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While the onset of dendrites found inside solid polymer electrolytes was typically analyzed by the dilute solution theory, nonideal behaviors such as dendrites at underlimiting current densities were often reported. Here, we consider two critical factors that were often neglected in existing studies, the severe heterogeneous current distribution and the dynamic change of modulus during the polarization process. Polymers with different dynamic mechanical properties were assessed, exploiting the recently discovered mechanism of phase transformation inside low-salt-concentration polymers. Analyses of the operando images revealed two characteristic points on the potential curve, the local and total concentration depletion which each corresponded to the starting and stopping point of dendrites. We further assess these dynamics at different degrees of heterogeneity controlled by different electrode sizes. The penetration dynamics and Sand’s time scaling exponent were heavily affected by both the initial concentration and the electrode size, which stress the significance of interfacial dynamic heterogeneity in working batteries.

 

Zinc metal anodes are attracting much attention to enable more economical and sustainable energy storage devices. However, like other metal anodes, dendritic growths and penetrations of porous separators are still challenging to eliminate. Introducing negative surface charges on the pore walls of separators have been exploited to enforce a uniform incoming Zn-ion flux toward more uniform electrodeposition, but penetrations induced by localized high current densities still remain in available systems. In this work, we report, for the first time, a bipolar separator that exploits the distinct electroosmotic effects of the negative and the positive surface charges. The surface charge effects on Zn dendrite growths were first verified in transparent capillary cells viaoperandovideo microscopy. By stacking the positively charged separator over the negatively charged separator as our proof-of-concept, the system offers preemptively a uniform Zn-ion flux through the negative layer yet starve-stops local metal growths that already penetrated the negative layer autonomously. Chronopotentiometry experiments with the symmetric cells reveal extended short-circuit time compared to control cells. Galvanostatic cycle-life experiments of full cells with the bipolar separator showed excellent cycle life of 5,000 cycles at the rate of 10 C, without signs of metal penetration.

 

We report the use of polymer N -heterocyclic carbenes (NHCs) to control the microenvironment surrounding metal nanocatalysts, thereby enhancing their catalytic performance in CO 2 electroreduction. Three polymer NHC ligands were designed with different hydrophobicity: hydrophilic poly(ethylene oxide) (PEO–NHC), hydrophobic polystyrene (PS–NHC), and amphiphilic block copolymer (BCP) (PEO- b -PS–NHC). All three polymer NHCs exhibited enhanced reactivity of gold nanoparticles (AuNPs) during CO 2 electroreduction by suppressing proton reduction. Notably, the incorporation of hydrophobic PS segments in both PS–NHC and PEO- b -PS–NHC led to a twofold increase in the partial current density for CO formation, as compared to the hydrophilic PEO–NHC. While polymer ligands did not hinder ion diffusion, their hydrophobicity altered the localized hydrogen bonding structures of water. This was confirmed experimentally and theoretically through attenuated total reflectance surface-enhanced infrared absorption spectroscopy and molecular dynamics simulation, demonstrating improved CO 2 diffusion and subsequent reduction in the presence of hydrophobic polymers. Furthermore, NHCs exhibited reasonable stability under reductive conditions, preserving the structural integrity of AuNPs, unlike thiol-ended polymers. The combination of NHC binding motifs with hydrophobic polymers provides valuable insights into controlling the microenvironment of metal nanocatalysts, offering a bioinspired strategy for the design of artificial metalloenzymes.