Zinc-ion batteries have demonstrated promising potential for future energy storage, whereas drawbacks, including dendrite growth, hydrogen evolution reaction, and localized deposition, heavily hinder their development for practical applications. Herein, unlike elaborated structural design and electrolyte excogitation, we introduce an effective parts-per-million (ppm)-scale electrolyte additive, phosphonoglycolic acid (PPGA), to overcome the intrinsic issues of zinc negative electrode in mild acidic aqueous electrolytes. Profiting from absorbed PPGA on zinc surface and its beneficial interaction with hydrogen bonds of adjacent water molecules, stable symmetric stripping/plating of zinc in aqueous ZnSO electrolyte at around 25 C was achieved, procuring 362 and 350 days of operation at 1 mA cm, 1 mAh cm and 10 mA cm, 1 mAh cm, respectively.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2025
Two-dimensional structure of cathode materials possesses fast kinetics in aqueous zinc ion batteries. However, in organic linear polymers it is rare to form two-dimensional structures due to the bond rotations of the polymerization reaction. In this work, inspired by the process of forming carbon fibers from polyacrylonitrile, a novel two-dimensional linear polymer (2DLP) of poly(2H,11H-bis[l,4]triazino[3,2-b : 3',2'-m]triphenodithiazine-3,12-diyl-2,11-diyli-dene-11,12-bis[methyldene]) (PTL) cathode materials were prepared for aqueous zinc-ion battery cathode materials by designing ladder structure polymer molecules with highly restricted bond rotations.
View Article and Find Full Text PDFRechargeable zinc metal batteries (ZMBs) represent a promising solution for large-scale energy storage due to their safety, cost-effectiveness, and high theoretical capacity. However, the development of zinc metal anodes is hindered by challenges such as dendrite formation, hydrogen evolution reaction (HER), and low Coulombic efficiency stemming from undesirable interfacial processes in aqueous electrolytes. This review explores various strategies to enhance zinc anode performance, focusing on artificial SEI, morphology adjustments, electrolyte regulation, and flowing electrolyte.
View Article and Find Full Text PDFOrganic compounds present promising options for sustainable zinc battery electrodes. Nevertheless, the electrochemical properties of current organic electrodes still lag behind those of their inorganic counterparts. In this study, nitro groups were incorporated into pyrene-4, 5, 9, 10-tetraone (PTO), resulting in an elevated discharge voltage due to their strong electron-withdrawing capabilities.
View Article and Find Full Text PDFAqueous Zn batteries are gaining increasing research attention in the energy storage area due to their intrinsic safety, potentially low cost and environmental friendliness; however, the zinc dendrite formation, zinc corrosion, passivation and the hydrogen evolution reaction induced by water at the anode side, and materials dissolution as well as intrinsic poor reaction kinetics at cathode side in aqueous systems, seriously shorten the cycling life and decrease energy density of batteries and greatly hinder their development. Recent advancements in asymmetric electrolytes with various functions are promising to overcome such challenges for zinc batteries at the same time. It has been proved that the applications of asymmetric electrolytes show significant contributions in the field of zinc-based batteries in suppressing side reactions while maintaining electrochemical performance to satisfy both anode and cathode.
View Article and Find Full Text PDFRecently, aqueous proton batteries have shown promise for electrochemical energy storage using MXene electrodes. However, designing high-performance MXene proton batteries remains challenging due to the inevitable hydrogen evolution reaction (HER), the vast chemical composition space of MXene, and the unclear proton transport mechanism. To tackle these challenges, we established a general descriptor based on structural units of MXenes, termed the octahedral net charge descriptor (Q).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Conventional solid-electrolyte interface (SEI) in aqueous Zn-ion batteries mainly acts as a physical barrier to prevent hydrogen evolution reaction (HER), while such SEI is prone to structural deterioration stemming from uneven Zn deposition at high current densities. Herein, we propose an in situ structural design of polymer-inorganic bilayer SEI with a proton holder feature by aniline-modulated electrolytes. The Zn(OTF) exhibits a lower LUMO energy level in comparison to aniline, resulting in the formation of a bilayer structure characterized by an inner ZnF layer and an outer polyaniline (PANI) layer.
View Article and Find Full Text PDFThe growing potential of low-dimensional metal-halide perovskites as conversion-type cathode materials is limited by electrochemically inert B-site cations, diminishing the battery capacity and energy density. Here, we design a benzyltriethylammonium tellurium iodide perovskite, (BzTEA)TeI, as the cathode material, enabling X- and B-site elements with highly reversible chalcogen- and halogen-related redox reactions, respectively. The engineered perovskite can confine active elements, alleviate the shuttle effect and promote the transfer of Cl on its surface.
View Article and Find Full Text PDFWhile many cathode materials have been developed for mild electrolyte-based Zn batteries, the lack of cathode materials hinders the progress of alkaline zinc batteries. Halide iodine, with its copious valence nature and redox possibilities, is considered a promising candidate. However, energetic alkaline iodine redox chemistry is impeded by an alkali-unadapted I element cathode and thermodynamically unstable reaction products.
View Article and Find Full Text PDFCompared with widely established monovalent-ion batteries, aqueous multivalent-ion batteries promise higher capacity release by achieving multiple electron-transfer events per ion intercalation in the host material. Despite plausibility, this high-capacity dream is untenable with the total tolerable redox charge-transfer limit of the host material for all carrier species equally, which is historically assumed to depend on the material rather than the guest carrier itself, and the kinetic hysteresis induced by larger charge/radius ratios induced kinetic hysteresis further enlarges the divide. Herein, we report that copper carrier redox in vanadium sulfide (VS) exceeds the intrinsic intercalation capacity boundary, with the highest capacity release as 675 mAh g at 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Ionogel polymer electrolyte (IPE), incorporating ionic liquid (IL) within a polymer matrix, presents a promising avenue for safe quasi-solid-state lithium metal batteries. However, sluggish Li kinetics, resulting from the formation of [Li(anion)] clusters and the occupation of Li transport sites by organic cations, limit their practical applications. In this study, we have developed zwitterionic bottlebrush polymers-based IPE with promoted Li conduction by employing poly(sulfobetaine methacrylate)-grafted poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVC-g-PSBMA) bottlebrushes as matrices of IL.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
The solid polymer electrolytes (SPEs) used in Zn-ion batteries (ZIBs) have low ionic conductivity due to the sluggish dynamics of polymer segments. Thus, only short-range movement of cations is supported, leading to low ionic conductivity and Zn transference (t ). Zn-based supramolecular crystals (ZMCs) have considerable potential for supporting long-distance Zn transport; however, their efficiency in ZIBs has not been explored.
View Article and Find Full Text PDFAqueous zinc-bromine (Zn||Br) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br ) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN) in a mesoporous carbon framework (FeSAC-CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN species for enhanced confinement and electrocatalytic effect.
View Article and Find Full Text PDFOrganic materials are promising candidates for the electrodes of aqueous zinc-ion batteries due to their nonmetallic nature, environmental friendliness, and cost-effectiveness. However, they often suffer from significant dissolution during the charge-discharge process, which poses a major hurdle to their practical applications. Inspired by membrane-less organelles in cells, a simple and versatile strategy is proposed-constructing a Janus catholyte/cathode structured electrode based on liquid-liquid phase separation, in which redox-active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Efficient and stable bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts are urgently needed to unlock the full potential of zinc-air batteries (ZABs). High-valence oxides (HVOs) and high entropy oxides (HEOs) are suitable candidates for their optimal electronic structures and stability but suffer from demanding synthesis. Here, a low-cost fluorine-lodged high-valent high-entropy layered double hydroxide (HV-HE-LDH) (FeCoNiF(OH)) is conveniently prepared through multi-ions co-precipitation, where F are firmly embedded into the individual hydroxide layers.
View Article and Find Full Text PDFIn the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH-producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal-organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen-bond-regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni-NO molecular catalyst (Ni-NO/rGO).
View Article and Find Full Text PDFElectroactive organic electrode materials exhibit remarkable potential in aqueous zinc ion batteries (AZIBs) due to their abundant availability, customizable structures, sustainability, and high reversibility. However, the research on AZIBs has predominantly concentrated on unraveling the storage mechanism of zinc cations, often neglecting the significance of anions in this regard. Herein, bipolar poly(thionine) is synthesized by a simple and efficient polymerization reaction, and the kinetics of different anions are investigated using poly(thionine) as the cathode of AZIBs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
The main challenges faced by aqueous rechargeable nickel-zinc batteries are their comparatively low energy density and poor cycling stability, mainly due to the limited capacity and reversibility of existing Ni-based cathodes. Moreover, the preparation procedures of these cathodes are complex and not easily scalable, which makes them less promising for large-scale energy storage. Herein, we utilized MXene as a functional additive to effectively improve the electrodeposition preparation of NiCo layered double hydroxides (LDH).
View Article and Find Full Text PDFAqueous zinc metal batteries are regarded as a promising energy storage solution for a green and sustainable society in the future. However, the practical application of metallic zinc anode is plagued by the thermodynamic instability issue of water molecules in conventional electrolytes, which leads to severe dendrite growth and side reactions. In this work, an ultra-thin and high areal capacity metallic zinc anode is achieved by utilizing crystalline water with a stable stoichiometric ratio.
View Article and Find Full Text PDF: We have developed a baroreceptor-inspired microneedle skin patch for pressure-controlled drug release. : This design is inspired by the skin baroreceptors, which are mechanosensitive elements of the peripheral nervous system. We adopt the finger touching to trigger the electric stimulation, ensuring a fast-response and user-friendly administration with potentially minimal off-target effects.
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