Interspace and Vacancy Modulation: Promoting the Zinc Storage of an Alcohol‐Based Organic–Inorganic Cathode in a Water–Organic Electrolyte

Abstract

Expanding interspace and introducing vacancies are desired to promote the mobility of Zn ions and unlock the inactive sites of layered cathodes. However, this two‐point modulation has not yet been achieved simultaneously in vanadium phosphate. Here, a strategy is proposed for fabricating an alcohol‐based organic–inorganic hybrid material, VO1−xPO4·0.56C6H14O4, to realize the conjoint modulation of the d‐interspace and oxygen vacancies. Peculiar triglycol molecules with an inclined orientation in the interlayer also boost the improvement in the conversion rate of V5+ to V4+ and the intensity of the PO bond. Their synergism can ensure steerable adjustment for intercalation kinetics and electron transport, as well as realize high chemical reactivity and redox‐center optimization, leading to at least 200% increase in capacity. Using a water–organic electrolyte, the designed Zn‐ion batteries with an ultrahigh‐rate profile deliver a long‐term durability (fivefold greater than pristine material) and an excellent energy density of ≈142 Wh kg−1 (including masses of cathode and anode), thereby substantially outstripping most of the recently reported state‐of‐the‐art zinc‐ion batteries. This work proves the feasibility to realize the two‐point modulation by using organic intercalants for exploiting high‐performance new 2D materials.

2D VOPO4 Pseudocapacitive Ultrafast‐Charging Cathode with Multi‐Electron Chemistry for High‐Energy and High‐Power Solid‐State Lithium Metal Batteries

“…[ 17 ] It is observed that VOPO 4 @G‐Air exhibits a higher resonance amplitude than that of VOPO 4 @G‐O 2 (Figure 1i), indicating a higher concentration of V 4+ in VOPO 4 @G‐Air. [ 28 ]…”

Polycation‐Regulated Electrolyte and Interfacial Electric Fields for Stable Zinc Metal Batteries

“…Dramatic progress has been accomplished in the pursuit of high performance cathode materials such as transition metal (manganese, vanadium) oxide, organic molecule, and so on. [1][2][3][4][5] Nevertheless, unbounded dendrite growth, corrosion and passivation of zinc (Zn) metal anodes, resulting in low coulombic efficiency (CE) and limited lifetime, which may lead to battery short circuit, is one of the most crucial obstacles for the development of aqueous ZIBs. [6][7][8][9][10][11][12] Several strategies have been executed to enhance the electrochemical stability of Zn metal anodes by inhibiting the dendrite formation and banishing the water-induced parasitic reaction, including electrolyte regulation, interfacial manipulation, substrate modification, etc.…”

“…Aqueous rechargeable zinc‐ion batteries (ZIBs) are regarded as one of the most competitive candidates for large‐scale energy storage due to their high safety, low cost and environmental friendliness, and have become a research hotspot in recent years. Dramatic progress has been accomplished in the pursuit of high performance cathode materials such as transition metal (manganese, vanadium) oxide, organic molecule, and so on [1–5] . Nevertheless, unbounded dendrite growth, corrosion and passivation of zinc (Zn) metal anodes, resulting in low coulombic efficiency (CE) and limited lifetime, which may lead to battery short circuit, is one of the most crucial obstacles for the development of aqueous ZIBs [6–12] .…”

N-Methylpyrrolidone assisted tetrachlorobenzoquinone intercalating V2O5as cathode for aqueous zinc-ion battery

“…3–6 Therefore, the modification of inorganic intercalation (mostly using metal ions such as Li + , Na + , K + , and Al 3+ , and NH 4 + ) has been adopted to address this problem, producing numerous intercalated vanadium oxides such as Li x V 2 O 5 · n H 2 O, 7 Na x V 2 O 5 · n H 2 O, 8 K 0.5 V 2 O 5 ·0.76H 2 O, 9 Al–V 2 O 5 , 10,11 NVO 12 etc. On the other hand, organics are also frequently used for intercalation, including polyaniline, 13 polypyrrole, 14 and various small molecules (ethylenediamine, 15 triethylene glycol, 16 dodecyl amine, 17 etc. ).…”

“…to address this problem, producing numerous intercalated vanadium oxides such as Li 9 Al-V 2 O 5 , 10,11 NVO 12 etc. On the other hand, organics are also frequently used for intercalation, including polyaniline, 13 polypyrrole, 14 and various small molecules (ethylenediamine, 15 triethylene glycol, 16 dodecyl amine, 17 etc.). However, these attempts have tried to regulate the zinc ion transport by changing the layer spacing, which has no benefit for capacity enhancement.…”