Gradient Quasi-Solid Electrolyte Enables Selective and Fast Ion Transport for Robust Aqueous Zinc-Ion Batteries.

The quasi-solid electrolytes (QSEs) attract extensive attention due to their improved ion transport properties and high stability, which is synergistically based on tunable functional groups and confined solvent molecules among the polymetric networks. However, the trade-off effect between the polymer content and ionic conductivity exists in QSEs, limiting their rate performance. In this work, the epitaxial polymerization strategy is used to build the gradient hydrogel networks (GHNs) covalently fixed on zinc anode. Then, it is revealed that the asymmetric distribution of negative charges benefits GHNs with fast and selective ionic transport properties, realizing a higher Zn2+ transference number of 0.65 than that (0.52) for homogeneous hydrogel networks (HHNs) with the same polymer content. Meanwhile, the high-density networks formed at Zn/GHNs interface can efficiently immobilize free water molecules and homogenize the Zn2+ flux, greatly inhibiting the water-involved parasitic reactions and dendrite growth. Thus, the GHNs enable dendrite-free stripping/plating over 1000 h at 8 mA cm-2 and 1 mAh cm-2 in a Zn||Zn symmetric cell, as well as the evidently prolonged cycles in various full cells. This work will shed light on asymmetric engineering of ion transport channels in advanced quasi-solid battery systems to achieve high energy and safety.

Skeleton engineering of rigid covalent organic frameworks to alter the number of binding sites for improved radionuclide extraction.

Crystalline porous covalent frameworks (COFs) have been considered as a platform for uranium extraction from seawater and nuclear waste. However, the role of rigid skeleton and atomically precise structures of COFs is often ignored in the design of defined binding configuration. Here, a COF with an optimized relative position of two bidentate ligands realizes full potential in uranium extraction. Compared with the para-chelating groups, the optimized ortho-chelating groups with oriented adjacent phenolic hydroxyl groups on the rigid skeleton endow an additional uranyl binding site, thereby increasing the total number of binding sites up to 150%. Experimental and theoretical results indicate that the uranyl capture is greatly improved via the energetically favored multi-site configuration and the adsorption capacity reaches up to 640 mg g-1, which exceeds that of most reported COF-based adsorbents with chemical coordination mechanism in uranium aqueous solution. This ligand engineering strategy can efficiently advance the fundamental understanding of designing the sorbent systems for extraction and remediation technology.

Tunable Ion Transport in Two-Dimensional Nanofluidic Channels.

Layered two-dimensional (2D) materials with interlayer channels at the nanometer scale offer an ideal platform to control ion transport behaviors, including high-precision separation, ultrafast diffusion, and tunable permeation flux, which show great potential for energy conversion and storage, water treatment, catalysis, biosynthesis, and sensing. Recent advances in controlling the structure and functionality of 2D nanofluidic channels sustainably open doors for more revolutionary applications. In this Perspective, we first present a brief introduction to the fundamental mechanisms for ion transport in 2D nanofluidic channels and an overview of state-of-the-art assembly technologies of nanochannel membranes. We then point out new avenues for developing advanced nanofluidics, combining molecular-level cross-linking, and surface modification in nanoconfinement. Finally, we outline the potential applications of these 2D nanofluidic channel membranes and their technical challenges that need to be addressed to afford for practical applications.

Anion Concentration Gradient-Assisted Construction of a Solid-Electrolyte Interphase for a Stable Zinc Metal Anode at High Rates.

Coulombic efficiency (CE) and cycle life of metal anodes (lithium, sodium, zinc) are limited by dendritic growth and side reactions in rechargeable metal batteries. Here, we proposed a concept for constructing an anion concentration gradient (ACG)-assisted solid-electrolyte interphase (SEI) for ultrahigh ionic conductivity on metal anodes, in which the SEI layer is fabricated through an in situ chemical reaction of the sulfonic acid polymer and zinc (Zn) metal. Owing to the driving force of the sulfonate concentration gradient and high bulky sulfonate concentration, a promoted Zn2+ ionic conductivity and inhibited anion diffusion in the SEI layer are realized, resulting in a significant suppression of dendrite growth and side reaction. The presence of ACG-SEI on the Zn metal enables stable Zn plating/stripping over 2000 h at a high current density of 20 mA cm-2 and a capacity of 5 mAh cm-2 in Zn/Zn symmetric cells, and moreover an improved cycling stability is also observed in Zn/MnO2 full cells and Zn/AC supercapacitors. The SEI layer containing anion concentration gradients for stable cycling of a metal anode sheds a new light on the fundamental understanding of cation plating/stripping on metal electrodes and technical advances of rechargeable metal batteries with remarkable performance under practical conditions.

High-Entropy Atomic Layers of Transition-Metal Carbides (MXenes).

High-entropy materials (HEMs) have great potential for energy storage and conversion due to their diverse compositions, and unexpected physical and chemical features. However, high-entropy atomic layers with fully exposed active sites are difficult to synthesize since their phases are easily segregated. Here, it is demonstrated that high-entropy atomic layers of transition-metal carbide (HE-MXene) can be produced via the selective etching of novel high-entropy MAX (also termed Mn +1 AXn (n = 1, 2, 3), where M represents an early transition-metal element, A is an element mainly from groups 13-16, and X stands for C and/or N) phase (HE-MAX) (Ti1/5 V1/5 Zr1/5 Nb1/5 Ta1/5 )2 AlC, in which the five transition-metal species are homogeneously dispersed into one MX slab due to their solid-solution feature, giving rise to a stable transition-metal carbide in the atomic layers owing to the high molar configurational entropy and correspondingly low Gibbs free energy. Additionally, the resultant high-entropy MXene with distinct lattice distortions leads to high mechanical strain into the atomic layers. Moreover, the mechanical strain can efficiently guide the nucleation and uniform growth of dendrite-free lithium on HE-MXene, achieving a long cycling stability of up to 1200 h and good deep stripping-plating levels of up to 20 mAh cm-2 .

Selective Etching Quaternary MAX Phase toward Single Atom Copper Immobilized MXene (Ti3C2Clx) for Efficient CO2 Electroreduction to Methanol.

Single atom catalysts possess attractive electrocatalytic activities for various chemical reactions owing to their favorable geometric and electronic structures compared to the bulk counterparts. Herein, we demonstrate an efficient approach to producing single atom copper immobilized MXene for electrocatalytic CO2 reduction to methanol via selective etching of hybrid A layers (Al and Cu) in quaternary MAX phases (Ti3(Al1-xCux)C2) due to the different saturated vapor pressures of Al- and Cu-containing products. After selective etching of Al in the hybrid A layers, Cu atoms are well-preserved and simultaneously immobilized onto the resultant MXene with dominant surface functional group (Clx) on the outmost Ti layers (denoted as Ti3C2Clx) via Cu-O bonds. Consequently, the as-prepared single atom Cu catalyst exhibits a high Faradaic efficiency value of 59.1% to produce CH3OH and shows good electrocatalytic stability. On the basis of synchrotron-based X-ray absorption spectroscopy analysis and density functional theory calculations, the single atom Cu with unsaturated electronic structure (Cuδ+, 0 < δ < 2) delivers a low energy barrier for the rate-determining step (conversion of HCOOH* to absorbed CHO* intermediate), which is responsible for the efficient electrocatalytic CO2 reduction to CH3OH.