Rechargeable Aqueous Zinc-Ion Batteries in MgSO4/ZnSO4 Hybrid Electrolytes.
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ABSTRACT:
SUBMITTER: Zhang Y
PROVIDER: S-EPMC7770650 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Rechargeable aqueous zinc ion batteries (ZIBs) are considered as one of the most promising systems for large-scale energy storage due to their merits of low cost, environmental friendliness, and high safety. The utilization of aqueous electrolyte also brings about some problems such as low energy density, fast self-discharge, and capacity fading associated with the dissolution of metals in water. To combat the issues, we utilize a freestanding vanadium oxide hydrate/carbon nanotube (V2O5·nH2O/CNT) film as the cathode and probe the performance in aqueous/organic hybrid electrolytes. The corresponding structural and morphological evolution of both V2O5·nH2O/CNT cathode and Zn anode in different electrolytes is explored. The integrity of electrodes and the suppression of zinc dendrites during cycles are largely improved in the hybrid electrolytes. Accordingly, the battery in hybrid electrolyte exhibits high capacities of 549?mAh?g-1 at 0.5?A?g-1 after 100 cycles and 282?mAh?g-1 at 4?A?g-1 after 1000 cycles, demonstrating an excellent energy density of 102?Wh?kg-1 at a high power of 1500?W?kg-1 based on the cathode.
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Project description:Aqueous zinc-ion batteries (AZIBs) are promising candidates for large-scale electrical energy storage due to the inexpensive, safe, and non-toxic nature of zinc. One key area that requires further development is electrode materials that store Zn2+ ions with high reversibility and fast kinetics. To determine the viability of low-cost organosulfur compounds as OEMs for AZIBs, we investigate how structural modification affects electrochemical performance in Zn-thiolate complexes 1 and 2. Remarkably, modification of one thiolate in 1 to sulfide in 2 reduces the voltage hysteresis from 1.04 V to 0.15 V. While 1 exhibits negligible specific capacity due to the formation of insulating DMcT polymers, 2 delivers a capacity of 107 mA h g-1 with a primary discharge plateau at 1.1 V vs. Zn2+/Zn. Spectroscopic studies of 2 suggest a Zn2+ and H+ co-insertion mechanism with Zn2+ as the predominant charge carrier. Capacity fading in Zn-2 cells likely results from the formation of (i) soluble H+ insertion products and (ii) non-redox-active side products. Increasing electrolyte concentration and using a Nafion membrane significantly enhances the stability of 2 by suppressing H+ insertion. Our findings provide insight into the molecular design strategies to reduce the polarization potential and improve the cycling stability of the thiolate/disulfide redox couple in aqueous battery systems.
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Project description:This study reports the phase transformation behaviour associated with electrolytic manganese dioxide (EMD) utilized as the positive electrode active material for aqueous zinc-ion batteries. Electrochemical techniques, including galvanostatic charge-discharge and rotating ring-disk electrode measurements, and microstructural techniques, using X-ray powder diffraction, scanning electron microscopy, and transmission/scanning transmission electron microscopy, were utilized to characterize the positive electrode at different stages of discharge and charge of zinc-ion cells. The results indicate that, during discharge, a fraction of EMD undergoes a transformation to ZnMn2O4 (spinel-type) and Zn2+ is intercalated into the tunnels of the γ- and ε-MnO2 phases, forming ZnxMnO2 (tunnel-type). When a critical concentration of Mn3+ in the intercalated ZnxMnO2 species is reached, a disproportionation/dissolution reaction is triggered leading to the formation of soluble Mn2+ and hydroxide (OH-) ions; the latter precipitates as zinc hydroxide sulfate (ZHS, Zn4(OH)6(SO4)·5H2O) by combination with the ZnSO4/H2O electrolyte. During charge, Zn2+ is reversibly deintercalated from the intergrown tunneled phases (γ-/ε-ZnxMnO2), Mn2+ is redeposited as layered chalcophanite (ZnMn3O7·3H2O), and ZHS is decomposed by protons (H+) formed during the electrochemical deposition of chalcophanite.
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Project description:Manganese (Mn)-based cathode materials have garnered huge research interest for rechargeable aqueous zinc-ion batteries (AZIBs) due to the abundance and low cost of manganese and the plentiful advantages of manganese oxides including their different structures, wide range of phases, and various stoichiometries. A novel in situ generated Mn-deficient ZnMn2O4@C (Mn-d-ZMO@C) nanoarchitecture cathode material from self-assembly of ZnO-MnO@C for rechargeable AZIBs is reported. Analytical techniques confirm the porous and crystalline structure of ZnO-MnO@C and the in situ growth of Mn deficient ZnMn2O4@C. The Zn/Mn-d-ZMO@C cell displays a promising capacity of 194 mAh g-1 at a current density of 100 mA g-1 with 84% of capacity retained after 2000 cycles (at 3000 mA g-1 rate). The improved performance of this cathode originates from in situ orientation, porosity, and carbon coating. Additionally, first-principles calculations confirm the high electronic conductivity of Mn-d-ZMO@C cathode. Importantly, a good capacity retention (86%) is obtained with a year-old cell (after 150 cycles) at 100 mA g-1 current density. This study, therefore, indicates that the in situ grown Mn-d-ZMO@C nanoarchitecture cathode is a promising material to prepare a durable AZIB.
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