Libao Chen

A boron- and fluorine-containing boronate ester additive, BTFPD, is introduced as a molecular interphase programmer for carbonate-based lithium metal batteries.

A stable anode‐electrolyte interface is vital for battery cycling. Translating the successful anion‐derived interphase paradigm from Li‐ion to aqueous Zn‐ion batteries (ZIBs) is hindered by narrow electrochemical windows and chaotic interfacial reactions. Here we overcome this by programming interphase formation via exogenous cation–anion synergy. Hydrolysable anions drive the rapid formation of an inorganic‐rich interphase, while weakly hydrated bulky cations with low ionic potential ( φ ) dually function as noncorrosive electrostatic shields and field‐driven anion receptors to dynamically regulate the interfacial environment without parasitic reactions. As a proof of concept, importing tetramethylfluorourea hexafluorophosphate into ZnSO ₄ electrolyte enables precise modulation of the distribution and conversion of H ₂ O, SO ₄ ²⁻ and Zn ²⁺ at the Zn interface. This resulting composite interface (ZnF ₂ , ZnS, ZnO, and C─N species) improves Zn ²⁺ transport, and promotes uniform deep Zn deposition. As a result, Zn//Zn cells operate for 3400 h at 1 mA cm ⁻² and 1 mAh cm ⁻² , for 1800 h at 5 mA cm ⁻² and 5 mAh cm ⁻² , and for 410 h at a depth of discharge of 42.7%. Zn//KVO full cells and pouch cells also show improved cycling stability. These results establish exogenous cation‐anion pairing as a practical route for ZIB interphase engineering.

A stable anode‐electrolyte interface is vital for battery cycling. Translating the successful anion‐derived interphase paradigm from Li‐ion to aqueous Zn‐ion batteries (ZIBs) is hindered by narrow electrochemical windows and chaotic interfacial reactions. Here we overcome this by programming interphase formation via exogenous cation–anion synergy. Hydrolysable anions drive the rapid formation of an inorganic‐rich interphase, while weakly hydrated bulky cations with low ionic potential ( φ ) dually function as noncorrosive electrostatic shields and field‐driven anion receptors to dynamically regulate the interfacial environment without parasitic reactions. As a proof of concept, importing tetramethylfluorourea hexafluorophosphate into ZnSO ₄ electrolyte enables precise modulation of the distribution and conversion of H ₂ O, SO ₄ ²⁻ and Zn ²⁺ at the Zn interface. This resulting composite interface (ZnF ₂ , ZnS, ZnO, and C─N species) improves Zn ²⁺ transport, and promotes uniform deep Zn deposition. As a result, Zn//Zn cells operate for 3400 h at 1 mA cm ⁻² and 1 mAh cm ⁻² , for 1800 h at 5 mA cm ⁻² and 5 mAh cm ⁻² , and for 410 h at a depth of discharge of 42.7%. Zn//KVO full cells and pouch cells also show improved cycling stability. These results establish exogenous cation‐anion pairing as a practical route for ZIB interphase engineering.

Lithium metal anodes hold great promise for next‐generation high‐energy‐density batteries owing to their ultrahigh capacity and low electrochemical potential, yet their deployment is plagued by dendritic growth and unstable SEI. Herein, we construct an oxygen‐vacancy‐rich interlayer, consisting of antimony tin oxide (ATO) at the top surface and Li─Sn/Li─Sb/Li ₂ O phases at the bottom surface, on the lithium anode by coating plasma treated ATO. With unreacted ATO providing rich oxygen vacancies at the top surface, the interlayers can facilitate lithium‐salt dissociation and accelerate anion decomposition at the initial cycle, yielding robust LiF‐rich SEI layers. Subsequently, the progressive lithiation of the remaining ATO results in the formation of Li ₂₂ Sn ₅ , Li ₃ Sb, and Li ₂ O phases. These phases act as a lithophilic interlayer, which homogenizes lithium nucleation and reduces nucleation overpotential during cycling. Benefiting from the hybrid interface design, Li@ATO symmetric cells stably operate for over 3000 h at 3 mA cm ⁻² and 3 mAh cm ⁻² , and a 400 Wh/kg Li@ATO‖NCM811 pouch cell cycles more than 130 cycles. This work highlights oxygen‐vacancy engineering as a key strategy to simultaneously regulate the SEI components, providing a new pathway toward practical high‐energy‐density lithium metal batteries.

High‐voltage lithium (Li) metal batteries (LMBs) are regarded as strong candidates for next‐generation high‐specific‐energy storage devices. However, interfacial side reactions (ISRs) (particularly the often‐overlooked chemical corrosion) and Li dendrite lead to severe depletion of active Li and even pose safety hazards, significantly hindering the practical applications of LMBs. Herein, an oxygen‐vacancy‐engineered BaTiO ₃ pre‐adsorbed with NO ₃ ⁻ (BTOVN) layer is integrated onto a polypropylene separator to selectively lower the energy level of target anion via ferroelectric dipoles, thus passivating the anode/electrolyte interface and improving the long‐term storage and cycle stability of LMBs. Combining cryo‐electron microscopy with multi‐scale spectroscopies, we reveal that the ferroelectric BTOVN layer targets NO ₃ ⁻ to the interface and promotes the reductive decomposition of both NO ₃ ⁻ and PF ₆ ⁻ to form a thinner and tougher solid‐electrolyte interphase (SEI) rich in inorganic Li ₂ O, Li ₃ N, and LiF, which effectively suppresses persistent ISRs and Li dendrite proliferation while enhancing Li ⁺ transport kinetics and interfacial stability. As a result, high‐voltage Li metal full cells delivery a substantially enhanced capacity retention of 89.1% after 500 cycles, and remarkably, even after long‐term resting, they maintain exceptionally stable operation. The work provides a novel perspective on precisely engineering SEI chemistry through targeting anionic species into the interphase layer.

Designing electrolyte capable of stabilizing electrode interfaces and regulating solvation structures to ensure efficient ion transport is critical for high‐energy lithium metal batteries (LMBs). However, conventional ether‐based electrolytes compatible with lithium metal anodes are limited by oxidative decomposition at high potential and high desolvation energy barriers. Here, we propose a preferential coordination strategy that reconstructs the Li ⁺ solvation structure by leveraging the Li ⁺ binding strength disparity among solvent molecules in ether‐siloxane hybrid electrolytes. In this approach, the high steric hindrance of substituents around the silicon atoms in siloxane solvents restricts their coordination distance with Li ⁺ . This guides the strongly coordinating ether solvents to preferentially form a stable solvation shell around Li ⁺ , reducing the concentration of free ether molecules prone to oxidative decomposition at high voltage. This anion‐rich solvation structure concurrently constructs a robust interphase and accelerates Li ⁺ desolvation. A 5.2 Ah LiNi _0.8 Co _0.1 Mn _0.1 O ₂ || Li pouch cell based on the electrolyte demonstrates an energy density of 510.7 Wh kg ⁻¹ and maintains over 80% capacity retention after 100 cycles. The cell retains 356.7 Wh kg ^{− 1} even at an extremely low temperature of −50°C. This work provides a generalizable electrolyte design principle for high‐voltage lithium metal battery by a solvent coordination engineering strategy.

Ester‐based electrolytes offer high ionic conductivity but suffer from insufficient stability against lithium metal, leading to continuous electrolyte decomposition and lithium dendrite growth. This study proposes the design and construction of a luminescent polymer P‐FMA as an artificial solid electrolyte interphase (SEI) for lithium metal anodes. Integrating a unique spiropyran‐derived fluorescent moiety, fluorine‐containing groups, and flexible methoxyethoxy segments, the polymer features dual functional advantages: the spiropyran fluorescent moiety provides an optical readout associated with the evolution of the electrode‐electrolyte interface through its fluorescence response; meanwhile, the fluorine‐containing groups facilitate the formation of a LiF‐rich SEI layer with high mechanical strength and ionic conductivity, while the flexible methoxyethoxy segments optimize interfacial compatibility. Collectively, these functional components synergistically regulate lithium‐ion deposition behavior and effectively suppress lithium dendrite growth. The Li||Li symmetric cells assembled with P‐FMA@Li anodes exhibited stable cycling for over 1200 h at 1 mA cm ⁻² and 1 mAh cm ⁻² in carbonate‐based electrolytes. Additionally, P‐FMA@Li||LiFePO ₄ full cells retained 82.2% of the initial capacity after 480 cycles, demonstrating significantly improved cycling stability and electrochemical performance compared to bare lithium anodes. This work provides a novel strategy for developing intelligent SEI materials that combine interface visualization with performance enhancement.

Polymer‐based electrolytes offer processability and interfacial compliance but suffer from low ionic conductivity, narrow electrochemical windows, and uncontrolled Li ⁺ transport, limiting their viability for high‐voltage cathodes. Herein, we design an order‐engineered ferroelectric solid electrolyte (OE‐FSE) by integrating a relaxor ferroelectric terpolymer, P(VDF‐TrFE‐CTFE‐FA) (PVTCF), with ambient Curie temperature and double‐bond defects, into a covalently cross‐linked triazine‐based gel network. The spontaneously aligned ferroelectric dipoles within the electrolyte create an internal electric field that promotes lithium‐salt dissociation and facilitates rapid, decoupled, and directional Li‐ion transport. The optimized OE‐FSE exhibits exceptional electrochemical stability up to 5.2 V and liquid‐like ionic conductivity of 5.39 mS cm ⁻¹ at room temperature. Consequently, LRMO||Li coin cell shows a capacity of up to 160.4 mAh/g at a high rate of 10 C with a capacity retention of 81.3% after 280 cycles. LRMO||graphite solid‐state pouch cells achieve a long cycle life of up to 700 cycles and exhibit significantly reduced voltage decay, while LRMO||Li metal pouch cells with an energy density of 502 Wh kg ⁻¹ retain 80% of capacity after 70 cycles. This work establishes molecular‐scale ferroelectric ordering as a powerful paradigm for regulating bulk ion transport and interfacial electrochemistry, paving the way for next‐generation, high‐energy solid‐state batteries.