Atomic-level coupled spinel@perovskite dual-phase oxides toward enhanced performance in Zn–air batteries

Ran, Jiaqi; Wu, Jianfeng; Hu, Yongfeng; Shakouri, Mohsen; Xia, Baorui; Gao, Daqiang

doi:10.1039/d1ta09457b

Cited by 32 publications

(19 citation statements)

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“…The oxygen electrode properties were tested by the difference between OER and ORR (Δ E = E j10 − E 1/2 ). [ 50 ] In Figure 4h, the overpotential △ E of the F 0.2 ‐LCO catalyst is 0.96 V, exceeding most reported transition metal‐based bifunctional oxygen catalysts (Table S2, Supporting Information). Stability is another important factor in determining oxygen electrocatalytic performance.…”

Section: Resultsmentioning

confidence: 80%

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis

Ran

Wang

et al. 2022

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Promoting the initially deficient but economical catalysts to high‐performing competitors is important for developing superior catalysts. Unlike traditional nano‐morphology construction methods, this work focuses on intrinsic catalytic activity enhancement via heteroatom doping strategies to induce lattice distortion and optimize spin‐dependent orbital interaction to alter charge transfer between catalysts and reactants. Experimentally, a series of different concentrations of fluorine‐doped lanthanum cobaltate (Fx‐LaCoO3) exhibiting excellent electrocatalytic activity is synthesized, including a low overpotential of 390 mV at j = 10 mA cm−2 for OER and a large half‐wave potential of 0.68 V for ORR. Meanwhile, the assembled rechargeable Zn–air batteries deliver an excellent performance with a large specific capacity of 811 mAh/gZn under 10 mA cm−2 and stability of charge/recharge (120 h). Theoretically, taking advantage of density functional theory calculations, it is found that the prominent OER/ORR performance arises from the spin state transition of Co3+ (Low spin state (LS, t2g6eg0) → Intermediate spin state (IS, t2g5eg1) and the mediated d‐band center upshift by F atom incorporation. This work establishes a novel avenue for designing superior electrocatalysts in perovskite‐based oxides by regulating spin states.

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Section: Resultsmentioning

confidence: 80%

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis

Ran

Wang

et al. 2022

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“…Until now, much research efforts have been devoted toward the preparation of biphasic spinel-perovskite structures to understand the operating conditions relevant to energy efficiency. 16,18 Regretfully, there is no research report on the electrochemical behavior of the Li−Mn−Fe−Si dual-phase oxides in energy storage devices.…”

Section: Introductionmentioning

confidence: 99%

“…In recent years, mixed-metal oxide engineering of diphase structures has received extensive attention owing to its new opportunities in advanced electronic devices. , To resolve the capacitance and conductivity limitations, combining perovskite-type oxides with other materials including noble metals, spinel oxides, and carbonaceous coatings has been proposed. Among them, spinel-structured materials have aroused considerable interest owing to their rich redox reaction, plentiful supplement, low cost, and steady specific capacitance .…”

Section: Introductionmentioning

confidence: 99%

“…These systems can simultaneously offer fantastic characteristics such as magnetoelectric, piezoelectricity, and superconductivity effects in memory devices, capacitors, and energy storage systems. , Specifically, the synergistic effect between the spinel and perovskite structures will enable well-defined transport kinetics during the charge/discharge processes via three pioneering strategies: (i) Employing multiple redox-active moieties and ordered active sites, (ii) interface engineered nanoarray structures with porous networks, and (iii) considering the nature of the rich mixed-valences of metals in nanocomposites, endowing them with the formation of vacancy- and misplaced-ion defects, and the dramatic enhancement in the electrocatalytic performances. − Consequently, the choice of the appropriate method with the side benefits has become an essential step for precious dual-phase oxides. Until now, much research efforts have been devoted toward the preparation of biphasic spinel-perovskite structures to understand the operating conditions relevant to energy efficiency. , Regretfully, there is no research report on the electrochemical behavior of the Li–Mn–Fe–Si dual-phase oxides in energy storage devices.…”

Section: Introductionmentioning

confidence: 99%

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Hydrothermal Synthesis of Spinel-Perovskite Li–Mn–Fe–Si Nanocomposites for Electrochemical Hydrogen Storage

2022

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Owing to the extensive requirement for renewable energy sources such as hydrogen, great efforts are being devoted to optimizing the active ingredients for advanced hydrogen storage. In this regard, an ideal spinel-perovskite nanocomposite based on Li−Mn−Fe−Si materials was successfully fabricated via a one-pot hydrothermal route to store hydrogen electrochemically. To optimize both the phase composition and morphological features of nanostructures, the reaction was engineered under different conditions. Li−Mn−Fe−Si spinel-perovskite diphase structures were created with diverse shapes of polyhedral-shaped bulk particles, nanoparticles, nanoplates, and hierarchical structures. The alteration of multiple factors such as hydrothermal reaction time, temperature, polymeric surfactant type, and calcination temperature was surveyed to achieve the optimized size and morphology of the nanoproducts to be obtained. The morphological changes, structural regulations, porosity, and magnetic properties of the nanosized products were studied via field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray powder diffraction (XRD), Raman spectroscopy, Brunauer−Emmett−Teller (BET), and vibrating sample magnetometer (VSM) analyses. In addition, the electrochemistry features of the Li 0.66 Mn 1.85 Fe 0.43 O 4 /Fe 2.57 Si 0.43 O 4 /FeSiO 3 (LMFO/FSO) nanocomposites were introduced on the basis of discharge capacity, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry(CV) methods in an alkaline electrolyte. The discharge capacity of the LMFO/FSO nanostructures with a nanoplate-like morphology as an optimal sample was calculated to be 910 mAh/g after 15 cycles at a constant current of 1 mA. The electrochemistry results confirm that the hydrogen storage capability of nanoplate composites is higher than those of other morphologies due to their superior surface area and faster electron transfer. Besides, this proposed strategy could simultaneously manipulate the architectural and compositional complexities to generate a superior electrochemical behavior in energy storage devices.

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“…As observed in Figure1i, the spectrum for high-resolution Co 2p in Co 3 O 4 /CC is segmented to four obvious peaks at 797.5, 795.9, 782.4, and 780.8 eV, which belonged to Co 2+ 2p 1/2 , Co 3+ 2p 1/2 , Co 2+ 2p 3/2 , and Co 3+ 2p 3/2 , respectively 49. Binding energies located at 786.7, 790.5, and 805.3 eV are assigned to satellite peaks 50. As compared to Co 3 O 4 /CC, Al-Co 3 O 4 /CC has similar fitting peaks (Figure…”

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confidence: 99%

High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co₃O₄ Nanoarray Catalyst with Cobalt Vacancies

Deng

et al. 2022

ACS Appl. Mater. Interfaces

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Electrocatalytic nitrate reduction reaction (NO 3 RR) affords a bifunctional character in the carbon-free ammonia synthesis and remission of nitrate pollution in water. Here, we fabricated the Co 3 O 4 nanosheet array with cobalt vacancies on carbon cloth (v Co -Co 3 O 4 /CC) by in situ etching aluminum-doped Co 3 O 4 /CC, which exhibits an excellent Faradaic efficiency of 97.2% and a large NH 3 yield as high as 517.5 μmol h −1 cm −2 , better than the pristine Co 3 O 4 /CC. Theoretical calculative results imply that the cobalt vacancies can tune the local electronic environment around Co sites of Co 3 O 4 , increasing the charge and reducing the electron cloud density of Co sites, which is thus conducive to adsorption of NO 3 − on Co sites for greatly enhanced nitrate reduction. Furthermore, the v Co -Co 3 O 4 (311) facet presents excellent NO 3 RR activity with a low energy barrier of about 0.63 eV on a potentialdetermining step, which is much smaller than pristine Co 3 O 4 (1.3 eV).

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Atomic-level coupled spinel@perovskite dual-phase oxides toward enhanced performance in Zn–air batteries

Abstract: Interface engineering has been proved to be an efficient strategy for boosting electrocatalytic performance and has attracted increasing interest in past few decades. Herein, Co3O4@LaCoO3 heterojunctions with abundant oxygen vacancies,...

Cited by 32 publications

References 55 publications

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis

Hydrothermal Synthesis of Spinel-Perovskite Li–Mn–Fe–Si Nanocomposites for Electrochemical Hydrogen Storage

High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co₃O₄ Nanoarray Catalyst with Cobalt Vacancies

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Atomic-level coupled spinel@perovskite dual-phase oxides toward enhanced performance in Zn–air batteries

Abstract: Interface engineering has been proved to be an efficient strategy for boosting electrocatalytic performance and has attracted increasing interest in past few decades. Herein, Co3O4@LaCoO3 heterojunctions with abundant oxygen vacancies,...

Cited by 32 publications

References 55 publications

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis

Tailoring Spin State of Perovskite Oxides by Fluorine Atom Doping for Efficient Oxygen Electrocatalysis

Hydrothermal Synthesis of Spinel-Perovskite Li–Mn–Fe–Si Nanocomposites for Electrochemical Hydrogen Storage

High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co3O4 Nanoarray Catalyst with Cobalt Vacancies

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High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co₃O₄ Nanoarray Catalyst with Cobalt Vacancies