A Stable Triazole-Based Covalent Gel for Long-Term Cycling Zn Anode in Zinc-Ion Batteries.

In this work, a functional covalent gel material is developed to resolve the severe dendritic growth and hydrogen evolution reaction toward Zn/electrolyte interface in aqueous zinc-ion batteries (ZIBs). A covalent gel layer with superior durability forms homogeneously on the surface of Zn foil. The covalent gel with triazole functional groups can uniformize the transport of Zn2+ due to the interactions between Zn2+ ions and the triazole groups in the covalent gel. As a consequence, the symmetrical battery with triazole covalent gel maintains stable Zn plating/stripping for over 3000 h at 1 mA cm-2 and 1 mAh cm-2 , and the full cell combined with a V2 O5 cathode operates steadily and continuously for at least 1800 cycles at 5 A g-1 with a capacity retention rate of 67.0%. This work provides a train of thought to develop stable covalent gels for the protection of zinc anode toward high-performance ZIBs.

Suppression of Vanadium Oxide Dissolution via Cation Metathesis within a Coordination Supramolecular Network for Durable Aqueous Zn-V2 O5 Batteries.

Aqueous zinc metal batteries (ZMBs) are a promising sustainable technology for large-scale energy storage applications. However, the water is often associated with problematic parasitic reactions on both anode and cathode, leading to the low durability and reliability of ZMBs. Here, a multifunctional separator for the Zn-V2 O5 batteries by growing the coordination supramolecular network (CSN:Zn-MBA, MBA = 2-mercaptobenzoic acid) on the conventional non-woven fabrics (NWF) is developed. CSN tends to form a stronger coordination bond as a softer cation, enabling a thermodynamically preferred Zn2+ to VO2 + substitution in the network, leading to the formation of VO2 -MBA interface, that strongly obstructs the VO2 (OH)2 - penetration but simultaneously allows Zn2+ transfer. Moreover, Zn-MBA molecules can adsorb the OTF- and distribute the interfacial Zn2+ homogeneous, which facilitate a dendrite-free Zn deposition. The Zn-V2 O5 cells with Zn-MBA@NWF separator realize high capacity of 567 mAh g-1 at 0.2 A g-1 , and excellent cyclability over 2000 cycles with capacity retention of 82.2% at 5 A g-1 . This work combines the original advantages of the template and new function of metals via cation metathesis within a CSN, provides a new strategy for inhibiting vanadium oxide dissolution.

Elastomeric Electrolyte for High Capacity and Long-Cycle-Life Solid-State Lithium Metal Battery.

High room-temperature ionic conductivity and good compatibility with lithium metal and cathode materials are prerequisites for solid-state electrolytes used in lithium metal batteries. Here, the solid-state polymer electrolytes (SSPE) are prepared by combining the traditional two-roll milling technology with interface wetting. The as-prepared electrolytes consisting of elastomer matrix and high-mole-loading of LiTFSI salt show a high room temperature ionic conductivity of 4.6×10-4 S cm-1 , a good electrochemical oxidation stability up to 5.08 V, and improved interface stability. These phenomena are rationalized with the formation of continuous ion conductive paths based on sophisticated structure characterization including synchrotron radiation Fourier-transform infrared microscopy, wide- and small-angle X-ray scattering. Moreover, at room temperature, the Li||SSPE||LFP coin cell shows a high capacity (161.5 mAh g-1 at 0.1 C), long-cycle-life (retaining 50% capacity and 99.8% Coulombic efficiency after 2000 cycles), and good C-rate compatibility up to 5 C. This study, therefore, provides a promising solid-state electrolyte that meets both the electrochemical and mechanical requirements of practical lithium metal batteries.

A Two-Dimensional Porphyrin Coordination Supramolecular Network Cathode for High-Performance Aqueous Dual-Ion Battery.

Iodine has great potential in the energy storage, but high solubility of I3 - has seriously delayed its promotion. Benefited from abundant active sites and the open channel, two-dimensional coordination supramolecular networks (2D CSNs) is considered to be a candidate for the energy storage. Herein, a 2D porphyrin-CSN cathode named Zn-TCPP for aqueous iodine dual-ion battery (DIB) shows an excellent specific capacity of 278 mAh g-1 , and a high energy density of 340 Wh kg-1 at 5 A g-1 , as well as a durable cycle performance of 5000 cycles and a high Coulombic efficiency of 98 %. Molecular orbital theory, UV/VIS, Raman spectroscopy and density functional theory (DFT) calculations reveal charge-transfer interaction between the donor of porphyrin nitrogen and the acceptor of I3 - , and computational fluid dynamics (CFD) simulations demonstrate the contribution of 2D layered network structure of Zn-TCPP to the penetration of I3 - .

Anchoring I3- via Charge-Transfer Interaction by a Coordination Supramolecular Network Cathode for a High-Performance Aqueous Dual-Ion Battery.

Iodine is considered to have broad application prospects in the field of electrochemical energy storage. However, the high solubility of I3- severely hampers its practical application, and the lack of research on the anchoring mechanism of I3- has seriously hindered the development of advanced cathode materials for iodine batteries. Herein, based on the molecular orbital theory, we studied the charge-transfer interaction between the acceptor of I3- with a σ* empty antibonding orbital and the donor of pyrimidine nitrogen with lone-pair electrons, which is proved by the results of UV-vis absorption spectroscopy, Raman spectroscopy, and density functional theory (DFT) calculations. The prepared dual-ion battery (DIB) exhibits a high voltage platform of 1.2 V, a remarkable discharge-specific capacity of up to 207 mAh g-1, and an energy density of 233 Wh kg-1 at a current density of 5 A g-1, as well as outstanding cycle stability (operating stably for 5000 cycles) with a high Coulombic efficiency of 97%, demonstrating excellent electrochemical performance and a promising prospect in stationary energy storage.

Scalable Manufacturing of Solid Polymer Electrolytes with Superior Room-Temperature Ionic Conductivity.

A scalable manufacturing protocol is developed to prepare polymer-based solvent-free all-solid flexible energy storage devices based on a two-roll mill and adapted rubber mixing technology. The as-prepared solid polymer electrolytes (SPEs) consisting of commercial poly(methyl methacrylate)-grafted natural rubber (MG30) and lithium bis(trifluoromethanesulfonyl)imide achieve a superior ionic conductivity of 2.7 × 10-3 S cm-1 at 30 °C. The superior ionic conductivity is attributed to the formation of an ionic cluster network in the composite as proved by small-angle X-ray scattering and infrared spectroscopy measurements. Moreover, the as-prepared SPEs show good mechanical stability over a broad temperature range, that is , a storage modulus above 1 × 104 Pa from 30 to 120 °C as indicated by the rheology data. Furthermore, the SPEs were assembled with the carbon black-filled MG30 (i.e., MG30C) electrode into a flexible supercapacitor cell, which had a wide voltage window of 3.5 V, good energy density of 28.4 µW h·cm-2 at 160 °C, and good temperature tolerance up to 160 °C. This scaling-up manufacture strategy shows tremendous potential to the advancing of SPEs in applications of flexible energy storage device.

Constructing Hydrophobic Interface with Close-Packed Coordination Supramolecular Network for Long-Cycling and Dendrite-Free Zn-Metal Batteries.

Commercialization of aqueous zinc-metal batteries remains unrealistic due to the substantial dendrite growth and side reaction issues on the zinc anodes. It is highly demanded to develop easy-to-handle approaches for constructing stable, dense, as well as homogeneous solid anode/electrolyte interfaces. Herein, the authors construct the zinc anode interface with a close-packed Zn-TSA (TSA = thiosalicylate) coordination supramolecular network through the facile and up-scalable wet-chemical method. The hydrophobic Zn-TSA network can block solvated water and establish a solid-state diffusion barrier to well-distribute the interfacial Zn2+ , thus inhibiting hydrogen evolution and zinc dendrite growth on the anode. Meanwhile, the Zn-TSA network induces the formation of a uniform and stable solid electrolyte interphase composed of multiple inorganic-organic compounds. This denser structure can accommodate and self-heal the crack/degradation of the anode interphase associated with the repeated volume changes, and suppress the generation of detrimental by-product, Znx (OTF- )y (OH)2x-y ·nH2 O. Such a rationally fabricated anode/electrolyte interface further endows the assembled symmetric cells with superior plating/stripping stability for over 2000 h without dendrite formation (at 1 mA cm-2 and 1 mAh cm-2 ). Furthermore, this zinc anode has practical application in the Zn-MoS2 and Zn-V2 O5 full cells. This study provides a new train of thought for constructing the dense interface of zinc-metal anode.

A nano interlayer spacing and rich defect 1T-MoS2 as cathode for superior performance aqueous zinc-ion batteries.

Aqueous Zn-ion batteries (ZIBs) are considered very promising alternatives to lithium-ion batteries. However, the low reversibility and slow diffusion of zinc ions in the positive electrode limit their commercial applications. Herein, we successfully prepared the metallic 1T phase of MoS2 (1T-MoS2) with a nano interlayer spacing of 1.025 nm through a simple one-step hydrothermal method, and used it as a cathode in ZIBs. By adjusting the hydrothermal temperature, the crystallinity and Zn2+ storage capacity of MoS2 as a cathode for ZIBs are effectively improved. MoS2 had the most favorable structure when the hydrothermal temperature was 200 °C, such as larger layer spacing and more lattice distortion. When employed as a cathode, 200-MoS2 exhibited a considerable specific capacity of 125 mA h g-1 at the current density of 2 A g-1 and high capacity retention of 100% after 500 cycles. This strategy provides a new option for improving the performance of the layered structure as an aqueous zinc ion battery.

Plane Double-Layer Structure of AC@S Cathode Improves Electrochemical Performance for Lithium-Sulfur Battery.

Due to the high theoretical specific capacity of lithium-sulfur batteries, it is considered the most promising electrochemical energy storage device for the next generation. However, the development of lithium-sulfur battery has been restricted by its low cycle efficiency and low capacity. We present a Plane double-layer structure of AC@S cathode to improve the electrochemical performance of lithium-sulfur batteries. The battery with this cathode showed good electrochemical performance. The initial discharge capacity of the battery with the structure of AC@S cathode could reach 1,166 mAhg-1 at 0.1 C. After 200 cycles, it still remains a reversible capacity of 793 mAh g-1 with a low fading rate of 0.16% per cycle. Furthermore, the batteries could hold a discharge capacity of 620 mAh g-1 after 200 cycles at a typical 0.5 C rate. The improvement of electrochemical performance is attributed to that the polysulfide produced during charge/discharge can be better concentrated in the cathode by the planar double-layer structure, thus reducing the loss of sulfur.

High-Performance Lithium-Sulfur Batteries With an IPA/AC Modified Separator.

To inhibit the polysulfide-diffusion in lithium sulfur (Li-S) batteries and improve the electrochemical properties, the commercial polypropylene (PP) was decorated by an active carbon (AC) coating with lots of electronegative oxygenic functional group of -OH. Owing to the strong adsorption of AC and the electrostatic repulsion between the -OH and negatively charged polysulfide ions, the Li-S batteries demonstrated a high initial discharge capacity of 1,656 mAh g-1 (approximately 99% utilization of sulfur) and the capacity can still remain at 830 mAh g-1 after 100 cycles at 0.2 C. Moreover, when the rate was increased to 1 C, the batteries could also possess a discharge capacity of 1,143 mAh g-1. The encouraging cycling stability make clear that this facile approach can successfully restrain the shuttle effect of polysulfides and make further progress to the practical application of Li-S batteries.