Miao Yu

Current H ₂ ‐selective polymer membranes face an inescapable permeability‐selectivity trade‐off. We report a hydrogen‐bond crosslinking strategy mediated by pyrophosphoric acid (PPA) to engineer chain packing in unprotonatable 6FDA‐TFMB polyimides (PI) for ultra‐selective H ₂ separation. Through molecular design, rigid non‐coplanar 6FDA‐TFMB PI featuring trifluoromethyl side groups was subsequently incorporated with hydroxyl‐rich PPA. Collaborative simulation‐experimental validation confirmed that the hydrogen‐bond (C═O···H−O) crosslinking between PI and PPA in the PI ₂ ‐PPA ₁ ‐60°C membrane achieved 4% compression of polymer chain spacing (d‐spacing from 3.95 to 3.69 Å) compared to pristine PI, constructing a hierarchically graded chain‐spacing architecture with 2.18–5.17 Å gradient distribution. This engineering structure endowed the PI ₂ ‐PPA ₁ ‐60°C membrane with extremely high H ₂ permeability (167.24 Barrer), while achieving efficient molecular sieving, elevating H ₂ /CH ₄ and H ₂ /N ₂ selectivity to 708.51 and 443.56 respectively (PI–H ₂ /CH ₄ : 95.34; H ₂ /N ₂ : 40.59). The breakthrough separation performance surpassed the 2015 Robeson upper bound, providing an engineerable supramolecular solution to decouple the permeability‐selectivity conflict in membrane technology.

Due to Zn ²⁺ uneven dispersion and aggregated deposition, zinc dendrite causes poor cycling stability in aqueous Zn‐ion batteries (AZIBs). Herein, we proposed constructing an Ag gradient hierarchical porous membrane to regulate reaction deposition and bottom‐up growth of Zn, by combining “electroless plating” with “phase inversion” not only utilizing polar functional groups (─COOH and ─C≡N) of membrane materials to adsorb Ag ⁺ , but regulating the solvent exchange rate to control the reduction rate of Ag ⁺ to induce gradient Ag distribution during membrane formation. The membrane is benefit to guide Zn ²⁺ dispersion and homogenization uniformly on the electrode surface via an interlaced porous structure. The Ag sites react with Zn ²⁺ to form Ag ₅ Zn ₈ during charging, which preferably induces Zn ²⁺ to deposit along the 002‐crystal plane on Zn surface. The synergistically promotional effect of porous membrane skeleton with Ag gradient and alloy phases as optimized deposition sites can enhance stable deposition on Zn anode. Zn//Cu and Zn symmetrical batteries with the interlayers exhibit high stability after 1100 cycles and 1200 h. The corresponding Zn//CVO coin cells and pouch cells are stable for 3000 and 1000 cycles. The work presents a new method to prepare a functional membrane interlayer to solve Zn dendrites in AZIBs.

Constructing vertically aligned, penetrating metal–organic framework (MOFs) gas transfer pathways within mixed matrix membranes (MMMs) is an effective strategy for optimizing gas transport under low filler loading (≤25 wt.%). Herein, we developed a novel “stack‐polymerize‐section” process to construct vertically aligned ZIF‐8 pathways in MMMs by tailoring the density and channel size of PAN@ZIF‐8 NFM for optimizing CO ₂ ultrafast and in‐parallel transport. The designed XLPEO/PAN@ZIF‐8 MMM exhibits excellent performance far exceeding the 2019 McKeown upper bound, with CO ₂ permeability and CO ₂ /N ₂ selectivity of 369.2 Barrer and 90.0, respectively. Meanwhile, a novel parallel computational model that synergistically integrates the Maxwell model with resistance‐based (RB) model methodology was proposed to introduce the interfacial resistance coefficient derived from polymer–MOFs interface heterogeneous concentration gradients. This work demonstrates the potential of vertically aligned MOFs channels for high‐performance gas separation, providing a scalable and controllable fabrication pathway for maximizing the efficiency of MOFs in membrane technology.

Gel polymer electrolytes (GPEs) hold promise for lithium metal batteries because they are processable and can form conformal electrode contact. However, tortuous ion‐transport pathways and pronounced interfacial polarization severely constrain fast‐charging capability. Herein, a vertically aligned ion transport interface is constructed via a single‐step dopamine‐regulated phase inversion strategy, designed to couple low‐tortuosity pathways with solvation‐tuning chemistry for efficient transport and interfacial regulation. During phase inversion, dopamine simultaneously drives rapid demixing to generate finger‐like vertical channels, stabilizes the polar β‐PVDF‐HFP framework via dipole interactions, and oxidatively polymerizes to enrich the pore walls with Lewis‐basic catechol/amine sites. Theoretical simulations and ⁷ Li ssNMR reveal that the high‐dielectric framework within vertically aligned pores provides low‐tortuosity pathways and low Li ⁺ migration barrier for rapid ion transport, while Lewis‐basic pore walls modulate Li ⁺ solvation to weaken anion association, thereby homogenizing Li ⁺ flux and suppressing concentration polarization. Consequently, the electrolyte exhibits high ionic conductivity of 1.2 × 10 ⁻³ S cm ⁻¹ and Li ⁺ transference number of 0.666. It enables stable cycling of symmetric cells for over 2500 h and supports LiFePO ₄ full cells with operation even at ultrahigh rates up to 20 C. A small molecule enables one‐step tri‐functionalization to build ion‐transport interface for fast‐charging quasi‐solid‐state lithium metal batteries.

Simultaneously regulating the local electronic microenvironment of dual phases in heterostructures remains a significant challenge. Herein, we propose a lattice‐inherited single‐atom strategy to construct Re‐doped MoS ₂ /MoP dual phases, where Re atoms remain atomically dispersed throughout the MoS ₂ to MoP transformation. This strategy enables concurrent regulation of the diffusion of MoS ₂ and catalytic MoP phases, thereby overcoming the intrinsic adsorption, diffusion, and catalytic limitations of individual phases in conventional dual‐phase heterostructures. DFT calculations reveal that, in Re‐MoS ₂ , Re incorporation induces reconfiguration of surface S 3 p orbitals, weakening Li‐S orbital overlap and lowering Li ⁺ diffusion barrier. In Re‐MoP, unpaired delocalized electrons upshift the d ‐band center and strengthen interfacial charge coupling, thereby accelerating polysulfide redox kinetics. Meanwhile, the dual‐phase distribution of Re atoms enhances the built‐in electric field, promoting directional polysulfide migration toward catalytic domains. Structurally, the constructed hetero‐nanotube catalysts, featuring ultrathin Re‐doped MoS ₂ /MoP coaxially encapsulating carbon nanotubes, ensure intimate face‐to‐face contact and efficient electron transport. The cell exhibits remarkable cycling stability (0.035% decay over 1000 cycles at 5 C) and achieves a high areal capacity of 9.16 mAh cm ⁻² at 10.59 mg cm ⁻² sulfur loading. This work opens a new avenue for enhancing heterostructure synergistic effects, extending beyond Li‐S batteries to other multi‐electron‐transfer systems.

Sulfonated carbon nitride is proposed to functionalize glass fiber separators. The enhanced Zn²⁺ affinity, electrostatic repulsion against SO₄²⁻, and promoted hydrated Zn²⁺ de-solvation can enable uniform Zn deposition and suppress side reactions.

The poor reversibility of Zn stripping/plating processes leads to unsatisfactory cycling stability of Zn anodes, limiting the practical application of aqueous zinc-ion batteries. Herein, sulfobutylether-β-cyclodextrin (SCD) was introduced into the electrolyte as a multi-functional additive. The zincophilic sulfonate groups were found to interact with Zn²⁺ to modulate the solvation structure, enhance adsorption and govern the adsorption configuration of SCD on the Zn surface. This specific adsorption configuration could in situ construct two planes on the Zn surface with progressively improved affinity to Zn²⁺, which could drive the diffusion of Zn²⁺ through the hydrophobic toroidal inner channel, enable the uniform dispersion of Zn²⁺ flux and facilitate the de-solvation process. The synergistic promotional effect of the functional groups and specific structural features remarkably improved the stability of the Zn anode. With the addition of SCD, the Zn//Cu cell exhibited an extended cycle life of over 3000 cycles with an average CE exceeding 99.7%. The Zn//Zn symmetric cell also demonstrated superior cycling stability of over 3900 h at 2 mA cm⁻². The corresponding Zn//NH₄V₄O₁₀ full cells delivered a higher specific capacity and better cycling stability than cells using bare electrolytes. The assembled pouch cells were also stable for over 300 cycles, demonstrating the practical application potential of this electrolyte in high-performance AZIBs.