Guozhao Fang

Anti‐freezing cosolvents are commonly introduced to maintain electrolyte fluidity at subzero temperatures. However, their weak participation in the primary Zn ²⁺ solvation sheath can leave desolvation‐coupled interfacial kinetics largely unimproved. Here, we introduce a molecular cosolvation‐promotion strategy that activates an otherwise passive anti‐freezing solvent. Tris(2‐chloropropyl) phosphate (TCPP), featuring an electron‐rich phosphoryl center and a bulky, weakly solvating periphery, promotes methanol incorporation into the primary Zn ²⁺ solvation sheath. Remarkably, although the coordination number of TCPP is only 0.17, its addition increases the methanol coordination number from 0.21 to 1.19 while decreasing the water coordination number from 4.01 to 3.07. This coordination amplification lowers the apparent activation energy for desolvation‐coupled charge transfer from 18.46 to 13.91 kJ mol ⁻¹ and preserves an ionic conductivity of 4.6 mS cm ⁻¹ at −40°C. Meanwhile, preferential interfacial adsorption of TCPP excludes reactive water, homogenizes the Zn ²⁺ flux, and suppresses corrosion and dendritic deposition. Consequently, Zn||Zn cells operate stably for over 2700 h at −40°C, while Zn||MnVO full cells retain 84.8% of their capacity after 8000 cycles at −20°C. This work establishes molecular promotion of cosolvent coordination as a general electrolyte‐design principle for decoupling anti‐freezing fluidity from sluggish subzero charge‐transfer kinetics.

Anti‐freezing cosolvents are commonly introduced to maintain electrolyte fluidity at subzero temperatures. However, their weak participation in the primary Zn ²⁺ solvation sheath can leave desolvation‐coupled interfacial kinetics largely unimproved. Here, we introduce a molecular cosolvation‐promotion strategy that activates an otherwise passive anti‐freezing solvent. Tris(2‐chloropropyl) phosphate (TCPP), featuring an electron‐rich phosphoryl center and a bulky, weakly solvating periphery, promotes methanol incorporation into the primary Zn ²⁺ solvation sheath. Remarkably, although the coordination number of TCPP is only 0.17, its addition increases the methanol coordination number from 0.21 to 1.19 while decreasing the water coordination number from 4.01 to 3.07. This coordination amplification lowers the apparent activation energy for desolvation‐coupled charge transfer from 18.46 to 13.91 kJ mol ⁻¹ and preserves an ionic conductivity of 4.6 mS cm ⁻¹ at −40°C. Meanwhile, preferential interfacial adsorption of TCPP excludes reactive water, homogenizes the Zn ²⁺ flux, and suppresses corrosion and dendritic deposition. Consequently, Zn||Zn cells operate stably for over 2700 h at −40°C, while Zn||MnVO full cells retain 84.8% of their capacity after 8000 cycles at −20°C. This work establishes molecular promotion of cosolvent coordination as a general electrolyte‐design principle for decoupling anti‐freezing fluidity from sluggish subzero charge‐transfer kinetics.

Anode-free Zn batteries are attractive for zero-excess-Zn operation and maximized anode utilization, but reversible high-areal-capacity Zn plating/stripping over large hostless interfaces remains difficult, especially in Ah-level Zn–I2 pouch cells where polyiodide shuttling accelerates capacity decay and corrodes the nascent anode interface. Here, we integrate machine-learning-guided polyiodide regulation with dynamic interfacial reconstruction to establish a self-activating Zn deposition pathway for reversible anode-free Zn–I2 cells. DFT-supervised screening reveals multidentate weak O–C–H···I interactions and chain-assisted confinement as key molecular design principles for polyiodide confinement, guiding the selection of polyethylene glycol 4000 (PE4000). More importantly, PE4000 gates trace reversible Sn/Sn2+ interfacial conversion, enabling dynamic Zn–Sn reconstruction, persistent zincophilic sites, and orientation-regulated Zn nucleation/growth during repeated plating/stripping. Consequently, the optimized anode-free Zn–I2 cells sustain 16,000 cycles at 10 mA cm–2. Single-layer pouch cells operate for over 3000 cycles at 4.65 mAh cm–2, with recovered Sn remaining reusable for another 1000 cycles. Ah-level pouch cells further deliver 2390 Ah cumulative capacity over 2800 cycles. This work establishes a system-level interface-matching strategy for practical high-utilization anode-free batteries.

Developing practical aqueous zinc metal batteries is crucial for safe grid energy storage. However, zinc anode imposes severe interfacial mass transfer and kinetic bottlenecks at high rates and high capacities, driven by thermodynamically competitive hydrogen evolution reaction and significant polarization. In this work, we establish a predictive design paradigm that resolves this dilemma by integrating active‑learning materials screening and a composition‑gradient alloy (GL) anode with an interfacial kinetic compensation. Moreover, the gradient grain boundaries preclude structural failure under high capacities arising from stress concentration at high rates. Consequently, GL anode achieves 20,000 cycles at 40 mA cm ⁻² and the cumulative capacity of 81.36 Ah at 80 mA cm ⁻² . The symmetric cell endures more than 400 h at 80% depth of discharge and 20 mA cm ⁻² , while pouch cells exceed 1000 h at 5 mAh cm ⁻² . Coupled with high‐loading vanadium‐based cathode (30 mg cm ⁻² , 4.5 mAh cm ⁻² ), the full cell retains 91% capacity after 1500 cycles. Notably, a 560 mAh pouch cell stable for 350 cycles over 90% capacity retention at a high rate of 20 mA cm ⁻² . This work offers a design concept of practical zinc anode with high‐rate stability for zinc pouch cells.

Developing practical aqueous zinc metal batteries is crucial for safe grid energy storage. However, zinc anode imposes severe interfacial mass transfer and kinetic bottlenecks at high rates and high capacities, driven by thermodynamically competitive hydrogen evolution reaction and significant polarization. In this work, we establish a predictive design paradigm that resolves this dilemma by integrating active‑learning materials screening and a composition‑gradient alloy (GL) anode with an interfacial kinetic compensation. Moreover, the gradient grain boundaries preclude structural failure under high capacities arising from stress concentration at high rates. Consequently, GL anode achieves 20,000 cycles at 40 mA cm ⁻² and the cumulative capacity of 81.36 Ah at 80 mA cm ⁻² . The symmetric cell endures more than 400 h at 80% depth of discharge and 20 mA cm ⁻² , while pouch cells exceed 1000 h at 5 mAh cm ⁻² . Coupled with high‐loading vanadium‐based cathode (30 mg cm ⁻² , 4.5 mAh cm ⁻² ), the full cell retains 91% capacity after 1500 cycles. Notably, a 560 mAh pouch cell stable for 350 cycles over 90% capacity retention at a high rate of 20 mA cm ⁻² . This work offers a design concept of practical zinc anode with high‐rate stability for zinc pouch cells.

Fe‐Mn‐based layered oxides with high specific capacity and natural abundance are among the most promising cathode materials for sodium‐ion batteries. However, their low discharge plateau and the issue of irreversible transition metal migration and dissolution significantly impair their electrochemical performance, hindering further commercial application. To address the inherent constraints of Fe‐Mn‐based cathodes, this work developed a π ‐bond engineering enables Mn‐valency self‐regulation strategy and designed a low‐cost and environmentally friendly P2‐type cathode material Na _0.67 Fe _0.2 Mn _0.5 Cu _0.15 Zn _0.1 Ti _0.05 O ₂ (CZT321) without expensive metal elements such as Co, Li, and Ni. In situ testing and DFT calculations reveal that the enhanced TM─O bonds suppress the unfavorable P2−O2/OP4 phase transitions. The unique “ π ‐type” Cu─O─Mn bond, where the 3d orbitals of Cu and Mn are bridged via the O 2p orbital, endows the system with a self‐regulating mechanism (SRM) for the Mn ³⁺ /Mn ⁴⁺ redox potential. This mechanism inhibits the Jahn‐Teller effect of Mn and significantly enhances the long‐term cycling stability of the electrode material. The half‐cell delivers a specific capacity of 144.0 mAh g ⁻¹ , with a capacity retention rate of 86.1% after 150 cycles at 200 mA g ⁻¹ . This work provides new insights for the further design and application of Fe‐Mn‐based cathode materials in sodium‐ion batteries.

Interfacial modification is a widely adopted strategy for stabilizing zinc metal anodes in aqueous zinc‐ion batteries. However, most reported designs rely on strictly insoluble interphases, largely due to routine path dependence in the prevailing assumption that soluble modification layers would rapidly dissipate and lose functionality. Herein, a partially soluble zinc acetate surface modification is constructed via temperature‐controlled etching, enabling simultaneous regulation of the electrode interface and the electrolyte environment. Upon electrolyte immersion, the residual interphase homogenizes the interfacial electric field and mitigates surface corrosion, while released acetate anions which dynamically reconstruct the Zn ²⁺ solvation structure by partially displacing coordinated water molecules. This cooperative regulation promotes uniform Zn deposition while suppressing parasitic corrosion reactions on Zn anode. As a result, the zinc modified Zn anode delivers stable dendrite‐free plating/stripping for over 2000 h at 10 mA cm ⁻² and maintains reversible cycling under a 30% depth of discharge for 600 h. Full cells with an ammonium vanadate cathode exhibit a capacity retention of 67.8% after 1500 cycles at 5 A g ⁻¹ . This work demonstrates that controlled interphase solubility can be intentionally leveraged as a viable parameter for interface engineering in aqueous zinc batteries.

Decreasing the pore curvature of the current collector suppresses the corrosion of metal dusts, enabling electricity generation from the dust.