Shilin Zhang

Polyvinylidene fluoride (PVDF)‐based polymer electrolytes are promising candidates for solid‐state lithium metal batteries owing to their favorable overall electrochemical properties. However, conventional PVDF‐based polymer electrolytes suffer from uneven solvation distribution, discontinuous ion‐transport pathways, and unstable electrode/electrolyte interfaces caused by residual solvents and porous PVDF frameworks. Herein, we report an anchored fluoro‐shielded solvation strategy to construct a high‐performance PVDF‐based polymer electrolyte. By integrating polyanionic anchoring sites with fluorinated shielding segments, the optimized electrolyte enables spatially distributed anion‐rich solvation pathways, homogeneous Li ⁺ transport, and robust LiF‐rich solid electrolyte interphase (SEI). The polymer electrolyte delivers a high ionic conductivity of 1.26×10 ⁻³ S cm ⁻¹ , a Li ⁺ transference number of 0.69, an oxidative onset potential of 5.27 V, and a critical current density of 6.4 mA cm ⁻² . Spectroscopic and interfacial analyses reveal that the anchored fluoro‐shielded solvation structure promotes LiF‐rich SEI formation and suppresses solvent decomposition. Consequently, Li||LiNi _0.8 Co _0.1 Mn _0.1 O ₂ batteries retain 80.2% capacity after 2000 cycles under high‐voltage and high‐rate conditions of 4.5 V and 5 C. This work highlights anchored fluoro‐shielded solvation as an effective molecular design principle for advanced polymer electrolytes toward practical high‐voltage and high‐rate solid‐state Li metal batteries.

A hybrid-entropy regulation strategy is proposed for constructing O3@P2 layered oxide cathodes for sodium-ion batteries. This structural regulation effectively enhances the electrochemical performance of the cathode materials.

Lithium‐rich manganese‐based oxides (LRMO) derive high capacity from lattice‐oxygen redox, but oxygen release at high voltage oxidizes solid electrolytes and drives rapid interfacial resistance growth. Nanosizing improves solid‐state kinetics yet exposes more under‐coordinated surface oxygen, aggravating interfacial degradation. Here, density functional theory screening identifies phosphate as the most effective oxyanion motif for stabilizing surface oxygen. Guided by this insight, a Li─P─F─O bonding topology is constructed through a one‐step mechanochemical reaction between LRMO and LiPO ₂ F ₂ . This process simultaneously refines the particles, introduces near‐surface fluorine, and forms a conformal amorphous interphase featuring P─O, P─F, and Li─F bonding environments. P–O coordination stabilizes surface oxygen, delocalizes oxidation holes, and suppresses O─O coupling, while near‐surface fluorine widens the Li layers and facilitates Li ⁺ transport. Together, these effects suppress oxygen loss, electrolyte oxidation, impedance growth, and interfacial contact failure. The modified cathode delivers 248.5 mAh g ⁻¹ at 25°C and 268 mAh g ⁻¹ at 60°C (0.1 C), retains 85% capacity after 2000 cycles at 10 C, and operates up to 16 000 cycles. A high‐loading lithium‐metal pouch cell achieves 212 mAh g ⁻¹ with specific energy of 277 Wh kg ⁻¹ . This work demonstrates bonding‐topology regulation as an effective strategy for stabilizing oxygen redox in solid‐state batteries.

Via a coordinate-then-dehydrate process, hydrated In ³⁺ binds I ⁻ to form [In(H ₂ O) ₅ I] ²⁺ . This complex shields and blocks charge transfer between I ⁻ and I ₂ , reducing I ₃ ⁻ formation and the shuttle effect.

Aqueous four‐electron zinc‐iodine batteries (4eZIBs) hold great promise for long‐term energy storage, but their practical application is severely hindered by the multiple drawbacks, including Zn dendrite growth, polyiodide shuttle, and I ⁺ hydrolysis. Such limitations can be effectively mitigated by employing biphasic electrolytes featuring a liquid‐liquid interface, which enables efficient immobilization of the dissolved reaction intermediates. However, such systems frequently employ toxic organic solvents, which not only pose flammability risks but also struggle to adapt to extreme temperature conditions. Herein, we design a novel self‐stratified biphasic electrolyte via liquid‐liquid phase separation of choline chloride (ChCl)‐trifluoroacetamide (TFA) deep eutectic solvent (DES) and ZnSO ₄ /H ₂ O/ ethylene glycol solution. The upper DES phase effectively confines polyiodide anions, suppresses shuttle effect and stabilizes I ⁺ species, while the bottom aqueous phase regulates Zn ²⁺ solvation structure and inhibits dendrite formation and side reactions. Benefiting from the synergistic functional separation, the Zn‐I ₂ battery realizes highly reversible four‐electron conversion, effectively suppresses battery self‐discharge, and delivers superior cycling stability over 21000 cycles as well as wide temperature tolerance ranging from −30°C to 50°C. This work offers novel insights into the design of safe and eco‐friendly biphasic electrolytes and provides an effective strategy for the construction of high‐performance 4eZIBs.

All-solid-state Li-metal batteries (ASSLMBs) are promising for next-generation energy storage due to their high energy density and enhanced safety. However, their commercialization remains constrained by complex interfacial phenomena that critically govern the electrochemical performance and durability. In this Review, we present a comprehensive and integrated overview of interfacial science in ASSLMBs, spanning both fundamental studies and practical developments. We begin with a general introduction to typical and state-of-the-art solid-state electrolytes (SEs), followed by a detailed discussion of key interfacial challenges, including the Li anode/SEs interface, the cathode/SEs interface, and internal interfaces within the SEs. Strategies developed to address these issues were critically evaluated and compared. Further, advanced characterization techniques and computational simulations are then examined as essential tools to probe, diagnose, and understand the interfacial evolution. Most importantly, from an interface-centered perspective, we highlight recent progress in safety, electrochemical performance, scalability, and cost effectiveness, helping to bridge the gap between laboratory research and real-world applications. Finally, we provide our forward-looking insights into future research directions aimed at accelerating the commercialization of the ASSLMBs.

Rechargeable Li‐CO ₂ batteries (LCBs) hold great promise for dual‐function CO ₂ utilization and energy storage, yet their practical application is hindered by the sluggish kinetics of the conventional Li ₂ CO ₃ pathway, resulting in low discharge voltages (below 2.0 V) and large overpotentials (over 1.0 V). Herein, we propose a strategy of CO ₂ reduction pathway engineering via alloy‐support interaction to unlock high‐performance LCBs. We designed a Ru ₂ Cu ₄ /NC ₁₀₀₀ catalyst, where spectroscopy confirms distinct charge redistribution driven by strong coordination between the Ru ₂ Cu ₄ alloy and N‐doped support. Theoretical simulations validate that this interaction shifts the Ru and Cu d‐band centers toward the Fermi level and induces interfacial charge redistribution, thus optimizing the electronic structure of the Ru‐Cu active sites for CO ₂ reduction. More importantly, this electronic restructuring thermodynamically favors the formation of metastable Li ₂ C ₂ O ₄ over insulating Li ₂ CO ₃ , thus significantly reducing the activation energy barrier for the rate‐determining step by 0.56 eV. As a result, the cell achieves a minimal overpotential of 0.50 V, an exceptional discharge voltage of 3.23 V, and a high specific capacity of 33 922 mAh g ⁻¹ (at 100 mA g ⁻¹ ). Our work establishes electron‐state engineering via alloy‐support interactions as a protocol for directing reaction pathways and achieving high‐voltage and durable LCBs.

Hydrogel electrolytes are promising for aqueous energy storage, yet their compatibility with kosmotropic salts remains fundamentally limited by the salting-out effect. In conventional hydrophilic polymer networks, strongly hydrated kosmotropic anions preferentially retain their hydration shells, leading to polymer dehydration and structural instability. Here, we show that this incompatibility can be overcome by reversing the Hofmeister response of the hydrogel through anion-polymer affinity chemistry. Guided by the law of matching water affinities, we introduce chaotropic quaternary ammonium groups (-(CH₃)₃N⁺) into a polymer backbone (ATAC-PEA) to enable selective coordination with kosmotropic SO₄^2- anions. This interaction alters the hydration competition among anions, water, and the polymer network, resulting in a reverse Hofmeister behavior. Kosmotropic anions stabilize the hydrogel swelling state, whereas chaotropic anions induce phase separation. This is evidenced by a 3-fold increase in both the correlation length (ξ) and the polymer bundle radius of gyration (R_g) when compared to the chaotropic counterparts. This hydrogel design regulates water activity while maintaining structural stability, expanding the electrochemical stability window to 2.03 V and enabling Zn anodes to cycle for over 1800 h with ∼99.5% Coulombic efficiency. Furthermore, this design principle extends to seawater-based electrolytes and other aqueous metal chemistries, including lithium, potassium, and magnesium systems. This work establishes a fundamental chemical framework for reversing the Hofmeister response via specific anion-polymer interactions, providing a new design strategy for advanced aqueous electrolytes.

Expanding the electrochemical stability window of aqueous electrolyte solutions is a viable strategy to improve battery performance. Using water-in-salt aqueous electrolyte solutions, the solid electrolyte interphase formed on the negative electrode enables an electrochemical stability window up to 3.0 V, but this often reduces ionic conductivity and increases costs. Here, to circumvent these issues, we report the use of hydrophobic and electrode-philic ether-based additives in 3-molal aqueous zinc trifluoromethanesulfonate electrolyte solutions. These additives, characterized by a weak Zn-ion solvation capability, are soluble in the aqueous electrolyte solution at low concentrations (below 2 mol%). They can be adsorbed on both positive and negative electrode surfaces, inhibiting Zn dendrite growth, forming a liquid electrolyte interphase that extends the electrochemical stability window to 3.08 V, enabling high bulk ionic conductivity (about 54 mS cm ⁻¹ at 25 °C) and ensuring the non-flammability of the aqueous electrolyte solution. This nanoengineered electrolyte approach enables a Zn||NaV ₃ O ₈ single-layer pouch cell to operate 500 stable cycles (average Coulombic efficiency of 99.95%) with a specific discharge capacity retention of 80% at 500 mA g ⁻¹ and 25 °C with a calculated initial specific energy of 132 Wh kg ⁻¹ (based on the mass of the negative and positive electrode active materials).