Catalysts For Zinc-air Batteries Research Articles

Plasma-Enhanced Copper Sulfide/Oxide Electrode for Zinc-Air/Copper Dual Mode Battery

As search for novel electrochemical energy storage systems continues, metal-air batteries are one of the possible solution. Consisting of a metal anode and an air-breathing cathode, by design, they achieve much higher gravimetric energy density in theory. However, s-orbital metals suffer passivation issues and poses safety threats due to their reactivity with air and humidity. As a solution to this issue, safer d-block metals are being studied as an alternative. Zinc air batteries (ZABs) utilizes earth-abundant and cost-effective zinc as its anode, and has high theoretical capacity. At its cathode, oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) occur during charging and discharge processes. Sluggish kinetics of ORR degrades the discharge performance, and is the bottleneck in commercial application of the zinc air battery. Additionally, irreversibility of the cathode reaction results in dissatisfactory retention of battery capacity. Current state-of-the-art noble metal catalysts achieves nearly 80% of the theoretical capacity. However, its cycling stability is severely limited to less than 200 cycles despite low discharge rate applied.Herein, we present a nitrogen plasma-enhanced copper sulfide/oxide catalyst (referred to as N-CuS) that exhibits good catalytic activity for its application as the air-breathing cathode for ZABs. The material is grown directly on metal foam surface using anodization, which is then treated using nitrogen plasma. Anodization creates defect-rich flakes of copper sulfide on the oxide surface, highly increasing surface area and creating the active sites. The material has good electrical conductivity and highly open porous structure that alleviates mass transport issues. Additionally, nitrogen plasma treatment further increases the surface area about 80%, and is expected to introduce nitrogen dopants to the surface, enhancing conductivity of the material. ECSA estimated by measuring Cdl shows that each process increases the ECSA by over 40 times and about 1.8 times, respectively.LSV of CuS and N-CuS half-cells have been performed to measure and compare catalytic performance of the material. N-CuS shows far higher current density and better catalytic activity (35mV less overpotential) than CuS, and higher output voltage is observed with N-CuS cells with the same current density. By assessing the GCPL (potential limited galvanostatic cycling) results, it was concluded that N-CuS requires lower charging voltage and exhibits higher discharge voltages than CuS.The overall performance was evaluated in a stack cell configuration, utilizing thin zinc foil as its anode to minimize mass error. The measured specific capacity of the cell was 789.3 mA·h·g-1, which approximately is 85% of the theoretical specific capacity of zinc-air cells (820 mA·h·g-1). This cell yields gravimetric energy density of about 666 Wh·kg-1. It is notable that these ZAB characteristics are comparable to Pt/C, the state-of-the-art catalyst as of now. N-CuS may be a viable replacement for the Pt/C electrode, resulting in the cost-saving effect. The cycling stability of both N-CuS and Pt/C-based ZAB has been assessed to show that N-CuS-based ZAB has much prolonged (more than twice the cycles) cyclability compared to Pt/C-based ZAB (Fig. S11).Additionally, ZAB constructed using N-CuS can operate in oxygen-deficient environments. As the counter reaction it utilizes redox reaction of copper oxides (Zn-Cu mode) in the substrate when operating in anaerobic conditions. The reduction of divalent and monovalent copper oxides appears as plateaus at 1.1 V and 0.8 V versus the zinc anode during GCPL. Due to this alternate reaction, the cell can operate even at low concentrations of oxygen or even in its absence.DFT calculations have been performed to elucidate the reaction mechanism and the intrinsic catalytic activity of the material, and shows nitrogen dopants improve reactivity of the active sites, thus reducing the overpotential.In summary, we have synthesized N-CuS as the OER/ORR catalyst for ZAB. Through anodization the catalyst was directly grown on the substrate and nitrogen plasma treatment further enhances the catalyst properties to render it higher surface area, conductivity, and better stability. This allows better reversibility in the OER/ORR and results in enhanced cyclability of the overall cell. The constructed RZAB exhibited high specific capacity of 789.3 mA·h·g-1, which, has higher capacity than the analogue using Pt/C catalyst. In addition, N-CuS based RZAB is capable of operating under oxygen-deficient conditions utilizing the metal oxide substrate. This allows the dual mode operation of zinc-air and zinc-copper modes, and results in a more consistent output from the RZAB, as short-term air supply issues could be buffered by this effect. Figure 1

Performance of Nitrogen-Doped Carbon Nanoparticles Carrying FeNiCu as Bifunctional Electrocatalyst for Rechargeable Zinc-Air Battery.

Catalysts for zinc-air batteries (ZABs) must be stable over long-term charging-discharging cycles and exhibit bifunctional catalytic activity. In this study, by doping nitrogen-doped carbon (NC) materials with three metal atoms (Fe, Ni, and Cu), a single-atom-distributed FeNiCu-NC bifunctional catalyst is prepared. The catalyst includes Fe(Ni-doped)-N4 for the oxygen evolution reaction (OER), Fe(Cu-doped)-N4 for the oxygen reduction reaction (ORR), and the NiCu-NC catalytic structure for the oxygen reduction reaction (ORR) in the nitrogen-doped carbon nanoparticles. This single-atom distribution catalyst structure enhances the bifunctional catalytic activity. If a trimetallic single-atom catalyst is designed, it will surpass the typical bimetallic single-atom catcalyst. FeNiCu-NC exhibits outstanding performance as an electrocatalyst, with a half-wave potential (E1/2) of 0.876V versus RHE, overpotential (Ej = 10) of 253mV versus RHE at 10mA cm-2, and a small potential gap (ΔE = 0.61V). As the anode in a ZAB, FeNiCu-NC can undergo continuous charge-discharged cycles for 575h without significant attenuation. This study presents a new method for achieving high-performance, low-cost ZABs via trimetallic single-atom doping.

In situ Construction of Multistage Core-Shell Nanostructure as Bifunctional Catalyst for Ultrastable Zinc-Air Batteries.

Many efforts have been devoted to obtaining excellent cathode catalysts for Zinc air batteries (ZABs), but the inevitable use of binder will damage the catalytic activity and weaken long-term stability, inefficient mass transfer of oxygen is also chargable for the limited activity. Herein, in situ grown hydrogen substituted graphdiyne (HGDY) on carbon paper has been prepared and used as cathode catalyst layer in ZABs. Multiple catalytic sites are firmly combined and end with the boosted bifunctional catalytic activity of oxygen reduction and oxygen evolution. Moreover, the specific surface area, sufficient active sites, multilevel pore nanostructure and robust conductivity are fully exposed to establish efficient catalytic interface and skeleton. Cu/Co nanoparticles are uniformly distributed and warped by HGDY network, which can stably exist during the catalytic process. As a result, a current density of 18.75mAcm-2 and a Tafel slope of 61.06mVdec-1 for oxygen reduction and a ultralong operation for more than 2300h in aqueous ZAB have been achieved, which is beyond many reported bifunctional catalysts in ZAB system.

Electronic structure modification of FeWO4 through F doping for enhanced oxygen reduction performance in zinc–air batteries

Exploring efficient and stable oxygen reduction reaction (ORR) catalysts for zinc-air batteries (ZABs) holds tremendously significant. Tungsten-based materials have attracted the attention of researchers thanks to abundant resources and excellent stability. Nevertheless, due to the strong adsorption energy for O-containing intermediates, *O and *OH are difficult to desorb from tungsten-based materials during ORR. Here, an F-doping strategy was employed to construct F-doped FeWO4 species composited on a multi-dimensional N-doped carbon (F–FeWO4/NC) as the ORR catalyst for ZABs. The incorporation of F atoms into the main lattice of FeWO4 enhanced the polarity of chemical bonds in FeWO4 through hydrogen bond interactions between H2O molecules and F atoms, further enhancing the polarity and hydrophilicity of F–FeWO4/NC. These changes favored the adsorption and desorption of intermediates as well as the diffusion of electrolyte, and ultimately reduced the ORR overpotential. Therefore, the F–FeWO4/NC catalyst demonstrated excellent ORR activity (E1/2 = 0.85 V vs. RHE). Furthermore, the ZAB with F–FeWO4/NC yielded satisfactory a specific capacity of 800.2 mAh g−1, a peak power density of 173.5 mW cm−2, and charge-discharge cycling stability (over 170 h at 5 mA cm−2). This study is beneficial to improve the ORR intrinsic activity of cheap tungsten-based materials and provides theoretical guidance for their practical application in ZABs.

Dispersed cobalt nanoparticles in the nitrogen doped carbon black as efficient catalysts for oxygen reduction reaction and Zinc-Air batteries

Developing an effective and durable Pt-free oxygen reduction reaction (ORR) catalyst for Zinc-Air batteries (ZABs) is propitious to easing the energy and pollution crisis. Herein, we have prepared Co nanoparticles/N-doped carbon (Co/N/C) with tunable Co contents by the pyrolysis of polydopamine-coated cobalt phthalocyanine/carbon black precursors. Benefiting from the well-dispersed Co nanoparticles and the formation of various active sites (i.e. pyridinic, graphitic N and Co-Nx), the resulting Co/N/C-2.86 wt% catalysts possess a half-wave potential of 0.84 V and a mass activity of 5.18 A/g, illustrating the superior ORR performance. Noteworthy, the ZABs with the cathode of Co/N/C-2.86 wt% display an outstanding cell performance with a large open-circuit voltage (1.542 V), a high specific discharge capacity (744 mAh g−1) and an excellent maximum power density (236 mW cm−2). This work offers a promising approach to rationally design and fabricate high-performance ORR electrocatalysts for advanced ZABs.

Cryogenic electrolytes and catalysts for zinc air batteries

The challenges of enabling zinc air batteries to operate at ultralow temperatures are twofold. The Prerequisite is preventing the electrolyte from freezing while maintaining high ionic conductivity. Secondly, the catalyst has to work efficiently at low temperatures. This highlight presents the latest development to resolve the challenges by tuning the structures of the electrolyte and catalyst, offering a new paradigm to widen the working temperature range of zinc air batteries.

Recent advances of bifunctional catalysts for zinc air batteries with stability considerations: from selecting materials to reconstruction.

With the growing depletion of traditional fossil energy resources and ongoing enhanced awareness of environmental protection, research on electrochemical energy storage techniques like zinc-air batteries is receiving close attention. A significant amount of work on bifunctional catalysts is devoted to improving OER and ORR reaction performance to pave the way for the commercialization of new batteries. Although most traditional energy storage systems perform very well, their durability in practical applications is receiving less attention, with issues such as carbon corrosion, reconstruction during the OER process, and degradation, which can seriously impact long-term use. To be able to design bifunctional materials in a bottom-up approach, a summary of different kinds of carbon materials and transition metal-based materials will be of assistance in selecting a suitable and highly active catalyst from the extensive existing non-precious materials database. Also, the modulation of current carbon materials, aimed at increasing defects and vacancies in carbon and electron distribution in metal-N-C is introduced to attain improved ORR performance of porous materials with fast mass and air transfer. Finally, the reconstruction of catalysts is introduced. The review concludes with comprehensive recommendations for obtaining high-performance and highly-durable catalysts.

Highly durable Cu–N–C active sites towards efficient oxygen reduction for zinc-air battery: Carbon matrix effect, reaction mechanism and pathways

The thorough understanding of ORR mechanism provides insights into the design of efficient ORR catalysts. Despite remarkable progress has been made in the development of Cu–N–C ORR catalysts, fundamental understanding of molecular governing factors is still lacking. The carbon matrix with varying π-electron delocalization degree can modulate electron density at the metal ion center rather than merely acting as the electron-conducting path. A volcano relationship is established between oxygen-reduction intrinsic activity and full-width at half-maxima (FWHM) of C 1s photoemission spectra (depicting electron donating/withdrawing capability of carbon matrix to metal ion center). The mechanistic origin of ORR on carbon matrix, N–C sites, and Cu sites in Cu–N–C catalyst in different reaction regions is also illuminated. This work will be likely to offer a new insight in the development of more selective and durable Cu–N–C catalysts for zinc-air batteries.

A pair of metal organic framework (MOF)-derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for zinc-air batteries

Metal organic frameworks (MOFs) are amazing precursors for the development of functional catalysts due to their ability of being modified both structurally and in terms of composition. This work presents a pair of MOF - derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for the advancement of zinc-air batteries. Zeolitic imidazolate frameworks (ZIF) are known as ideal materials to create doped carbons. Combining with a sacrificial tellurium template, we have developed a “pseudo-carbon nanotube” with a ZIF-8 that is doped with a mixture of zinc, cobalt, and iron. The resulting mixed-metal doped porous carbon nanotubes (CoFeZn@pCNT) show excellent catalytic activity for ORR with a half-way ORR potential (E1/2) of 0.87 V vs. RHE (reverse hydrogen electrode). Iridium-based catalysts are known as the best option for OER so far, but it is not viable for practical applications due to cost restrictions. Previous research into alternative catalysts has focused on metal oxides with first-row transition metals. Metal sulfides provide superior conductivity compared to metal oxides and are a new frontier in the search for affordable, active, and stable OER catalysts. By combining cobalt, iron, and nickel into a MOF structure (ZIF-67), followed by a sulfurization process, a MOF-derived mixed-metal sulfide catalyst (FeCoNi–S@ZIF) has been developed in this study. The resulting catalysts show an onset OER potential of 1.65 V vs. RHE at 10 mA cm−2 and exhibit remarkable stability for the operation of zinc-air batteries.

Porous phosphorus-rich CoP3/CoSnO2 hybrid nanocubes for high-performance Zn-air batteries

Porous metal phosphide cubes with exposed vertices and edges containing abundant catalytically active sites are promising electrocatalysts. Herein, by integrating the advantages of the phosphorus-rich cobalt phosphides and bimetallic oxides to form hybrid architectures, we prepared CoP3/CoSnO2 via phosphating CoSn(OH)6 nanocubes, which has unique porous nanocubic structure. The optimized CoP3/CoSnO2 porous nanaocubes showed excellent electrocatalytic activity for OER/ORR. What’s more, the electrochemical performances of CoP3/CoSnO2 porous nanaocubes as air cathode catalyst for zinc air batteries were better than that of commercial RuO2 and 20 wt% Pt/C with a mass ratio of 1:1 as the air cathode catalyst. This work offers a new strategy to fabricate metal phosphide with porous nanocubic structures.

Ultrathin cobalt pyrophosphate nanosheets with different thicknesses for Zn-air batteries

Two dimensional (2D) ultrathin nonprecious metal based catalysts show excellent electrocatalytic activities, due to the larger surface areas, more catalytic sites and more interconnected electron-transfer access than their bulk counterparts. Here, we synthesized cobalt pyrophosphate (Co2P2O7) nanosheets with different thickness by a simple and efficient one-step hydrothermal process. The catalytic performance of the obtained Co2P2O7 was investigated via diverse electrochemical measurement. Due to the unique 2D structure and the flexible coordination of pyrophosphate group, the as-prepared Co2P2O7 catalyst had excellent electrocatalytic performance and good stability, which could rank among the most active nonprecious metal catalysts for oxygen evolution reaction and oxygen reduction reaction. In addition, the ultrathin Co2P2O7 nanosheets exhibited good performance as the air cathode catalyst for zinc air batteries.

Recent Advances in Isolated Single-Atom Catalysts for Zinc Air Batteries: A Focus Review.

Recently, zinc–air batteries (ZABs) have been receiving attention due to their theoretically high energy density, excellent safety, and the abundance of zinc resources. Typically, the performance of the zinc air batteries is determined by two catalytic reactions on the cathode—the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Therefore, intensive effort has been devoted to explore high performance electrocatalysts with desired morphology, size, and composition. Among them, single-atom catalysts (SACs) have emerged as attractive and unique systems because of their high electrocatalytic activity, good durability, and 100% active atom utilization. In this review, we mainly focus on the advance application of SACs in zinc air batteries in recent years. Firstly, SACs are briefly compared with catalysts in other scales (i.e., micro- and nano-materials). A main emphasis is then focused on synthesis and electrocatalytic activity as well as the underlying mechanisms for mono- and dual-metal-based SACs in zinc air batteries catalysis. Finally, a prospect is provided that is expected to guide the rational design and synthesis of SACs for zinc air batteries.

Synthesis and electrochemical evaluation of La1−x Sr x MnO3 catalysts for zinc-air batteries

La1-x Sr x MnO3 (x = 0.1∼0.4) catalysts for primary and rechargeable zinc-air batteries have been successfully synthesized by the citrate method and their electrochemical properties measured. The materials can catalyze both ORR and OER, and the one with ideal composition of La0.8Sr0.2MnO3 catalyst exhibits the highest catalytic activity and durability in alkaline medium. The resulting primary zinc-air cell shows a peak power density of 146 mW cm−2 at 235 mA cm−2. The secondary cell exhibits a charge-discharge voltage gap of 1.0 V at 10 mA cm−2, which is highly stable over many charge-discharge cycles.

Highly durable and active non-precious air cathode catalyst for zinc air battery

The electrochemical stability of non-precious FeCo-EDA and commercial Pt/C cathode catalysts for zinc air battery have been compared using accelerated degradation test (ADT) in alkaline condition. Outstanding oxygen reduction reaction (ORR) stability of the FeCo-EDA catalyst was observed compared with the commercial Pt/C catalyst. The FeCo-EDA catalyst retained 80% of the initial mass activity for ORR whereas the commercial Pt/C catalyst retained only 32% of the initial mass activity after ADT. Additionally, the FeCo-EDA catalyst exhibited a nearly three times higher mass activity compared to that of the commercial Pt/C catalyst after ADT. Furthermore, single cell test of the FeCo-EDA and Pt/C catalysts was performed where both catalysts exhibited pseudolinear behaviour in the 12–500 mA cm −2 range. In addition, 67% higher peak power density was observed from the FeCo-EDA catalyst compared with commercial Pt/C. Based on the half cell and single cell tests the non-precious FeCo-EDA catalyst is a very promising ORR electrocatalyst for zinc air battery.