High-performance Bifunctional Electrocatalysts Research Articles

Co-CoSe heterogeneous fibers with strong interfacial built-in electric field as bifunctional electrocatalyst for high-performance Zn-air battery

The explorations of efficient electrocatalysts to accelerate oxygen reactions in a wide temperature range is a crucial issue to the development of zinc-air batteries (ZAB) for all-climate applications. Herein, the Co-CoSe heterogeneous furry fibers (Co-CoSe@NHF) are developed as a bifunctional oxygen electrocatalyst for ZAB towards wide-temperature range applications. The Co-CoSe heterostructure with large work function difference (ΔWF) endows interfacial electron redistribution, which builds strong interfacial built-in electric field (BIEF) and improves the oxygen reactions. Meanwhile, the Co-CoSe heterostructure is encapsulated by in-situ grown carbon nanotubes, and forms the hollow fiber (NHF) with furry surface and beads-on-string configuration. The highly porous and conductive NHF configuration facilitates the fast kinetics and favors to accommodates volume change during cycling. As a result, the Co-CoSe@NHF achieves the superior bifunctional properties and good reliability for oxygen reactions. Integrated with the Co-CoSe@NHF fiber, the ZAB cell delivers the superior power density (301 mW cm−2) and long-term cycling stability over 280 h at 25 °C, and maintains the power densities of 126 mW cm−2 even the temperature decreases to −25 °C. Moreover, the solid-state ZAB exhibits significant flexibility and superior properties in a wide temperature range. Therefore, this work not only proposes a new strategy to design the high-performance bifunctional electrocatalysts, but also propels the development of flexible power sources for all-climate applications.

Effective Non-Precious Metal Oxide Supported Carbon as a High Performance Bifunctional Electrocatalyst for All Vanadium Redox Flow Batteries

As one of the most promising electrochemical energy storage systems, vanadium redox flow batteries (VRFBs) have received increasing attention owing to their attractive features for large-scale storage applications. However, their high production cost and relatively low energy efficiency still limit their feasibility. One of the critical components of VRFBs that can significantly influence the effectiveness and final cost is the electrode. Therefore, the development of an ideal electrocatalyst with low cost, large active surface area, good chemical stability, and excellent electrochemical activity toward the VO2+/VO2 + and V2+/V3+ redox reactions is essential for the design of VRFBs. Hence, we prepared a stable, high catalytic activity and uniformly distributed non-precious metal oxide nanoparticles on the surface graphene sheets via two step routes, hydrothermal followed by annealing at optimum temperature for VRFB applications. Among the samples, the prepared electrocatalyst shows the best electrochemical activity with lowest peak potential separation and highest peak current density toward VO2 +/VO2+ and V2+/V3+ redox reactions. This observation is due to the synergistic effects related to the presence of excess oxygen vacancies on the metal oxide, the high content of oxygen functional groups, and the high electrical conductivity of the graphene sheets. Hence, the prepared electrocatalyst grown on the surface of graphite felt (GF) support demonstrates the optimal electrochemical activity with the energy and voltage efficiencies of 76.8% and 80.9%, respectively, which are much greater than those of the 59.8% and 63.2% attained from pristine GF at 100 mA cm–2. Moreover, the electrode presented good stability and durability in acidic electrolyte during long-term operations for 100 cycles at a higher current density of 100 mA cm–2.

Rapid Synthesis of Ruthenium-Copper Nanocomposites as High-Performance Bifunctional Electrocatalysts for Electrochemical Water Splitting.

Development of high-performance, low-cost catalysts for electrochemical water splitting is key to sustainable hydrogen production. Herein, ultrafast synthesis of carbon-supported ruthenium-copper (RuCu/C) nanocomposites is reported by magnetic induction heating, where the rapid Joule's heating of RuCl3 and CuCl2 at 200A for 10s produces Ru-Cl residues-decorated Ru nanocrystals dispersed on a CuClx scaffold, featuring effective Ru to Cu charge transfer. Among the series, the RuCu/C-3 sample exhibits the best activity in 1m KOH toward both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with an overpotential of only -23 and +270mV to reach 10mAcm-2, respectively. When RuCu/C-3 is used as bifunctional catalysts for electrochemical water splitting, a low cell voltage of 1.53V is needed to produce 10mAcm-2, markedly better than that with a mixture of commercial Pt/C+RuO2 (1.59V). In situ X-ray absorption spectroscopy measurements show that the bifunctional activity is due to reduction of the Ru-Cl residues at low electrode potentials that enriches metallic Ru and oxidation at high electrode potentials that facilitates the formation of amorphous RuOx. These findings highlight the unique potential of MIH in the ultrafast synthesis of high-performance catalysts for electrochemical water splitting.

Nitrogen-Tungsten Oxide Nanostructures on Nickel Foam as High Efficient Electrocatalysts for Benzyl Alcohol Oxidation.

Electrocatalytic alcohol oxidation (EAO) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts is a major challenge. Herein, we developed a nitrogen-doped bimetallic oxide electrocatalyst (WO-N/NF) by a one-step hydrothermal method for the selective electrooxidation of benzyl alcohol to benzoic acid in alkaline electrolytes. The WO-N/NF electrode features block-shaped particles on a rough, inhomogeneous surface with cracks and lumpy nodules, increasing active sites and enhancing electrolyte diffusion. The electrode demonstrates exceptional activity, stability, and selectivity, achieving efficient benzoic acid production while reducing the electrolysis voltage. A low onset potential of 1.38 V (vs. RHE) is achieved to reach a current density of 100 mA cm-2 in 1.0 M KOH electrolyte with only 0.2 mmol of metal precursors, which is 396 mV lower than that of water oxidation. The analysis reveals a yield, conversion, and selectivity of 98.41%, 99.66%, and 99.74%, respectively, with a Faradaic efficiency of 98.77%. This work provides insight into the rational design of a highly active and selective catalyst for electrocatalytic alcohol oxidation.

High-Performance Bifunctional Electrocatalysts for Flexible and Rechargeable Zn-Air Batteries: Recent Advances.

Flexible rechargeable Zn-air batteries (FZABs) exhibit high energy density, ultra-thin, lightweight, green, and safe features, and are considered as one of the ideal power sources for flexible wearable electronics. However, the slow and high overpotential oxygen reaction at the air cathode has become one of the key factors restricting the development of FZABs. The improvement of activity and stability of bifunctional catalysts has become a top priority. At the same time, FZABs should maintain the battery performance under different bending and twisting conditions, and the design of the overall structure of FZABs is also important. Based on the understanding of the three typical configurations and working principles of FZABs, this work highlights two common strategies for applying bifunctional catalysts to FZABs: 1) powder-based flexible air cathode and 2) flexible self-supported air cathode. It summarizes the recent advances in bifunctional oxygen electrocatalysts and explores the various types of catalyst structures as well as the related mechanistic understanding. Based on the latest catalyst research advances, this paper introduces and discusses various structure modulation strategies and expects to guide the synthesis and preparation of efficient bifunctional catalysts. Finally, the current status and challenges of bifunctional catalyst research in FZABs are summarized.

Built-in electric field and core-shell structure of the reconstructed sulfide heterojunction accelerated water splitting

The rational design of high-performance bifunctional electrocatalysts for overall water splitting (OWS) is the key to popularize hydrogen production technology. The active metal oxyhydroxide (MOOH) formed after surface self-reconfiguration of transition metal sulfide (TMS) electrocatalyst is often regarded as the "actual catalyst" in oxygen evolution reaction (OER). Herein, an Fe doped CoS2/MoS2 hollow TMS polyhedron (Fe-CoS2/MoS2) with rich Mott-Schottky heterojunction is reported and directly utilized as an OWS electrocatalyst. The spontaneous built-in electric field (BEF) at the heterogeneous interface regulates the electronic structure and D-band center of the catalyst. More importantly, the “TMS-MOOH” core-shell structure obtained in the KOH electrolyte shows enhanced OER properties. And the introduction of Fe ions activates the inert basal plane of MoS2, which greatly steps up the performance of HER. Hence, the preferable Fe-CoS2/MoS2–400 presents superior OER activity (η10 = 178 mV, η100 = 375 mV), HER activity (η10 = 92 mV) and ultra-high stability for 50 h. This work has deeply explored the catalytic mechanism of TMS and provided a new idea for the construction of efficient bifunctional catalysts.

Electron and surface engineering of Ni2P/MnP4 heterojunction as high performance bifunctional electrocatalyst for amperage-level overall water splitting

Producing hydrogen through electrocatalytic overall water splitting with ampere-level current density is still limited by the high cost and poor stability of electrocatalysts. In this work, a new type Ni2P/MnP4 heterojunction composite material was designed and prepared as bifunctional electrocatalyst. Based on XPS spectra and theoretical calculation, the formation of Ni2P/MnP4 heterojunction successfully modulates the local electronic structure of Ni2P and enhances the ionization of H and Ni by increasing the electron transfer rate. Moreover, the special nanovilli structure and superhydropholic/superaerophobic surface of Ni2P/MnP4 heterojunction accelerates the transfer of electrolyte and gaseous products. Benefiting from these advantages, the as-prepared Ni2P/MnP4/CF not only exhibits superior electrocatalytic performance, which can release 10 mA/cm2 current density with a low overpotential of 69 mV and 247 mV for HER and OER respectively, but also shows admirable stability of continuous overall water splitting to drive 1000 mA/cm2 for 180 h without notable activity degradation. We believe this material possesses outstanding potential for industrial applications, and our strategy may provide a new pathway to design relative materials.

Rapid heating synthesis of ultrafine PtCo nanoparticles anchored on carbon nanofibers as high-performance bifunctional oxygen electrocatalysts for zinc-air batteries

Herein, rapid heating strategy was introduced to synthesize ultrafine PtCo nanoparticles attached to carbon nanofibers (CNFs) by a high heating rate (HHR) up to about 50 °C s−1. This novel tactic is beneficial to the formation and the homogeneous distribution of ultrathin PtCo nanoparticles on CNFs. The acquired PtCo/CNFs-HHR exhibits a half-wave potential of 0.88 V for ORR, along with a low potential difference ΔE of 0.79 V. When used as the cathode catalyst of ZABs, PtCo/CNFs-HHR displays a high open circuit voltage of 1.454 V, large peak power density of 138.6 mW cm−2, and excellent charge–discharge cycle stability over 300 cycles.

Polyoxometalate-derived bi-functional crystalline/amorphous interfaces with optimized d-electron configuration for efficient self-powered hydrazine-seawater splitting

Hydrazine-assisted water electrolysis is a promising energy-efficient strategy for hydrogen production. Nonetheless, developing high-performance bi-functional electrocatalysts towards both hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) remains great challenges, especially for hydrazine-seawater splitting. Herein, we report a polyoxometalate-assisted in-situ synthesis protocol for constructing bi-functional crystalline/amorphous Pt/MoO3-x interfaces toward both efficient HER and HzOR. The polyoxometalate-derived crystalline/amorphous Pt/MoO3-x interfaces deliver working potentials of only –23 and −41 mV at 10 mA cm−2 for HER and HzOR in seawater electrolyte, respectively. Meanwhile, ultrahigh mass activities of 38.39 AmgPt-1 for HER at −100 mV potential and 23.84 AmgPt-1 for HzOR at 50 mV potential are also achieved, over 30.2 and 52.9 times higher than those of commercial Pt/C. As bi-functional electrocatalysts for overall hydrazine-seawater splitting, the electrolyzer requires a cell voltage of only 55/238 mV at 10/100 mA cm−2, 1.584/1.543 V lower than that of the seawater splitting system. Moreover, a proof-of-concept self-powered hydrazine-seawater electrolysis system driven by direct hydrazine fuel cell is further demonstrated, which achieves a hydrogen production rate of 0.29 mL cm−2min−1. DFT calculations verify that, the crystalline/amorphous interfaces endow Pt/MoO3-x an optimized d-electron configuration with favorable H* adsorption and promoted dehydrogenation kinetics of *N2H4 to *N2H3 in the potential-determining step. This work provides a novel strategy and inspiration toward the design of efficient bi-functional electrocatalysts for hydrazine-assisted hydrogen production from seawater.

Activating Interfacial Electron Redistribution in Lattice-Matched Biphasic Ni3N-Co3N for Energy-Efficient Electrocatalytic Hydrogen Production via Coupled Hydrazine Degradation.

The development of high-purity and high-energy-density green hydrogen through water electrolysis holds immense promise, but issues such as electrocatalyst costs and power consumption have hampered its practical application. In this study, we present a promising solution to these challenges through the use of a high-performance bifunctional electrocatalyst for energy-efficient hydrogen production via coupled hydrazine degradation. The biphasic metal nitrides with highly lattice-matched structures are deliberately constructed, forming an enhanced local electric field between the electron-rich Ni3N and electron-deficient Co3N. Additionally, Mn is introduced as an electric field engine to further activate electron redistribution. Our Mn@Ni3N-Co3N/NF bifunctional electrocatalyst achieves industrial-grade current densities of 500 mA cm-2 at 0.49 V without degradation, saving at least 53.3 % energy consumption compared to conventional alkaline water electrolysis. This work will stimulate the further development of metal nitride electrocatalysts and also provide new perspectives on low-cost hydrogen production and environmental protection.

P-Bridging Asymmetry Diatomic Catalysts Sites Drive Efficient Bifunctional Oxygen Electrocatalysis for Zinc-Air Batteries.

Rechargeable zinc-air batteries (ZABs) rely on the development of high-performance bifunctional oxygen electrocatalysts to facilitate efficient oxygen reduction/evolution reactions (ORR/OER). Single-atom catalysts (SACs), characterized by their precisely defined active sites, have great potential for applications in ZABs. However, the design and architecture of atomic site electrocatalysts with both high activity and durability present significant challenges, owing to their spatial confinement and electronic states. In this study, a strategy is proposed to fabricate structurally uniform dual single-atom electrocatalyst (denoted as P-FeCo/NC) consisting of P-bridging Fe and Co bimetal atom (i.e., Fe-P-Co) decorated on N, P-co-doped carbon framework as an efficient and durable bifunctional electrocatalyst for ZABs. Experimental investigations and theoretical calculations reveal that the Fe-P-Co bridge-coupling structure enables a facile adsorption/desorption of oxygen intermediates and low activation barrier. The resultant P-FeCo/NC exhibits ultralow overpotential of 340mV at 10mA cm-2 for OER and high half-wave potential of 0.95V for ORR. In addition, the application of P-FeCo/NC in rechargeable ZABs demonstrates enhanced performance with maximum power density of 115mW cm-2 and long cyclic stability, which surpass Pt/C and RuO2 catalysts. This study provides valuable insights into the design and mechanism of atomically dispersed catalysts for energy conversion applications.

Superstructure-Assisted Single-Atom Catalysis on Tungsten Carbides for Bifunctional Oxygen Reactions.

Single-atom catalysis (SAC) attracts wide interest for zinc-air batteries that require high-performance bifunctional electrocatalysts for oxygen reactions. However, catalyst design is still highly challenging because of the insufficient driving force for promoting multiple-electron transfer kinetics. Herein, we report a superstructure-assisted SAC on tungsten carbides for oxygen evolution and reduction reactions. In addition to the usual single atomic sites, strikingly, we reveal the presence of highly ordered Co superstructures in the interfacial region with tungsten carbides that induce internal strain and promote bifunctional catalysis. Theoretical calculations show that the combined effects from superstructures and single atoms strongly reduce the adsorption energy of intermediates and overpotential of both oxygen reactions. The catalyst therefore presented impressive bifunctional activity with an ultralow potential gap of 0.623 V and delivered a high power density of 188.5 mW cm-2 for assembled zinc-air batteries. This work opens up new opportunities for atomic catalysis.

Free‐Standing Multiscale Porous High Entropy NiFeCoZn Alloy as the Highly Active Bifunctional Electrocatalyst for Alkaline Water Splitting

Comprehensive SummaryIn the endeavor of searching for highly active and stable electrocatalysts toward overall water splitting, high‐entropy‐alloys have been the intense subjects owing to their advanced physicochemical property. The non‐noble metal free‐standing multiscale porous NiFeCoZn high‐entropy‐alloy is in situ constructed on the surface layer of NiZn intermetallic and Ni heterojunction over nickel foam (NiFeCoZn/NiZn‐Ni/NF) by one scalable dealloying protocal to fulfill the outstanding bifunctional electrocatalytic performances toward overall water splitting. Because of the high‐entropy effects and specific hierarchical porous architecture, the as‐made NiFeCoZn/NiZn‐Ni/ NF displays high intrinsic catalytic activities and durability toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. In particular, the in‐situ construction of bimodal porous NiFeCoZn high‐entropy‐alloy results in the small overpotentials (η1000 = 254/409 mV for HER and OER), low Tafel slopes, and exceptional long‐term catalytic durability for 400 h. Expressively, the electrolyzer constructed with NiFeCoZn/NiZn‐Ni/NF as both cathode and anode exhibits a low cell voltage of 1.72 V to deliver the current density of 500 mA·cm–2 for overall water splitting. This work not only provides a facile and scalable protocol for the preparation of self‐supporting high‐entropy‐alloy nanocatalysts but also enlightens the engineering of high performance bifunctional electrocatalysts toward water splitting.

In-situ construction of cation vacancies in amphoteric-metallic element-doped NiFe-LDH as ultrastable and efficient alkaline hydrogen evolution electrocatalysts at 1000 mA cm−2

Developing efficient and stable electrocatalysts at affordable costs is very important for large-scale production of green hydrogen. In this study, unique amphoteric metallic element-doped NiFe-LDH nanosheet arrays (NiFeCd-LDH, NiFeZn-LDH and NiFeAl-LDH) using as high-performance bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were reported, by tuning electronic structure and vacancy engineering. It was found that NiFeCd-LDH possesses the lowest overpotentials of 85 mV and 240 mV (at 10 mA cm−2) for HER and OER, respectively. Density functional theory (DFT) calculations reveal the synergistic effect of Cd vacancies and Cd doping on improving alkaline HER performance, which promote the achievement of excellent catalytic activity and ultrastable hydrogen production at a large current density of 1000 mA cm−2 within 250 h. Besides, the overall water splitting performance of the as-prepared NiFeCd-LDH requires only 1.580 V to achieve a current density of 10 mA cm−2 in alkaline seawater media, underscoring the importance of modifying the electronic properties of LDH for efficient overall water splitting in both alkaline water/seawater environments.

Three-dimensional heterostructured MnNiCoP/FeOOH cross-linked nano-flake supported by Ni Foam as a bifunctional electrocatalysts for overall water splitting

The production of three-dimensional heterogeneous structures is a vital approach for the creation of high-performance bifunctional electrocatalysts. Herein, three-dimensional heterostructure MnNiCoP/FeOOH (MNC-P/FeOOH) supported by Ni foam was prepared by simple electrodeposition and phosphorylation as a bifunctional electrocatalyst. The results showed that the required overpotential for MNC-P/FeOOH catalyst to reach 100 mA cm−2 current density was 124 mV and 251 mV in 1.0 M KOH solution, respectively. Construction of heterojunction not only improves the OER performance of MnNiCoP, but also reduces the potential required to drive the integral water splitting at 100 mA cm−2 current density. The electrocatalytic activity of MNC-P/FeOOH is greatly increased due to a distinctive interface synergy and strong electronic contacts in the MNC-P/FeOOH heterojunction. This design approach of bifunctional transition metal phosphides provides a potential route to achieve total water splitting.

Nitrogen and Sulfur Co-Doped Carbon-Coated Ni3S2/MoO2 Nanowires as Bifunctional Catalysts for Alkaline Seawater Electrolysis.

Bifunctional catalysts have inherent advantages in simplifying electrolysis devices and reducing electrolysis costs. Developing efficient and stable bifunctional catalysts is of great significance for industrial hydrogen production. Herein, a bifunctional catalyst, composed of nitrogen and sulfur co-doped carbon-coated trinickel disulfide (Ni3S2)/molybdenum dioxide (MoO2) nanowires (NiMoS@NSC NWs), is developed for seawater electrolysis. The designed NiMoS@NSC exhibited high activity in alkaline electrolyte with only 52 and 191mV overpotential to attain 10mAcm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Significantly, the electrolyzer (NiMoS@NSC||NiMoS@NSC) based on this bifunctional catalyst drove 100mAcm-2 at only 1.71V along with a robust stability over 100h in alkaline seawater, which is superior to a platinum/nickel-iron layered double hydroxide couple (Pt||NiFe LDH). Theoretical calculations indicated that interfacial interactions between Ni3S2 and MoO2 rearranged the charge at interfaces and endowed Mo sites at the interfaces with Pt-like HER activity, while Ni sites on Ni3S2 surfaces at non-interfaces are the active centers for OER. Meanwhile, theoretical calculations and experimental results also demonstrated that interfacial interactions improved the electrical conductivity, boosting reaction kinetics for both HER and OER. This study presented a novel insight into the design of high-performance bifunctional electrocatalysts for seawater splitting.

Brush-like Co/CoSe nanoheterostructures embedded in N-doped carbon for rechargeable Zn-air batteries.

Rational design and preparation of high-performance bifunctional oxygen electrocatalysts with effective sites and excellent mass/electron transfer structures are in demand for Zn-air batteries to overcome the sluggish oxygen reduction/evolution kinetics. Herein, a scalable and facile strategy is proposed to obtain brush-like Co/CoSe nanoheterostructures embedded in N-doped carbon catalysts with optimized active sites and hierarchical nanostructures. Systematic investigation indicates that nanoheterogeneous interfaces with appropriate composition deliver significantly improved electrochemical activity. As a result, a zinc-air battery assembled with the obtained Co/CoSe nanoheterostructures embedded in the N-doped carbon (CoSe/Co@NC-1) catalyst exhibits outstanding electrochemical performance with a peak power density of 215 mW cm-2 and excellent stability for 475 hours (2850 cycles). These results indicate that this strategy is an effective method for fabricating multicomponent and hierarchically nanostructured materials with enhanced catalytic efficiency for advanced energy devices.

Thermal evaporation-driven fabrication of Ru/RuO2 nanoparticles onto nickel foam for efficient overall water splitting.

Developing high-performance bifunctional electrocatalysts towards the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) holds great significance for efficient water splitting. This work presents a two-stage metal-organic thermal evaporation strategy for the fabrication of Ru-based catalysts (Ru/NF) through growing ruthenium (Ru)/ruthenium dioxide (RuO2) nanoparticles (NPs) on nickel foam (NF). The optimal Ru/NF shows remarkable performance in both the HER (26.1 mV) and the OER (235.4 mV) at 10 mA cm-2 in an alkaline medium. The superior OER performance can be attributed to the synergistic interaction between Ru and RuO2, facilitating fast alkaline water splitting. Density functional theory studies reveal that the resulting Ru/RuO2 with the (110) crystal surface reinforces the adsorption of oxygen on RuO2, while metallic Ru improves water dissociation in alkaline electrolytes. Besides, Ru/NF requires only 1.50 V at 10 mA cm-2 for overall water splitting, surpassing 20 wt% Pt/C/NF||RuO2/NF. This work demonstrates the promising potential of a thermal evaporation approach for designing stable Ru-based nanomaterials loaded onto conductive substrates for high performance overall water splitting.

Transition metal-based electrocatalysts for alkaline overall water splitting: advancements, challenges, and perspectives.

Water electrolysis is a promising method for efficiently producing hydrogen and oxygen, crucial for renewable energy conversion and fuel cell technologies. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are two key electrocatalytic reactions occurring during water splitting, necessitating the development of active, stable, and low-cost electrocatalysts. Transition metal (TM)-based electrocatalysts, spanning noble metals and TM oxides, phosphides, nitrides, carbides, borides, chalcogenides, and dichalcogenides, have garnered significant attention due to their outstanding characteristics, including high electronic conductivity, tunable valence electron configuration, high stability, and cost-effectiveness. This timely review discusses developments in TM-based electrocatalysts for the HER and OER in alkaline media in the last 10 years, revealing that the exposure of more accessible surface-active sites, specific electronic effects, and string effects are essential for the development of efficient electrocatalysts towards electrochemical water splitting application. This comprehensive review serves as a guide for designing and constructing state-of-the-art, high-performance bifunctional electrocatalysts based on TMs, particularly for applications in water splitting.

Ni-modified Co3O4 with competing electrochemical performance to noble metal catalysts in both oxygen reduction and oxygen evolution reactions

The commercial viability of zinc-air batteries (ZABs) depends upon the availability of cost-effective and high-performance bifunctional electrocatalyst, which can simultaneously accelerate both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Noble metal catalysts suffer from poor cycling stability and cost ineffectiveness. Here we report on a Ni-modified spinel Co3O4 catalyst, which exhibits competing electrochemical properties to Pt/C in ORR and to RuO2 in OER. A ZAB cell fabricated with the catalyst as cathode and Zn as anode exhibits a specific capacity of 803 mAh/g and a cycling stability of 240 h at 5 mA cm−2, comparable to commercial noble metal catalysts. Computational calculations reveal that Ni partially substitutes tetrahedral Co sites in spinel Co3O4 to induce the formation of oxygen vacancies, which play an important role in hindering peroxide formation and enhancing electron conductivity. The presence of Ni in Co3O4 also weakens the interaction between surface Co and OH*, lowering the overpotentials of ORR and OER.