NH4+ ions as charge carriers show potential for aqueous rechargeable batteries. Studied here for the first time is the NH4+‐storage chemistry using electrodeposited manganese oxide (MnOx). MnOx experiences morphology and phase transformations during charge/discharge in dilute ammonium acetate (NH4Ac) electrolyte. The NH4Ac concentration plays an important role in NH4+ storage for MnOx. The transformed MnOx with a layered structure delivers a high specific capacity (176 mAh g−1) at a current density of 0.5 A g−1, and exhibits good cycling stability over 10 000 cycles in 0.5 M NH4Ac, outperforming the state‐of‐the‐art NH4+ hosting materials. Experimental results suggest a solid‐solution behavior associated with NH4+ migration in layered MnOx. Spectroscopy studies and theoretical calculations show that the reversible NH4+ insertion/deinsertion is accompanied by hydrogen‐bond formation/breaking between NH4+ and the MnOx layers. These findings provide a new prototype (i.e., layered MnOx) for NH4+‐based energy storage and contributes to the fundamental understanding of the NH4+‐storage mechanism for metal oxides.
VOPO4⋅x H2O has been proposed as a cathode for rechargeable aqueous zinc batteries. However, it undergoes significant voltage decay in conventional Zn(OTf)2 electrolyte. Investigations show the decomposition of VOPO4⋅x H2O into VOx in the electrolyte and voltage drops after losing the inductive effect from polyanions.PO43− was thus added to shift the decomposition equilibrium. A high concentration of cheap, highly soluble ZnCl2 salt in the electrolyte further prevents VOPO4⋅x H2O dissolution. The cathode shows stable capacity and voltage retentions in 13 m ZnCl2/0.8 m H3PO4 aqueous electrolyte, in direct contrast to that in Zn(OTf)2 where the decomposition product VOx provides most electrochemical activity over cycling. Sequential H+ and Zn2+ intercalations into the structure are revealed, delivering a high capacity (170 mAh g−1). This work shows the potential issue with polyanion cathodes in zinc batteries and proposes an effective solution using fundamental chemical principles.
Transition metal layered double hydroxides (LDHs) are widely used as high‐performance cathode materials for aqueous alkaline zinc (Zn) batteries. Yet, the strongly alkaline electrolytes may lead to undesirable rechargeability of the alkaline devices and environmental issues. Herein, as a research prototype, CoNi LDH material is designed with abundant H vacancies using electrochemical methods (denoted as CoNi LDH(v)). As a Zn‐ion battery cathode, CoNi LDH(v) exhibits promising electrochemical performances in mild ZnSO4 electrolyte, such as a good specific capacity of 185 mAh g−1 at the current density of 1.2 A g−1, a high average discharge potential of 1.6 V versus Zn2+/Zn, and a large energy density of 296.2 Wh kg−1 at the power density of 1894 W kg−1, outperforming most of the cathode materials for aqueous Zn‐ion batteries. Experimental and computational results indicate that the introduced H vacancies in the double hydroxide matrix induce the improved electronic conductivity and cation adsorption thermodynamics, endowing the double hydroxides with good electrochemical activity for reversible cation insertion. Structural and spectroscopy studies identify that CoNi LDH(v) experiences reversible H+/Zn2+ co‐intercalation mechanism in an aqueous ZnSO4 electrolyte. As far as it is known, it is the first report on transition‐metal‐based double hydroxides used for mild aqueous Zn‐ion batteries.
Ammonium (NH 4 + ) ion as charge carrier is attracting attention in aqueous batteries. Yet, most NH 4 + host materials are still limited by the relatively low capacities. Here, we fabricated a manganese phosphate (MP-20) for NH 4 + ion storage. MP-20 displays a high capacity of 299.6 mAh g À 1 at 1 A g À 1 in ammonium acetate (NH 4 Ac) electrolyte, outperforming other reported NH 4 + host materials. Spectroscopy studies suggest a new NH 4+ /H + co-insertion mechanism. We surprisingly discover that the NH 4 Ac electrolyte plays an important role in improving the charge storage capability of the materials. Experimental and computational results indicate acetate ions can form coordination bonds with the Mn atoms, tailoring the electronic structure of the Mn atoms and the surrounding O atoms, and therefore facilitating the NH 4 + storage process. Our findings provide a new NH 4+ host material and propose the important role of the electrolyte-electrode coordination effect in aqueous ammonium batteries.
Conducting polymers (CPs) have been widely studied for electrochemical energy storage. However, the dopants in CPs are often electrochemically inactive, introducing “dead‐weight” to the materials. Moreover, commercial‐level electrode materials with high mass loadings (e.g., >10 mg cm−2) often encounter the problems of inferior electrical and ionic conductivity. Here, a redox‐active poly‐counterion doping concept is proposed to improve the electrochemical performance of CPs with ultra‐high mass loadings. As a study prototype, heptamolybdate anion (Mo7O246−) doped polypyrrole (PPy) is synthesized by electro‐polymerization. A 2 mm thick PPy electrode with mass loading of ≈192 mg cm−2 reaches a record‐high areal capacitance of ≈47 F cm−2, competitive gravimetric capacitance of 235 F g−1, and volumetric capacitance of 235 F cm−3. With poly‐counterion doping, the dopants also undergo redox reactions during charge/discharge processes, providing additional capacitance to the electrode. The interaction between polymer chains and the poly‐counterions enhances the electrical conductivity of CPs. Besides, the poly‐counterions with large steric hindrance could act as structural pillars and endow CPs with open structures for facile ion transport. The concept proposed in this work enriches the electrochemistry of CPs and promotes their practical applications.
NH4+ ions as charge carriers show potential for aqueous rechargeable batteries. Studied here for the first time is the NH4+‐storage chemistry using electrodeposited manganese oxide (MnOx). MnOx experiences morphology and phase transformations during charge/discharge in dilute ammonium acetate (NH4Ac) electrolyte. The NH4Ac concentration plays an important role in NH4+ storage for MnOx. The transformed MnOx with a layered structure delivers a high specific capacity (176 mAh g−1) at a current density of 0.5 A g−1, and exhibits good cycling stability over 10 000 cycles in 0.5 M NH4Ac, outperforming the state‐of‐the‐art NH4+ hosting materials. Experimental results suggest a solid‐solution behavior associated with NH4+ migration in layered MnOx. Spectroscopy studies and theoretical calculations show that the reversible NH4+ insertion/deinsertion is accompanied by hydrogen‐bond formation/breaking between NH4+ and the MnOx layers. These findings provide a new prototype (i.e., layered MnOx) for NH4+‐based energy storage and contributes to the fundamental understanding of the NH4+‐storage mechanism for metal oxides.
MnO2 cathodes typically undergo one-electron transfer in aqueous zinc batteries. The two-electron MnO2/Mn2+ reaction provides double capacity and higher voltage. However, this requires a highly acidic environment, which challenges the Zn metal anode. Herein, we present a proton reservoir for the MnO2/Mn2+ reaction. Zinc hydrophosphate is codeposited with MnO2 at the cathode. The former deprotonates to release protons and enhances the reduction of MnO2 to Mn2+. The resulting zinc phosphate further interacts with MnO2 and realizes spontaneous water desorption from the MnO2 surface as revealed by theoretical calculations, which facilitates the dissolution process. The hydrophosphate species is reversibly generated upon charge. Based on this reaction mechanism, the cathode achieves a high discharge voltage of 1.75 V. It also delivers 0.99 mAh cm–2 capacity with 99% Coulombic efficiency. Stable capacity retention is realized for over 3000 cycles. This work demonstrates an effective strategy to access the two-electron process of MnO2 cathode materials in aqueous zinc batteries.
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