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Hierarchical Nickel-Cobalt Dichalcogenide Nanostructure as an Efficient Electrocatalyst for Oxygen Evolution Reaction and a Zn-Air Battery.

ABSTRACT: A unique three-dimensional (3D) structure consisting of a hierarchical nickel-cobalt dichalcogenide spinel nanostructure is investigated for its electrocatalytic properties at benign neutral and alkaline pH and applied as an air cathode for practical zinc-air batteries. The results show a high oxygen evolution reaction catalytic activity of nickel-cobalt sulfide nanosheet arrays grown on carbon cloth (NiCo₂S₄ NS/CC) over the commercial benchmarking catalyst under both pH conditions. In particular, the NiCo₂S₄ NS/CC air cathode shows high discharge capacity, a narrow potential gap between discharge and charge, and superior cycle durability with reversibility, which exceeds that of commercial precious metal-based electrodes. The excellent performance of NiCo₂S₄ NS/CC in water electrolyzers and zinc-air batteries is mainly due to highly exposed electroactive sites with a rough surface, morphology-based advantages of nanosheet arrays, good adhesion between NiCo₂S₄ and the conducting carbon cloth, and the active layer formed of nickel-cobalt (oxy)hydroxides during water splitting. These results suggest that NiCo₂S₄ NS/CC could be a promising candidate as an efficient electrode for high-performance water electrolyzers and rechargeable zinc-air batteries.

SUBMITTER: Hyun S

PROVIDER: S-EPMC6644433 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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Hierarchical Nickel-Cobalt Dichalcogenide Nanostructure as an Efficient Electrocatalyst for Oxygen Evolution Reaction and a Zn-Air Battery.

Hyun Suyeon S Shanmugam Sangaraju S

ACS omega 20180802 8

A unique three-dimensional (3D) structure consisting of a hierarchical nickel-cobalt dichalcogenide spinel nanostructure is investigated for its electrocatalytic properties at benign neutral and alkaline pH and applied as an air cathode for practical zinc-air batteries. The results show a high oxygen evolution reaction catalytic activity of nickel-cobalt sulfide nanosheet arrays grown on carbon cloth (NiCo<sub>2</sub>S<sub>4</sub> NS/CC) over the commercial benchmarking catalyst under both pH co ...[more]

PMID: 31458992

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Project description:The quest for developing next-generation non-precious electrocatalysts has risen in recent times. Herein, we have designed and developed a low cost electrocatalyst by a ligand-assisted synthetic strategy in an aqueous medium. An oxalate ligand-assisted non-oxide electrocatalyst was developed by a simple wet-chemical technique for alkaline water oxidation application. The synthetic parameters for the preparation of nickel-cobalt oxalate (Ni2.5Co5C2O4) were optimized, such as the metal precursor (Ni/Co) ratio, oxalic acid amount, reaction temperature, and time. Microstructural analysis revealed a mesoporous block-like architecture for nickel-cobalt oxalate (Ni2.5Co5C2O4). The required overpotential of Ni2.5Co5C2O4 for the alkaline oxygen evolution reaction (OER) was found to be 330 mV for achieving 10 mA cmgeo -2, which is superior to that of NiC2O4, CoC2O4, NiCo2O4 and the state-of-the-art RuO2. The splendid performance of Ni2.5Co5C2O4 was further verified by its low charge transfer resistance, impressive stability performance, and 87% faradaic efficiency in alkaline medium (pH = 14). The improved electrochemical activity was further attributed to double layer capacitance (C dl), which indefinitely divulged the inferiority of NiCo2O4 compared to Ni2.5Co5C2O4 for the alkaline oxygen evolution reaction (OER). The obtained proton reaction order (ρ RHE) was about 0.80, thus indicating the proton decoupled electron transfer (PDET) mechanism for OER in alkaline medium. Post-catalytic investigation revealed the formation of a flake-like porous nanostructure, indicating distinct transformation in morphology during the alkaline OER process. Further, XPS analysis demonstrated complete oxidation of Ni2+ and Co2+ centres into Ni3+ and Co3+, respectively under high oxidation potential, thereby indicating active site formation throughout the microstructural network. Additionally, from BET-normalised LSV investigation, the intrinsic activity of Ni2.5Co5C2O4 was also found to be higher than that of NiCo2O4. Finally, Ni2.5Co5C2O4 delivered a TOF value of around 3.28 × 10-3 s-1, which is 5.56 fold that of NiCo2O4 for the alkaline OER process. This report highlights the unique benefit of Ni2.5Co5C2O4 over NiCo2O4 for the alkaline OER. The structure-catalytic property relationship was further elucidated using density functional theory (DFT) study. To the best of our knowledge, nickel-cobalt oxalate (Ni2.5Co5C2O4) was introduced for the first time as a non-precious non-oxide electrocatalyst for alkaline OER application.

Dataset Information

Hierarchical Nickel-Cobalt Dichalcogenide Nanostructure as an Efficient Electrocatalyst for Oxygen Evolution Reaction and a Zn-Air Battery.

Publications

Hierarchical Nickel-Cobalt Dichalcogenide Nanostructure as an Efficient Electrocatalyst for Oxygen Evolution Reaction and a Zn-Air Battery.

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