Rechargeable aqueous zinc ion hybrid capacitors (ZIHCs), as an up-and-comer aqueous electrochemical energy storage system, endure in their infancy because of the substandard reversibility of Zn anodes, structural deterioration of cathode materials, and narrow electrochemical stability window. Herein, a scalable approach is described that addresses Zn-anode/electrolyte interface and cathode materials associated deficiencies and boosts the electrochemical properties of ZIHCs. The Zn-anode/electrolyte interface is self-regulated by alteration of the traditional Zn 2+ electrolyte with Na-based supporting salt without surrendering the cost, safety, and green features of the Zn-based system which further validates the excellent reversibility over 1100 h with suppressed hydrogen evolution. The deficits of cathode materials were overcome by using a high-mass loaded, oxygen-rich, 3D, multiscaled graphene-like carbon (3D MGC) cathode. Due to the multiscaled texture, high electronic conductivity, and oxygen-rich functional groups of 3D MGC, reversible redox capacitance was obtained with a traditional adsorption/desorption mechanism. Prototype ZIHCs containing the modified electrolyte and an oxygen-rich 3D MGC cathode resulted in battery-like specific energy (203 Wh kg À1 at 1.6 A g À1 ) and supercapacitor-type power capability (4.9 kW kg À1 at 8 A g À1 ) with outstanding cycling durability (96.75% retention over 30 000 cycles at 10 A g À1 ).

Rechargeable aqueous zinc ion hybrid capacitors were developed in this work via engineering a Zn‐anode/electrolyte interface and 3D Graphene‐like Carbon Cathode. The designed hybrid device realizes the battery‐like specific energy (203 Wh kg–1) and supercapacitor‐type power capability (4.9 kW kg–1) and cycling stability (96.75% retention over 30000 cycles) at a much lower price than the commercial supercapacitors and Li‐ion batteries. This work (DOI: 10.1002/inf2.12344) provides a scalable yet cost‐effective approach for developing a next‐generation Zn‐ion‐based energy storage system. image

Summary Ni‐rich LiNixCoyMnzO2 (NCM) cathode material has received a lot of attention as an advanced cathode material for lithium‐ion batteries (LIBs). However, increasing internal resistance triggered by continuous electrolyte decomposition has become an important issue, as it seriously decreases the cycling retention of cells. Herein, this study will describe the means of a functional additive to improve the interfacial stability of Ni‐rich NCM cathode materials, 1,2‐propyleneglycol sulfite (PGS), which has a –SO3– functional group. The PGS can create layers of artificial cathode‐electrolyte interphase (CEI) through electrochemical oxidation reactions, which inhibit electrolyte decomposition in the cell. The cells without the PGS additive suffered seriously from low‐cycling retention (57.1%) after 100 cycles, but their cycling performance increased to 76.9% for the cell with 2.0 wt% PGS. Electrolyte decomposition is subsequently suppressed considerably in cells, indicating that artificial CEI layers incorporated by the electrochemical reaction of PGS improve the interfacial stability. First‐principle calculations reveal that PGS exhibited a higher oxidation preference and stronger Ni2+ affinity compared with solvents, and inhibited the formation of detrimental F−‐like species.

Propylene carbonate- (PC-) based electrolytes are gaining attention as electrolytes in next-generation batteries because of their high stability and excellent temperature characteristics at high voltages. Lithium-ion batteries using PC-based electrolytes with 3-methyl-1,4,2-dioxazol-5-one (MDO) showed excellent capacity retention and lifetime characteristics. Here, quantum chemical methods are used to examine the molecular characteristics of MDO, and they suggest the unique molecular properties of this additive. Our calculations reveal that MDO is reduced prior to ethylene carbonate (EC) and PC solvents and undergoes a remarkably fast reduction decomposition process while producing thermodynamically stable reduction reaction products compared to vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives. This implies that a thermodynamically stable solid-electrolyte interphase (SEI) can form on the anode surface through a very rapid reaction. Upon reduction, the most preferred thermodynamic reaction between MDO and PC forms Li2CO3, a major SEI component. These reaction characteristics are unique and not observed with VC or FEC. The binding energy with Li+ is lower for MDO than for VC, FEC, or the solvents, making MDO the best choice for desolvation. We demonstrate that the molecular characteristics derived from quantum chemical calculations for MDO can also be applied to various previously reported PC-based electrolyte additives.