Xu Liu

Advanced solid polymer electrolytes (SPEs) are indispensable for enabling durable, safe, and high‐energy‐density solid‐state lithium metal batteries (SSLMBs). However, the concurrent optimization of lithium‐salt dissociation, Li ⁺ transport, and lithium‐metal interfacial chemistry remains a challenge over decades. In this study, a PPy‐regulated solid polymer electrolyte (PPyPL) featuring chemically differentiated coordination sites is developed to reconstruct ion‐solvation chemistry through site‐selective Li ⁺ /anion coordination. The resulting coordination architecture affords differentiated molecular interactions in which pyrrolic nitrogen sites preferentially coordinate Li ⁺ , whereas hydrogen sites along the PPy backbone interact with bis(trifluoromethanesulfonyl)imide (TFSI ⁻ ) anions, thereby simultaneously promoting lithium‐salt dissociation, accelerating Li ⁺ transport, and directing LiF/Li ₃ N‐rich interphase formation. Benefiting from the synergistic regulation of ion‐solvation chemistry and interfacial evolution, PPyPL achieves an ionic conductivity of 0.76 mS cm ⁻¹ at room temperature (25°C), a Li ⁺ transference number of 0.65, and ultralong Li plating/stripping stability over 8000 h. It further enables outstanding rate capability and durable cycling in both Li||LiFePO ₄ (LFP) and Li||LiNi _0.8 Co _0.1 Mn _0.1 O ₂ (NCM811) solid‐state full cells. This work provides a new strategy for regulating Li ⁺ /anion coordination in advanced SPEs toward durable SSLMBs.

Conventional ethylene carbonate (EC)-based electrolytes are dominated by strong Li+-solvent coordination, which leads to sluggish reaction kinetics at low-temperature and severe interfacial side reactions under high-voltage operation. Herein, a ternary electrolyte with weak-solvation characteristics based on lithium difluoroxalate borate (LiDFOB) salt and synergistic propylene carbonate (PC)/ methyl difluoroacetate (MDFA)/ fluoroethylene carbonate (FEC) (4:4:2, v/v/v) solvent system is developed. MDFA serves as the primary weakly coordinating component to reconstruct the Li+ solvation environment by weakening Li+−PC coordination, while FEC complements this process by promoting the formation of robust inorganic-rich interphases on both electrodes. The reconstructed solvation structure facilitates Li+ desolvation, whereas the stabilized interphases effectively suppress electrolyte decomposition and transition-metal dissolution, leading to a thin and homogeneous cathode electrolyte interphase (∼7 nm) and a low-resistance LiF-rich solid electrolyte interphase. Benefiting from the synergistic regulation of bulk solvation and interfacial chemistry, Li||Li symmetric cells achieve stable cycling over 1000 h at −30 °C, outperforming EC-based electrolytes by ∼400 h. Moreover, Li||NCM811 full cells retain 98.16% capacity after 110 cycles at −30 °C (3.0−4.3 V). This work provides a feasible solvation modulation strategy for high-performance low-temperature lithium metal batteries.

Aqueous zinc (Zn) batteries are emerging as promising candidates for energy storage systems (ESS) and wearable electronics, but their practical application is hindered by low energy density and electrochemical instability at the Zn anode–electrolyte interface. Here, we report an orbital‐hybridizable nanoseed (OHNS) interphase composed of graphene oxide nanoribbons (GONRs) uniformly deposited on Cu current collectors via a scalable slot‐die coating process, enabling one‐minute‐rechargeable, energy‐dense anode‐free aqueous Zn batteries. The carbon edges (C‐edges) prevalent in the GONR facilitate orbital hybridization with Zn. This chemical interplay between the heteroatoms (C‐edge and Zn) enhances Zn nucleation kinetics and retards surface diffusion of adsorbed Zn, thereby promoting corrosion‐resistant, (002)‐oriented growth of Zn. Consequently, reversible Zn plating/stripping with high Coulombic efficiency (∼99.5%) was achieved even at a high current density of 120 mA cm ⁻² . Moreover, anode‐free full cells with the OHNS interphase delivered a maximum energy/power density of 140.6 Wh kg ⁻¹ /4138.1 W kg ⁻¹ . Notably, anode‐free pouch cells exhibited stable capacity retention of 82.2% after 800 cycles at a fast charge/discharge current density of 106C (equivalent to a time of 34 s).

Solid-state lithium metal batteries (SSLMBs) represent a prime direction for next-generation high-energy-density storage technologies. As the central component for developing SSLMBs, current research focuses on designing solid-state electrolytes featuring high ionic conductivity and low electronic conductivity, along with low cost. However, great challenges are encountered. This work develops a composite solid electrolyte (CSE) consisting of a doped Li₄Ti_4.95Zr_0.05O₁₂ (LTZO1) and poly(vinylidene fluoride) (PVDF), which has a network structure that enables rapid ion conduction and electron blocking. Density functional theory calculations confirm that Zr doping can get a reduced energy barrier for Li⁺ transport, with ionic conductivity increasing from 0.228 mS cm^-1 to 0.665 mS cm^-1 and dramatically suppressing its electronic conductivity from 0.11 mS cm^-1 to 2.4 × 10^-6 S cm^-1. The optimized CSE exhibits enhanced ionic conductivity from 0.171 mS cm^-1 to 0.581 mS cm^-1, further weakens electronic conductivity, and has a critical current density of up to 5.5 mA cm^-2. These excellent properties make solid-state batteries such as Li|LTZO1|LiFePO₄ and Li|LTZO1|NCM811 achieve good performance, including capacity and cycling. This study provides an effective strategy for preparing practical CSEs for SSLMBs.

The performance of lithium metal batteries is significantly affected by temperature variations, which makes it challenging for them to operate across a wide temperature range. Herein, a wide temperature adaption electrolyte is proposed, enabling excellent electrochemical performance of lithium metal batteries from −40 °C to 60 °C. Large, 5.8 Ah pouch cells employing such an electrolyte achieve high energy density of 503.3 Wh kg ⁻¹ at 25 °C with a lifespan of 260 cycles and outstanding energy density of 339 Wh kg ⁻¹ at −40 °C. The critical role of the solid electrolyte interphase (SEI) in determining the temperature‐dependent performance of lithium metal batteries is unveiled. It is demonstrated that the LiF‐rich, anion‐derived SEI facilitates Li ⁺ diffusion in SEI. Moreover, accelerated Li ⁺ desolvation at SEI is observed. These two aspects promote the kinetics of lithium metal anodes and further inhibit the dendrite growth at low temperatures. This work showcases the importance of understating the chemistry of SEI to enable wide temperature lithium metal batteries.

The performance of lithium metal batteries is significantly affected by temperature variations, which makes it challenging for them to operate across a wide temperature range. Herein, a wide temperature adaption electrolyte is proposed, enabling excellent electrochemical performance of lithium metal batteries from −40 °C to 60 °C. Large, 5.8 Ah pouch cells employing such an electrolyte achieve high energy density of 503.3 Wh kg ⁻¹ at 25 °C with a lifespan of 260 cycles and outstanding energy density of 339 Wh kg ⁻¹ at −40 °C. The critical role of the solid electrolyte interphase (SEI) in determining the temperature‐dependent performance of lithium metal batteries is unveiled. It is demonstrated that the LiF‐rich, anion‐derived SEI facilitates Li ⁺ diffusion in SEI. Moreover, accelerated Li ⁺ desolvation at SEI is observed. These two aspects promote the kinetics of lithium metal anodes and further inhibit the dendrite growth at low temperatures. This work showcases the importance of understating the chemistry of SEI to enable wide temperature lithium metal batteries.