Zinc-air Battery Application Research Articles

The application of S, N co-doped biomass carbon-based FeCoNi bifunctional electrocatalysis in zinc-air battery

The development of efficient Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalysts from biomass is of significant importance for the commercial application of zinc-air batteries (ZABs). Herein, a bifunctional catalyst (FeCoNi@SNC) is successfully synthesized through introducing Fe, Co and Ni atoms, fish scale-derived carbon (CFS) as the precursor, thiourea and dicyandiamide (DCDA) as the S and N sources, respectively. More importantly, FeCoNi@SNC is identified as a composite material containing FeCo, FeNi3 and metal sulfides. A large number of fluffy carbon nanotubes are induced to grow on the CFS surface by metal nanoparticles, while M-N, M-O and M-S are formed. The catalytic performance is positively influenced by the unique morphology and different active sites of FeCoNi@SNC. To our delight, FeCoNi@SNC exhibits excellent catalytic activity in both ORR (E1/2=0.85 V) and OER (Ej=10= 1.556 V). As a cathode in zinc-air batteries, FeCoNi@SNC possesses significant potential with a peak power density of 146.9 mW cm−2, a specific capacity of 706.9 mAh g−1, and an open circuit voltage of 1.525 V. A novel approach is provided by this work for designing biomass-derived ORR/OER bifunctional catalysts and their application in zinc-air batteries.

FeCo Bimetallic ZIF Derivatives Decorated with CoFe-LDH to Promote Bifunctional Oxygen Electrocatalysis Activation.

Reasonably screening the targeted oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) constituents and constructing high-efficiency and stabilized ORR/OER bifunctional electrocatalysts are pivotal for the advancement of rechargeable zinc-air batteries (ZABs). Here, CoFe layered double hydroxide (CoFe-LDH) nanosheets are deposited on nitrogen-doped graphite-carbon polyhedra with FeCo alloy nanoparticles (FeCo/LDH-NGCP). Due to the synergic effect between FeCo-NGCP, CoFe-LDH and FeCo/LDH-NGCP, the electrocatalyst with the abundant and accessible active sites can provide good charge/mass transfer, and thus shows wonderful ORR and OER bifunctional electrocatalytic performance. In ORR tests, FeCo/LDH-NGCP catalyst displays larger half-wave potential (E1/2, 0.89 V vs. 0.85 V), higher limiting current density (JL, 5.91 mA/cm2 vs. 5.14 mA/cm2) and better stability than commercial Pt/C. As for OER, FeCo/LDH-NGCP possesses a smaller overpotential (η) of 299.6 mV at a current density of 10 mA/cm2 and more durable stability than commercial RuO2 (330.6 mV). Furthermore, in ZAB tests, the cycling stability of ZAB-FeCo/LDH-NGCP (over 470 h) outperforms the ZAB-Pt/C+RuO2 (92 h) with commercial electrocatalyst (Pt/C+RuO2). Therefore, the FeCo/LDH-NGCP catalyst offers a new perspective to construct ZABs bifunctional catalysts and their commercial application in ZABs.

Enhanced bifunctional electrocatalysis of Co5.47N nanocrystals in porous carbon nanofibers for high-efficiency zinc-air batteries

As a promising energy conversion and storage device, recently, rechargeable zinc-air batteries (ZABs) have developed rapidly, and the exploitation of excellent electrode catalysts to improve the energy efficiency and long-term performance of ZABs has become a focus of current research. Herein, the Co5.47N nanocrystals embedded in porous carbon nanofibers (Co5.47N PCNFs) were designed to act as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and iodide oxidation reaction (IOR), which occur on the electrode in the charging-discharging process of ZABs. The electrochemistry results showed that the ORR activity of Co5.47N PCNFs is comparable to the commercial Pt/C electrocatalyst, and the IOR activity and stability are higher than those of the Pt/C electrocatalyst. Importantly, Co5.47N PCNFs electrocatalyst endows ZABs with a low charge–discharge voltage difference (0.49 V), a high round-trip energy efficiency (72.1 %), as well as a large specific capacity (791.5 mAh gZn−1), surpassing the performance of Pt/C electrocatalyst. Density functional theory calculation demonstrates that Co5.47N PCNFs have lower Gibbs free energy for the formation of IOR intermediate species, thereby displaying outstanding IOR catalytic performance compared to that of Pt/C electrocatalyst. These findings offer crucial insights into the rational design of cobalt nitride-based electrocatalysts for application in ZABs with high energy efficiency.

Carbon-coated ZnS as a high-performance ORR/OER bifunctional cathode catalyst for zinc-air batteries

The commercial application of zinc-air batteries (ZABs) is hindered by the high cost and scarcity of precious metal catalysts. In this paper, we prepared high-performance ORR/OER bifunctional catalysts with a carbon-coated ZnS spherical structure (ZnS@C) through a hydrothermal method followed by a carbonization process. Characterized by their unique spherical coated pore structure, exhibit impressive electrocatalytic activity. Specifically, ZnS@C-2, produced by a secondary carbonization process demonstrates an ORR half-wave potential of 0.82 V (relative to RHE) and an OER overpotential of 377 mV at 10 mA cm−2. When employed in a ZAB, it achieves a maximum power density of 120.4 mW cm−2, a specific capacity of 836 mAh gZn−1, and maintains cycle stabilization for up to 165 h at 10 mA cm−2. The research results demonstrate that the unique carbon-coated internal porous structure not only significantly enhances the stability of the catalyst but also increases the number of active sites, thereby providing more abundant activation energy for the catalytic reaction and facilitating its efficient progress. This underscores the catalyst's excellent ORR and OER properties, suggesting promising practical application potential.

Investigating the bifunctional electrocatalytic activity of nickel oxide/nitrogen-doped reduced graphene oxide nanocomposite for zinc-air battery application

Investigating the bifunctional electrocatalytic activity of nickel oxide/nitrogen-doped reduced graphene oxide nanocomposite for zinc-air battery application

Enhanced oxygen evolution and power density of Co/Zn@NC@MWCNTs for the application of zinc-air batteries

Rechargeable zinc-air batteries (ZABs) are viewed as a promising solution for electric vehicles due to their potential to provide a clean, cost-effective, and sustainable energy storage system for the next generation. Nevertheless, sluggish kinetics of the oxygen evolution reaction (OER), the oxygen reduction reaction (ORR) at the air electrode, and low power density are significant challenges that hinder the practical application of ZABs. The key to resolving the development of ZABs is developing an affordable, efficient, and stable catalyst with bifunctional catalytic. In this study, we present a series of bifunctional catalysts composed of Co/Zn nanoparticles uniformly embedded in nitrogen-doped carbon (NC) and multi-walled carbon nanotubes (MWCNTs) denoted as Co/Zn@NC@MWCNTs. The incorporation of MWCNTs using a facile and non-toxic method significantly decreased the overpotential of the OER from 570 to 430 mV at 10 mA cm−2 and the peak power density from 226 to 263 mW cm−2. Besides, the electrochemical surface area measurements and electrochemical impedance spectroscopy indicate that the three-dimensional (3D) network structure of MWCNTs facilitates mass transport for ORR and reduces electron transfer resistance during OER, leading to a small potential gap of 0.86 V between OER and ORR, high electron transfer number (3.92–3.98) of the ORR, and lowest Tafel slope (47.8 mV dec−1) of the OER in aqueous ZABs. In addition, in-situ Raman spectroscopy revealed a notable decrease in the ID/IG ratio for the optimally configured Co/Zn@NC@MWCNTs (75:25), indicating a reduction in defect density and improved structural ordering during the electrochemical process, which directly contributes to enhanced ORR activity. Hence, this study provides an excellent strategy for constructing a bifunctional catalyst material with a 3D MWCNTs conductive network for the development of advanced ZAB systems for sustainable energy applications.

Promoting Electrocatalytic Oxygen Reactions Using Advanced Heterostructures for Rechargeable Zinc-Air Battery Applications.

In order to facilitate electrochemical oxygen reactions in electrically rechargeable zinc-air batteries (ZABs), there is a need to develop innovative approaches for efficient oxygen electrocatalysts. Due to their reliability, high energy density, material abundance, and ecofriendliness, rechargeable ZABs hold promise as next-generation energy storage and conversion devices. However, the large-scale application of ZABs is currently hindered by the slow kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). However, the development of heterostructure-based electrocatalysts has the potential to surpass the limitations imposed by the intrinsic properties of a single material. This Account begins with an explanation of the configurations of ZABs and the fundamentals of the oxygen electrochemistry of the air electrode. Then, we summarize recent progress with respect to the variety of heterostructures that exploit bifunctional electrocatalytic reactions and overview their impact on ZAB performance. The range of heterointerfacial engineering strategies for improving the ORR/OER and ZAB performance includes tailoring the surface chemistry, dimensionality of catalysts, interfacial charge transfer, mass and charge transport, and morphology. We highlight the multicomponent design approaches that take these features into account to create advanced highly active bifunctional catalysts. Finally, we discuss the challenges and future perspectives on this important topic that aim to enhance the bifunctional activity and performance of zinc-air batteries.

Compressively Strained Fe3O4 in Core-Shell Oxygen Reduction Electrocatalyst Boosts Zinc-Air Battery Performance.

Fe3O4 is barely taken into account as an electrocatalyst for oxygen reduction reaction (ORR), an important reaction for metal-air batteries and fuel cells, due to its sluggish catalytic kinetics and poor electron conductivity. Herein, how strain engineering can be employed to regulate the local electronic structure of Fe3O4 for high ORR activity is reported. Compressively strained Fe3O4 shells with 2.0% shortened Fe─O bond are gained on the Fe/Fe4N cores as a result of lattice mismatch at the interface. A downshift of the d-band center occurs for compressed Fe3O4, leading to weakened chemisorption energy of oxygenated intermediates, and lower reaction overpotential. The compressed Fe3O4 exhibits greatly enhanced electrocatalytic ORR activity with a kinetic current density of 27 times higher than that of pristine one at 0.80V (vs reversible hydrogen electrode), as well as potential application in zinc-air batteries. The findings provide a new strategy for tuning electronic structures and improving the catalytic activity of other metal catalysts.

Fe and Cu co-encapsulated by nitrogen-doped carbon for zinc-air battery applications

Zinc-air batteries (ZABs) have attracted attention for their environmental friendliness, durability, safety and high energy density. The superior performance of rechargeable ZABs hinges on the activity of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Here, we successfully develop a Fe, Cu co-doped ZIF-derived N-doped carbon (FeCux-NC) catalyst, featuring a lamellar “red blood cell” structure. In the ORR process, the optimized FeCux-NC catalyst achieves a half-wave potential of 0.925 V under alkaline conditions, 70 mV higher than commercial Pt/C catalysts, and exhibits good stability. In the OER process, at 10 mA cm−2, the overpotential is measured at 510 mV and the Tafel slope value is 55.2 mV dec−1. When utilizing optimized FeCux-NC catalyst without RuO2 at a catalyst loading of 2 mg cm−1, the assembled ZABs demonstrate a power density of 85 mW cm−2 at 140 mA cm−2, while maintaining excellent cycling stability (with only a 0.11 V increase in the voltage interval between charging and discharging over 300 cycles), thereby realizing the dual function of ORR/OER.

Metal-Organic-Framework-Derived Nitrogen-Doped Carbon-Matrix-Encapsulating Co0.5Ni0.5 Alloy as a Bifunctional Oxygen Electrocatalyst for Zinc-Air Batteries.

The development of low-cost, high-performance oxygen electrocatalysts is of great significance for energy conversion and storage. As a potential substitute for precious metal electrocatalysts, the construction of efficient and cost-effective oxygen electrocatalysts is conducive to promoting the widespread application of zinc-air batteries. Herein, CoxNiyMOF nanoparticles encapsulated within a carbon matrix were synthesized and employed as cathode catalysts in zinc-air batteries. Co0.5Ni0.5MOF exhibits superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance and durability. The zinc-air battery assembled with Co0.5Ni0.5MOF as the air cathode exhibits a maximum power density of 138.6 mW·cm-2. These improvements are mainly attributed to the optimized metal composition of the cobalt-nickel alloy, which increases the specific surface area of the material and optimizes its pore structure. Significantly, the optimization of the electronic structure and active sites within the material has led to amplified ORR/OER activity and better zinc-air battery performance. This study underscores the immense promise of Co0.5Ni0.5MOF catalysts as feasible substitutes for commercial Pt/C catalysts in zinc-air batteries.

Heterostructured NiO/IrO2 synergistic pair as durable trifunctional electrocatalysts towards water splitting and rechargeable zinc-air batteries: An experimental and theoretical study

Constructing an ultra-durable trifunctional electrocatalyst with high efficiency for HER, OER and ORR has become critical for demanding water splitting and zinc air battery applications. Herein, we demonstrated a rational and efficient strategy to develop a porous nano foam like heterostructured NiO/IrO2 nano foam like electrocatalyst via a facile solvothermal and calcination approach. Experiments revealed that NiO/IrO2-NF shows outstanding HER (ƞ10=42 mV), OER (ƞ10=240 mV), and ORR (E1/2=0.80 V) performances with lower overpotentials than many reported trifunctional electrocatalysts. Theoretical investigations on reaction mechanism of NiO/IrO2-NF, S-IrO2 and S-NiO were carried out using density functional theory calculations. The fabricated water electrolyzer required minimum cell voltage of 1.51 V to reach 10 mA cm−2 current density with outstanding durability of 600 h and insignificant potential loss. Rechargeable zinc air battery with NiO/IrO2-NF air cathode displays a power density of 134.8 mW cm−2 with excellent durability of 100/80/40 h at 2/5/10 mA cm−2.

A High-Entropy Single-Atom Catalyst Toward Oxygen Reduction Reaction in Acidic and Alkaline Conditions.

The design of high-entropy single-atom catalysts (HESAC) with 5.2 times higher entropy compared to single-atom catalysts (SAC) is proposed, by using four different metals (FeCoNiRu-HESAC) for oxygen reduction reaction (ORR). Fe active sites with intermetallic distances of 6.1Å exhibit a low ORR overpotential of 0.44V, which originates from weakening the adsorption of OH intermediates. Based on density functional theory (DFT) findings, the FeCoNiRu-HESAC witha nitrogen-doped sample were synthesized. The atomic structures are confirmed with X-ray photoelectron spectroscopy (XPS), X-ray absorption (XAS), and scanning transmission electron microscopy (STEM). The predicted high catalytic activity is experimentally verified, finding that FeCoNiRu-HESAC has overpotentials of 0.41and 0.37V with Tafel slopes of 101 and 210mVdec-1 at the current density of 1mAcm-2 and the kinetic current densities of 8.2 and 5.3mAcm-2, respectively, in acidic and alkaline electrolytes. These results are comparable with Pt/C. The FeCoNiRu-HESAC is used for Zinc-air battery applications with an open circuit potential of 1.39V and power density of 0.16Wcm-2. Therefore, a strategy guided by DFT is provided for the rational design of HESAC which can be replaced with high-cost Pt catalysts toward ORR and beyond.

High-throughput screening of dual atom catalysts for oxygen reduction and evolution reactions and rechargeable zinc-air battery

We provide the rational design of dual atom catalysts (DACs) supported on nitrogen-doped graphene for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) through high-throughput computational screening of M1M2N6-DAC systems, where M1 and M2 represent Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, or Pt metals. We predict that FeRuN6-DAC at the summit of the volcano plot exhibits a low theoretical ORR overpotential (ηORR) of 0.24 V and a low theoretical OER overpotential (ηOER) of 0.19 V. The low ηORR and ηOER result from the catalytic performance of the Fe site being tuned to electronic properties that facilitate adsorption and desorption of the OH* intermediate. Inspired by these hybrid density functional theory (DFT) computational and machine learning (ML) results, we synthesized FeRuN6-DAC, FeN4-SAC, and RuN4-SAC and characterized them using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and in-situ electron spin resonance (ESR). Our in-situ ESR spectroscopy signifies that the spin of the Fe active site increases with increasing applied potential due to the increase in the concentration of OH* intermediate on Fe. We verified experimentally the predicted catalytic performances, finding that FeRuN6-DAC leads to an experimental ORR overpotential of 0.29 V with a Tafel slope of 104 mVdec−1 and an OER overpotential of 0.27 V with a Tafel slope of 124 mVdec−1. The rechargeable Zinc-air battery setup was fabricated with FeRuN6-DAC in place of the cathode, showing a maximum power density of 0.45 W/cm2 at the current density of 0.44 A/cm2 and good stability after 120 cycles. According to our findings, we demonstrate that DFT-guided strategies are useful for designing advanced DACs applicable to ORR, OER, and Zinc-air battery applications.

A Multi-Interfacial Material Design Leading Bifunctional Oxygen Reduction and Water Oxidation Electrocatalysis to Zinc–Air Battery Application

A Multi-Interfacial Material Design Leading Bifunctional Oxygen Reduction and Water Oxidation Electrocatalysis to Zinc–Air Battery Application

Nanoflower-like NiCo2O4 Composite Graphene Oxide as a Bifunctional Catalyst for Zinc-Air Battery Cathode.

Developing efficient bifunctional catalysts for nonprecious metal-based oxygen reduction (ORR) and oxygen evolution (OER) is crucial to enhance the practical application of zinc-air batteries. The study harnessed electrostatic forces to anchor the nanoflower-like NiCo2O4 onto graphene oxide, mitigating the poor inherent conductivity in NiCo2O4 as a transition metal oxide and preventing excessive agglomeration of the nanoflower-like structures during catalysis. Consequently, the resulting composite, NiCo2O4-GO/C, exhibited notably superior ORR and OER catalytic performance compared to pure nanoflower-like NiCo2O4. Notably, it excelled in OER catalytic activity of the OER relative to the precious metal RuO2. As a bifunctional catalyst for ORR and OER, NiCo2O4-GO/C displayed a potential difference of 0.88 V between the ORR half-wave potential and the OER potential at 10 mA·cm-2, significantly lower than the 1.08 V observed for pure flower-like NiCo2O4 and comparable to the 0.88 V exhibited by precious metal catalysts Pt/C + RuO2. The NiCo2O4-GO/C-based zinc-air battery demonstrated a discharge capacity of 817.3 mA h·g-1, surpassing that of precious metal-based zinc-air batteries. Moreover, charge-discharge cycling tests indicated the superior stability of the NiCo2O4-GO/C-based zinc-air battery compared to its precious metal-based counterparts.

Tailored bimetallic synergy of iron–cobalt sulfide anchored to S-doped carbonized wood fiber for high-efficiency oxygen evolution reaction

Decoupling the scaling relation of intermediates is an effective strategy to improve the oxygen evolution reaction (OER) catalytic efficiency. Herein, S-doped carbon-confined Fe.92Co.08S nanoparticles (Fe.92Co.08S@SC) anchored to S-doped carbonized wood fiber (SCWF) are fabricated via simple synchronous carbonization and sulfidation. Due to the synergistic catalytic effect of bimetallic and the unique structural effect of the supported catalyst, Fe.92Co.08S@SC/SCWF exhibit excellent OER catalytic efficiency with an overpotential of 238 mV at 50 mA cm and stability up to 100 h. Furthermore, a high current density of 500 mA cm−2 at an overpotential of 281 mV was achieved. Theoretical calculations and electrochemical characterizations confirm that bimetallic synergies can accelerate the surface reconstruction of Fe.92Co.08S@SC with highly efficient OER activity. For zinc–air battery applications, Fe.92Co.08S@SC/SCWF exhibits superior power density and stability over commercial RuO2. This work provides insights into the preparation of supported electrocatalysts with bimetallic synergy for high-efficiency OER.

Origin of the Oxygen Reduction Activity on Boron-Doped Fe–N–C Catalysts for Zinc–Air Battery Applications

Origin of the Oxygen Reduction Activity on Boron-Doped Fe–N–C Catalysts for Zinc–Air Battery Applications

Lithium-Induced Oxygen Vacancies in MnO2@MXene for High-Performance Zinc-Air Batteries.

The traditional methods for creating oxygen vacancies in materials present several challenges and limitations, such as high preparation temperatures, limited oxygen vacancy generation, and morphological destruction, which hinder the application of transition metal oxides in the field of zinc-air batteries (ZABs). In order to address these limitations, we have introduced a pioneering lithium reduction strategy for generating oxygen vacancies in δ-MnO2@MXene composite materials. This strategy stands out for its simplicity of implementation, applicability at room temperature, and preservation of the material's structural integrity. This research demonstrates that aqueous Ov-MnO2@MXene-5, with introduced oxygen vacancies, exhibits an outstanding oxygen reduction reaction (ORR) activity with an ORR half-wave potential reaching 0.787 V. DFT calculations have demonstrated that the enhanced activity could be attributed to adjustments in the electronic structure and alterations in adsorption bond lengths. These adjustments result from the introduction of oxygen vacancies, which in turn promote electron transport and catalytic activity. In the context of zinc-air batteries, cells with Ov-MnO2@MXene-5 as the air cathode exhibit outstanding performance, featuring a significantly improved maximum power density (198.3 mW cm-2) and long-term cycling stability. Through the innovative strategy of introducing oxygen vacancies, this study has successfully enhanced the electrochemical catalytic performance of MnO2, overcoming the limitations associated with traditional methods for creating oxygen vacancies. Consequently, this research opens up new avenues and directions for nonprecious metal catalyst application in ZABs.

Simultaneous regulation of thermodynamic and kinetic behavior on FeN3P1 single-atom configuration by Fe2P for efficient bifunctional ORR/OER

Single-atom catalysts have been extensively researched in electrocatalytic oxygen reduction and evolution reactions (ORR/OER) due to their tunable coordination environment. However, the linear scaling relationship (LSR) of oxygen intermediate adsorption energies imposes limitations in simultaneously enhancing ORR/OER. Herein, a unique asymmetrically coordinated FeN3P1 single-atom configuration coupled by Fe2P nanoparticle is synthesized via a prefabricated Fe-N/P coordination strategy. The accentuated structural distortion induced by Fe2P can effectively break the LSR, lowering the energy barriers for ORR/OER. Kinetically, a modulation of OH− concentration by Fe2P on the catalytic interface was identified by finite element simulation and molecular dynamics simulation, which can positively facilitate ORR/OER kinetics. The obtained Fe2P@FeN3P1-NC catalyst exhibits excellent bifunctional ORR/OER (∆E = 0.65 V) and a promising application in zinc-air battery. This work provides a valuable insight into simultaneous regulation of thermodynamic and kinetic behavior by tailored structure distortion and enriched surface ions for ORR/OER.

Modulating the Fe spin state in FeNC catalysts by Ru nanoparticles to facilitate the oxygen reduction reaction

FeNC is a promising non-precious metal catalyst that can replace platinum-based catalysts in proton-exchange membrane fuel cells (PEMFCs) and zinc–air battery applications.