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      Electrolyte Tuned Robust Interface toward Fast‐Charging Zn–Air Battery with Atomic Mo Site Catalyst

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          Abstract

          Stable operation of sustainable Zn–air batteries (ZABs) has attracted considerable attention, but it remains a huge challenge to achieve temperature‐adaptive and fast‐charging ZABs. The poor Zn |electrolyte interface and the sluggish charging kinetic are the major obstacles. Here, high‐performance ZABs are constructed by designing polarized zincophilic solid‐state electrolyte (SSE) with the unique solvation interaction of Zn 2+ with ethylene glycol (EG), and atomic Mo site cathode catalyst. On the one hand, the modulation of the solvation structure of Zn 2+ ions by partial substitution of H 2O with EG inhibits Zn dendrite growth and parasitic reactions, leading to the improvement of the Zn |electrolyte interface. Moreover, the polarized terminal groups in SSE are strongly coordinated with Zn/H 2O, which exerts a profound influence on Zn |electrolyte interface stability and low‐temperature properties. On the other hand, atomic Mo incorporated α‐Co(OH) 2 mesoporous nanosheets decrease the overpotential of oxygen evolution reaction via strong electronic interaction. Consequently, the assembled aqueous ZABs exhibit ten‐time fast‐charging ability and remarkable cycling stability. Moreover, the assembled solid‐state ZABs show unprecedented stability (1400 cycles at 5 mA cm −2) and high energy efficiency at −40 °C.

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          Interfacial Design of Dendrite‐Free Zinc Anodes for Aqueous Zinc‐Ion Batteries

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            An aqueous hybrid electrolyte for low-temperature zinc-based energy storage devices

            A frigostable aqueous hybrid electrolyte enabled by the solvation interaction of Zn 2+ –EG is proposed for low-temperature zinc-based energy storage devices. Aqueous zinc-based energy storage (ZES) devices are promising candidates for portable and grid-scale applications owing to their intrinsically high safety, low cost, and high theoretical energy density. However, the conventional aqueous electrolytes are not capable of working at low temperature. Here we report a frigostable, cost-effective, safe and eco-friendly hybrid electrolyte with high zinc-ion conductivity (6.9 mS cm −1 at −40 °C), and high reversibility of Zn plating/stripping, which consists of water, ethylene glycol (EG) and zinc sulfate salt (ZnSO 4 ). Experiments together with theoretical calculations demonstrated that the unique solvation interaction of Zn 2+ with EG can effectively enhance the hydrogen bonding between EG and H 2 O and weaken the solvation interaction of Zn 2+ with H 2 O, thus providing the hybrid electrolyte with a lower freezing point and reversible Zn/Zn 2+ chemistry. As a proof-of-concept, both Zn-ion hybrid supercapacitors (ZHSCs) and Zn-ion batteries (ZIBs) with the hybrid electrolytes delivered high energy densities (36 W h kg −1 for the ZHSC and 121 W h kg −1 for the ZIB), high power densities (3.1 kW kg −1 for the ZHSC and 1.7 kW kg −1 for the ZIB) and long-cycle life (5500 cycles over 110 days for the ZHSC and 250 cycles for the ZIB) at −20 °C. This work provides a new option for low-temperature energy storage devices.
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              Modulating electrolyte structure for ultralow temperature aqueous zinc batteries

              Rechargeable aqueous batteries are an up-and-coming system for potential large-scale energy storage due to their high safety and low cost. However, the freeze of aqueous electrolyte limits the low-temperature operation of such batteries. Here, we report the breakage of original hydrogen-bond network in ZnCl2 solution by modulating electrolyte structure, and thus suppressing the freeze of water and depressing the solid-liquid transition temperature of the aqueous electrolyte from 0 to –114 °C. This ZnCl2-based low-temperature electrolyte renders polyaniline||Zn batteries available to operate in an ultra-wide temperature range from –90 to +60 °C, which covers the earth surface temperature in record. Such polyaniline||Zn batteries are robust at –70 °C (84.9 mA h g−1) and stable during over 2000 cycles with ~100% capacity retention. This work significantly provides an effective strategy to propel low-temperature aqueous batteries via tuning the electrolyte structure and widens the application range of temperature adaptation of aqueous batteries.
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                Author and article information

                Contributors
                Journal
                Advanced Functional Materials
                Adv Funct Materials
                Wiley
                1616-301X
                1616-3028
                November 2023
                September 03 2023
                November 2023
                : 33
                : 47
                Affiliations
                [1 ] State Key Laboratory of Powder Metallurgy Central South University Changsha 410083 P. R. China
                [2 ] Hunan Provincial Key Laboratory of Chemical Power Sources College of Chemistry and Chemical Engineering Central South University Changsha 410083 P. R. China
                [3 ] Key Laboratory for Advanced Materials and Joint International Research Laboratory for Precision Chemistry and Molecular Engineering Feringa Nobel Prize Scientist Joint Research Center Centre for Computational Chemistry and Research Institute of Industrial Catalysis School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai 200237 P. R. China
                [4 ] State Key Laboratory of Fine Chemicals Department of Chemistry School of Chemical Engineering Dalian University of Technology Dalian 116024 P. R. China
                Article
                10.1002/adfm.202307390
                5f274654-8218-4141-9c64-68ca3157f68a
                © 2023

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