen redox in layered oxide cathodes. In the Na2/3Mn7/12Mg1/4Fe1/6O2 cathode, Fe ions act as redox mediators, with Fe4+ capturing electrons from lattice oxygen during charging and Fe2+ donating electrons back to oxidized oxygen during discharging through chemical pathways. With the assistance of iron mediation, the reversibility of lattice-oxygen redox is dramatically improved from 75% to 99%. As a result, the lattice-oxygen-activated cathode enables a sodium-ion pouch cell to achieve an energy density of 206 Wh kg−1 and operate stably for 100 cycles at 50 mA g−1, with a capacity retention of 87.8%. Lattice-oxygen redox can raise the energy density of layered oxide cathodes, but poor reversibility causes structural degradation and capacity loss. Here the authors use iron as a bulk redox mediator to boost oxygen-redox reversibility and stabilize high-energy sodium-ion batteries.

Li-O2 batteries, with an impressive theoretical specific energy of 3600 Wh kg-1, face challenges such as low discharge capacity, high charging overpotential, instability caused by singlet oxygen, and the shuttle effect, where soluble catalysts migrate to the anode, leading to degradation and lithium loss. An optimal strategy would incorporate three types of soluble additives: a catalyst to increase the discharge capacity, a redox mediator to lower the charging overpotential, and a scavenger to neutralize singlet oxygen. However, combining multiple additives poses compatibility issues and does not fully address the shuttle effect. To tackle these issues, we propose a multifunctional long-chain catalyst molecule equipped with a superoxide scavenger, redox mediator, and quencher for singlet oxygen. The long-chain structure anchors the molecule, preventing it from diffusing to the anode. Following this strategy, we designed P-TEMPO-TPA by grafting 2,2,6,6-tetramethyl-1-piperoxyl (TEMPO) and triphenylamine (TPA) onto a long-chain backbone. This molecule promotes Li2O2 formation, increasing the discharge capacity by 35 times and reducing singlet oxygen-driven side reactions. The soluble long-chain catalyst lowers the charging voltage to 3.65 V, extending the cycle life to 350 cycles (0.3 mAh cm-2) and 100 cycles (1.2 mAh cm-2). The long-chain design effectively mitigates the shuttle effect, paving the way for high-performance Li-O2 batteries.

The application of medium-/high-entropy materials has revolutionized the design of solid-state electrolytes (SSEs) by stabilizing single-phase solutions from otherwise incompatible elements. However, navigating the vast compositional space of entropy-stabilized materials remains a significant challenge. To overcome this, we introduce a machine learning (ML)-accelerated approach to identify multi-cation NASICON oxide SSEs. By training a Gaussian Naive Bayes model on four key descriptors (ionic radius, electronegativity, valence state, and configurational entropy), we found four promising compositions incorporating Zr, Ti, Hf, Lu, Ga, and Sc. These compositions exhibit notable entropy-driven stabilization, demonstrated by the complete suppression of Na3PO4/ZrO2 impurity formation. Among them, the medium-entropy phase Na3.5Zr1.0Ti0.5Lu0.5Si2PO12 achieved remarkable performance, delivering an ionic conductivity of 1.3 mS cm-1 at room temperature, a critical current density of 1.9 mA cm-2, and over 10 000 hours of stable Na plating/stripping. When integrated into all-solid-state sodium batteries with a high-voltage Na3V2(PO4)2F3 cathode and a sodium anode, it further demonstrated exceptional battery performance indicators, including high-rate capability (110 mAh g-1 at 5C) and long-term cycling stability (80% capacity retention after 700 cycles at 2C). This work establishes entropy engineering, coupled with ML guidance, as a powerful paradigm for the rational design of next-generation SSEs.

All-solid-state lithium-metal batteries offer devices with high specific energy and intrinsic safety, yet their practical implementation is impeded by interfacial instability at the lithium metal/electrolyte interface, especially under high current densities. Conventional interfacial stabilization approaches require complex and costly interfacial engineering, limiting their practicality, highlighting the urgent need for a simple yet effective electrolyte design strategy. Here, a multiple-cation-presetting (Ag and W) argyrodite electrolyte is developed to simultaneously achieve superionic conductivity (over 10 mS cm-1) and superior interfacial stability with softer texture. During cycling, Ag+ can be extracted from the electrolyte layer, reduced to Ag metal, and diffused into the lithium-metal anode to form a uniform Li-Ag alloy, while W can convert into minor conductive LiWS2 in the solid electrolyte interface. Benefiting from in situ anodic and interfacial modification by the SSE, it facilitates accelerated interfacial kinetics and homogeneous Li+ flux. As a result, the Li symmetric cells exhibit sustainable cycling over 4000 h at 0.5 mA cm-2 and beyond 1000 h at 1 mA cm-2. The Li//LiNi0.8Co0.1Mn0.1O2 cells demonstrate excellent rate capability and extended cycle life, maintaining 82.7% capacity retention after 1100 cycles at 2C. Moreover, the electrolyte sustains stable operation at high areal loading (3 mAh cm-2) and low temperature (-30 °C). Besides, such solid-state electrolytes can be extended to other all-solid-state lithium-metal rechargeable batteries. This scalable dual-cation modulation strategy provides a general and practical route to construct superionic electrolytes with compatibility with an anode by in situ interfacial and lithium metal decoration, advancing the realistic application of next-generation all-solid-state lithium-metal batteries.

Aqueous zinc (Zn) batteries have garnered considerable interest as a promising, safe, and sustainable energy storage technology. Nevertheless, their widespread commercialization is hindered by critical challenges, particularly the limited Zn reversibility caused by persistent electrolyte decomposition and uncontrolled dendritic growth. In this study, we propose a chemical strategy involving nucleophilic ethoxide ions, generated via ethanol deprotonation, to induce defluorination of the trifluoromethanesulfonate anion. This approach facilitates the in situ formation of a fluorinated protective interphase on the Zn anode surface. The engineered interphase exhibits remarkable mechanical robustness, as demonstrated by substantially improved Zn Coulombic efficiency at both high and low current densities as well as high Zn utilization rates. Furthermore, this surface modification strategy enables the Zn 0.25 V 2 O 5 /Zn powder batteries to achieve unprecedented cycling stability, including prolonged operation under demanding low N/P ratio conditions (<2:1) and high areal capacity (>2 mAh cm −2 ).

Achieving <15 min fast-charging technology for long-life sodium-ion batteries (SIBs) remains a formidable challenge, primarily due to parasitic reactions and unstable solid-electrolyte interphase (SEI) at the hard carbon (HC) interface. Here we develop a universal polymer-induced SEI strategy that enables an Ah-level SIB pouch cell to achieve <10 min fast-charging capability. We design a <4.0 nm functionalized polymer molecular layer, polyethylenesulfonyl fluoride (PESF), coated on the HC surface (PolyHC) to minimize electrolyte decomposition. The PESF with the -SO2F group attached has a powerful polar feature, which simultaneously induces an anion enriched at the PolyHC interface and tailors extra F atoms, contributing to the architecture of a ∼5.0 nm stable SEI that hybridizes polymer and NaF. This SEI with a resilient polymer skeleton permanently holds the generated inorganic component, enabling long-term structural stability during fast charging. The assembled 1.2 Ah pouch cell, paired with NaNi1/3Fe1/3Mn1/3O2 cathode and PolyHC anode, displays exceptional fast-charging capability and durability. This method is compatible with various HCs, offering a novel perspective for modulating the HC interface chemistry.

Lithium-rich manganese-based oxides (LRMO) with high reversible energy densities are considered as a promising candidate for overcoming the energy density bottleneck of lithium-ion batteries (LIBs). However, the volume variation associated with anisotropic lattice strain and stress during lithium (de)intercalation can lead to severe surface structure degradation and lattice oxygen loss in cathode materials, ultimately resulting in accelerated attenuation of energy density. Herein, we propose an epitaxial lattice matching strategy in which an epitaxial disordered rock-salt layer is coherently grown on the surface to effectively restrain the extension of strain and displacement. Specifically, the disordered rock-salt layer can alleviate lattice strain and inhibit irreversible oxygen release. While the incorporation of boron can adjust the electronic structure, enhance the interaction between transition metals and oxygen, and accelerate Li+ diffusion. The modified LRMO cathode exhibits significantly enhanced cycling stability (83% capacity retention after 300 cycles at 1C vs. 64% for the LRMO), superior rate capability (183.5 mAh g-1 at 5C vs. 147.3 mAh g-1), and improved voltage retention. This study offers a powerful interface engineering strategy to fundamentally resolve the strain-induced structural degradation, paving the way for the development of lithium-rich cathode materials with high adaptability to interface structures.