Zinc-air Research Articles

Freestanding Phosphonium Covalent Organic Frameworks with Efficient Hydroxide Conduction for Zinc–Air Batteries

Owing to their well‐defined crystalline pore structures and ordered functional ionic groups along the skeleton, ionic covalent organic frameworks (iCOFs) exhibit excellent performance and have significant potential for use in energy storage and conversion devices. Herein, we for the first time developed cationic phosphonium COFs with high hydroxide conduction even with low ion exchange capacity (IEC). Specifically, we synthesized COFs containing quaternary phosphonium groups as excellent ion transport moieties. Then, we fabricated freestanding phosphonium membranes through a vapor‐assisted method, which exhibited high hydroxide conductivity of 126 mS cm–1 at 80 °C from a minimal IEC of 1.17 mmol g–1. The resulting film was successfully applied to zinc–air batteries, demonstrating energy density of 96.1 mW cm–2, specific capacity of 95.0 mAh cm–2, and stable operation over 2,300 min. Overall, in addition to investigating a novel cationic functional group, we demonstrated a freestanding film formation method of COF‐based materials. The findings can provide a solid foundation for advancing the field of iCOFs to ion transport and promoting electrochemical applications.

Algae‐Derived Precursors for Sustainable Electrochemical Energy Storage

The simple production and harvesting of algae, along with its lower environmental impact and fewer geopolitical issues, make it a viable precursor for electrochemical energy storage devices. Algae represent a promising biomaterial for electrode materials in electrochemical energy storage devices, including hard carbon, sol–gel‐based anode batteries, sodium batteries, oxygen reduction reaction catalysts in zinc–air batteries, and cathode materials in zinc‐ion and lithium‐ion batteries. Algae‐based batteries are fabricated using methods like pyrolysis, hydrothermal processes, agar‐aided dissolution, electrolysis, annealing, and sol–gel methods. Among these, the sol–gel method using agar to construct refillable hydrogel batteries stands out. Agar's compatibility with acetylene black enhances electrochemical properties and offers the advantage of refill ability, which is challenging in metal‐ion batteries. Algae carbons have demonstrated enhanced specific capacity and cyclic performance, paving the way for their use in both medical and industrial applications. The article reviews the utilization of algae‐based batteries in different industrial and medical pacemaker applications as well as examines the feasibility of the operation of algae‐based batteries synthesized through various parameters and precursors.

Reconstructing the Coordination Environment of Fe/Co Dual-atom Sites towards Efficient Oxygen Electrocatalysis for Zn-Air Batteries.

Dual-atom catalysts with nitrogen-coordinated metal sites embedded in carbon can drive the oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc-air batteries (ZABs), and the further improvement is limited by the linear scaling relationship of intermediate binding energies in the absorbate evolution mechanism (AEM). Triggering the lattice oxygen mechanism (LOM) is promising to overcome this challenge, but has yet been verified since the lacking of bridge oxygen (O) in the rigid coordination environment of the metal centers. Here, we demonstrate that suitably tailored dual-atom catalysts of FeCo-N-C can undergo out-plane and in-plane reconstruction to form the both axial O and bridge O at the metal centers, and thus activate the LOM pathway. The tailored FeCo-N-C with shortened Fe-N bonds also favor the ORR process, therefore is a promising dual-atom oxygen catalyst. The assembled rechargeable ZABs demonstrate a peak power density of 332 mW cm-2, and exhibit no notable decline after ~ 720 h of continuous cycling.

Catalase‐Based Air‐Cathode for Biocompatible Zinc–Air Battery

AbstractThe use of catalase (CAT) from bovine liver as an electrocatalyst in the air electrode of a primary zinc–air battery (ZAB) with neutral electrolyte (pH 7.4) is reported. First, the use of Nafion for immobilizing CAT onto electrode surface allowed to obtain long‐term stability of the catalytic activity of CAT. Besides, analysis of the CAT and CAT‐Nafion as catalysts for oxygen reduction reaction (ORR) was carried out by linear sweep voltammetry (LSV) using a rotating ring‐disk electrode (RRDE), demonstrating a four‐electron ORR mechanism. Finally, CAT and CAT‐Nafion were tested as air electrodes in flooded ZAB and compared against human hemoglobin‐based ZAB. Our results demonstrated the significant influence of the protein coating of the heme groups on the ZAB performance, affecting greatly the discharge capacity and the power density.

Preparation of Hierarchical Porous Fe/N Codoped Carbon Nanosheets as Oxygen Reduction Reaction Electrocatalysts for the Zinc-Air Battery

Preparation of Hierarchical Porous Fe/N Codoped Carbon Nanosheets as Oxygen Reduction Reaction Electrocatalysts for the Zinc-Air Battery

Advanced Eutectogel Electrolyte for High-Performance and Wide-Temperature Flexible Zinc-Air Batteries.

Despite ongoing challenges, achieving further breakthroughs in the development of gel polymer electrolytes with a wide temperature range, excellent liquid retention capability and enhanced anode compatibility in flexible zinc-air batteries (FZABs) remains a significant objective. This study presents a significant advancement in the development of choline chloride/ethylene glycol-polyvinyl alcohol (ChCl/EG-PVA) eutectogel electrolyte, tailored for high-performance operation across a wide temperature range. Systematic in-situ and ex-situ characterizations and theoretical simulations confirm the formation of robust hydrogen bonding and denser polymer cross-linked networks within the prepared eutectogel, leading to enhanced liquid retention ability (93.7 % after 96 h exposure to air) and ion transport capacity (ionic conductivity of 171.3 mS cm-1). Additionally, the zincophilicity nature of the choline cation in eutectogel effectively suppresses dendrites growth. The assembled FZAB utilizing this eutectogel electrolyte achieves a peak power density of 109.3 mW cm-2 and a cycle life of 90 h. Notably, the power density of FZAB is maintained as high as 38.2 mW cm-2 at -40 °C and 63.2 mW cm-2 at 50 °C, demonstrating its prominent suitability for applications in extreme temperature conditions. The design of eutectogel provides a novel way to achieve the high-performance FZAB.

Composite Gel Polymer Electrolyte for High-Performance Flexible Zinc-Air Batteries.

Enhancing ionic conductivity and electrolyte uptake is of significance for gel polymer electrolytes (GPEs) for flexible zinc-air batteries (FZABs). Herein, a composite mesoporous silica/polyacrylamide (5 wt.% mPAM) GPE is constructed with comparable ionic conductivity to aqueous electrolytes, where the ionic conductivity is up to 337 mS cm-1, and the weight loss after exposing in air 72h is less than 18%, owing to the excellent electrolyte uptake and continuous ion migration network provided by the mesoporous silica fillers. When used as a quasi-solid-electrolyte, the rechargeable FZAB exhibited high electrochemical performance and structural stability, where the peak power density is up to 162.8mW cm-2, and the initial charge-discharge potential gap is as low as 0.62V, resulting in a long lifespan exceeding 110h, showcasing the combination of high durability, cost-effectiveness and easy production for practical applications.

Greatly Enhanced Oxygen Reduction Reaction in Anion Exchange Membrane Fuel Cell and Zn-Air Battery via Hole Inner Edge Reconstruction of 2D Pd Nanomesh.

Platinum group metals (PGM) have yet to be the most active catalysts in various sustainable energy reactions. Their high cost, however, has made maximizing the activity and minimizing the dosage become an urgent priority for the practical applications of emerging technologies. Herein, a novel 2DPd nanomesh structure possessing hole inner reconstructed edges (HIER) with exposed high energy facets and overstretched lattice parameters is fabricated through a facile room-temperature reduction method at gram-scale yields. The HIER enhances the catalytic performance of Pd in electrochemical oxygen reduction reaction (ORR), achieving superior mass activity (MA) of 2.672 A mgPd -1, which is 27.8 fold and 23.6 fold higher, respectively, than those of the commercial Pt/C (0.096 A mgPt -1) and Pd/C (0.113 A mgPd -1) at 0.9 VRHE. Most significantly, in H2-air anion exchange membrane fuel cell (AEMFC) and Zn-air battery (ZAB) applications, this unique Pd catalyst delivers a much-outperformed peak power density of 0.86 and 0.22W cm-2, respectively, compared with 0.54 and 0.13W cm-2 of the commercial Pt/C catalyst, indicating a novel pathway in electrocatalyst designs through HIER engineering.

Integration of Pre‐Activated Carbon‐Fabric Layers for Ampere‐Hour‐Scale Quasi‐Solid‐State Pouch‐Type Zinc–Air Batteries

AbstractAchieving ampere‐hour‐scale capacities in pouch‐type zinc–air batteries (ZABs) requires optimizing key factors, such as preventing inactive ZnO dendrite formation on zinc anodes and enhancing catalytic activity with efficient gas diffusion in the air cathode. Here, a pioneering flexible, large‐area, ampere‐hour‐scale quasi‐solid‐state ZAB is introduced, addressing these challenges through a novel preactivation strategy combined with a layered assembly approach. This method employs mass‐producible fibrous carbon textiles to form flexible fabrics that separate functions within multi‐stacked layers. Preactivated carbon fabric layers, independently functionalized and easily reassembled, enhance scalability and manufacturability. A bilayer catalytic air electrode, incorporating hydrophilic NiFe hydroxide and hydrophobic FeNC regions, ensures efficient charge and mass transfer, significantly boosting catalytic activity. To prevent dendrite formation on the zinc anode, a zincophilic copper interlayer is implemented. This configuration supports rapid, stable charge–discharge cycles at a high current density of 20 mA cm⁻2. The large‐area stacked bipolar structure pouch cells, exceeding 36 cm2, achieve a discharge capacity of up to 2500 mAh, maintaining high cycle stability through discharge–charge cycles with 200 mAh per cycle. This approach significantly enhances the scalability, manufacturability, and production potential of ultrahigh‐capacity wearable ZABs, making them practical for widespread application in various portable and flexible devices.

FeN4S1 Single-Atom Sites Anchored on Three-Dimensional Porous Carbon for Highly Efficient and Durable Oxygen Electrocatalysis.

Precisely designing asymmetric active centers and exploring their electronic regulation effects to prepare efficient bifunctional single-atom catalysts (SACs) is important for boosting the practical applications of zinc-air batteries (ZABs). Herein, an effective strategy has been developed by introducing an axial S atom to the FeN4 active center, simultaneously assisted by pyrolyzing the graphene oxide (GO) sheathed zeolitic-imidazolate framework-8 (ZIF8) composite and constructing a three-dimensional (3D) porous framework with abundant FeN4S1 moieties. This structure can accelerate the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics owing to the modulated electronic redistribution and d-band center with a reduced energy barrier. The optimal S-Fe-NC/rGO showcases a lower voltage gap (ΔE) of 0.64 V between both the ORR and OER half-wave potentials at 10 mA cm-2, highlighting the excellent bifunctional activities. The assembled S-Fe-NC/rGO rechargeable liquid ZABs deliver a power density of 154.05 mW·cm-2 and a desirable durability of >900 h. More importantly, the corresponding flexible solid-state ZABs exhibit considerable foldability.

Recent Advances in Rechargeable Zn-Air Batteries

Rechargeable Zn-air batteries are considered to be an effective energy storage device due to their high energy density, environmental friendliness, and long operating life. Further progress on rechargeable Zn-air batteries with high energy density/power density is greatly needed to satisfy the increasing energy conversion and storage demands. This review summarizes the strategies proposed so far to pursue high-efficiency Zn-air batteries, including the aspects of the electrocatalysts (from noble metals to non-noble metals), the electrode chemistry (from the oxygen evolution reaction to the organic oxidation reaction), electrode engineering (from powdery to free-standing), aqueous electrolytes (from alkaline to non-alkaline) and the battery configuration (from liquid to flexible). An essential evaluation of electrochemistry is highlighted to solve the challenges in boosting the efficiency of rechargeable metal-air batteries. In the end, the perspective on current challenges and future research directions to promote the industrial application of rechargeable Zn-air batteries is provided.

Fluorine-Induced Lattice Oxygen Participation in 2D Layered Double Hydroxide/MXene Hybrids for Efficient Oxygen Evolution.

In oxygen evolution reaction (OER), the participation of lattice oxygen can break the limitation of adsorption evolution mechanism, but the activation of lattice oxygen remains a critical challenge. Herein, a surface fluorinated highly active 2D/2D FeNi layered double hydroxide/MXene (F-LDH/MX) is demonstrated, boosting OER with the enhanced lattice-oxygen-mediated path. The introduction of fluorine promotes the self-evolution of catalyst in an alkaline environment, even without an external current. It further accelerates the formation of active metal oxyhydroxides with abundant oxygen vacancies under the operating potential. The introduced oxygen vacancy activates the lattice oxygen, increasing the proportion of lattice oxygen mechanism in OER. Owing to the synergistic effects of the 2D/2D hierarchical structure and the modulated active surface, F-LDH/MX possesses excellent electrochemical performances, including a low overpotential of 251 mV at 10 mA cm-2, a low Tafel slope of 40.28 mV dec-1, and robust stability. The water electrolyzer system with F-LDH/MX as the anode offers the benchmark current density at a low cell voltage of 1.53 V, while the Zn-air battery with F-LDH/MX as the air electrode exhibits a higher power density of 75.43 mW cm-2. This study presents a promising strategy to design highly active electrocatalysts for energy conversion and storage.

Promoting Reaction Kinetics of the Air Cathode for Neutral Zinc-Air Batteries by the Photothermal Effect.

Rechargeable neutral zinc-air batteries are attracting enormous research interest due to their long lifetime and low cost. However, the sluggish kinetics of the air cathode in the neutral electrolyte reduces the catalytic performance and impedes the power density and energy efficiency of zinc-air batteries. In this work, we propose a universal, sustainable, and effective approach to improve the kinetics of the air cathode through a solar-energy-induced photothermal effect. By illumination of the cost-effective carbon-black-based cathode, the temperature of the air cathode increases from room temperature to 40.5 °C, thereby accelerating the kinetics for the electrocatalytic reaction and reducing the interfacial resistance of the zinc-air battery. Attributed to the sunlight-promoted reaction kinetics, the neutral zinc-air battery exhibits a higher power density of 2.89 mW cm-2 and longer cycling durability over 250 h, 116 and 156% times the one without light illumination, significantly improved in contrast to the one without light illumination. Furthermore, we demonstrated solar energy-driven and solar-enhanced charging in the daytime and discharging at night, potentially applying in distributed energy storage applications. The proposed sustainable solar-energy-promoted reaction kinetics of air cathodes will drive the development of efficient zinc-air batteries and also inspire the rational design of electrocatalytic electrodes in other electrochemical devices.

Tailoring ORR Activity in Fe-N-C Catalysts through Phosphorus Incorporation.

Atomically dispersed iron and nitrogen co-doped carbon materials (Fe-N-C) represent promising non-precious metal catalysts for the oxygen reduction reaction (ORR), offering potential alternatives to noble metal-based benchmarks. In our study, we investigated the influence of phosphorus doping on the catalytic activity of Fe-N-C. The experimental research demonstrate that the doping of phosphorus significantly enhances the ORR activity. Specifically, the resulting Fe-NPC exhibits high metal loading and excellent ORR activity in 0.1 M KOH with an onset potential of 1.00 V and a half-wave potential of 0.864 V. Density functional theory (DFT) simulations reveal that phosphorus improves the electrocatalytic activity by activating O2 molecules and reducing the energy barrier (the hydrogenation reaction *OH→H2O) of the rate-determining step. Furthermore, Fe-NPC exhibits promising application prospects as an air cathode in Zn-air batteries, delivering a high maximum discharge power density of 180.3 mW cm-2 and outstanding discharge specific capacity (758.8 mAh g-1Zn) at a discharge current density of 10 mA cm-2.

Bamboo-derived aerogel with atomically dispersed Co as a high-performance bifunctional electrocatalyst for durable zinc-air batteries

The development of highly efficient and durable bifunctional electrocatalysts is crucial for rechargeable zinc-air batteries, which have garnered significant attention as a promising sustainable energy storage technology. Herein, a novel Co-N-C-1050 catalyst is synthesized using a high-temperature gas transport method, where high purity cobalt powder and bamboo biomass aerogel are treated with ammonia gas at 1050 °C. The resulting catalyst exhibits a 3D interconnected porous network composed of dense carbon fibers, which atomically dispersed Co, N, and C elements are uniformly distributed. The synergistic integration of highly active Co single atoms and N-doped 3D carbon fiber aerogel enables Co-N-C-1050 to demonstrate excellent bifunctional electrocatalytic performance for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), comparable to commercial Pt/C and RuO2 catalysts. This catalyst has a half-wave potential of 0.842 V for ORR and a potential of 1.472 V at 10 mA cm−2 for OER, outperforming N-C-1050 and benchmark catalysts. A zinc-air battery is driven by Co-N-C-1050 achieves a high power density of 135 mW/cm2 and exceptional stability over 138 h of charge/discharge cycling, surpassing the higher-cost Pt/C + RuO2 catalyst. This biomass aerogel based single-site Co-N-C catalyst offers a promising approach for developing high-efficiency and long-cycle-life zinc-air batteries.

Anion-induced optimization of non-aqueous zinc-air battery performance: Insights into OTF− selection

Rechargeable non-alkaline zinc-air batteries (ZABs) address the CO₂ incompatibility and instability issues of conventional alkaline batteries. However, the impact of solid discharge products like zinc oxide on discharge capacity at the air cathode remains unexplored. In this study, we investigate how anions influence ion pair solvation structures using Zinc trifluoromethanesulfonate (Zn(OTF)₂)-N, N-dimethylformamide (DMF) and Zinc acetate (Zn(Ac)₂)-DMF electrolytes, and how these structures affect the distribution of discharge product. Our finding shows that anions with lower donor numbers (DNs), like the weaker ligand OTF- (20.5), enhance the zinc ion activity and promote rapid Zn2⁺ reactions with oxygen during discharge, leading to a more than tenfold increase in discharge capacity. In contrast, acetate anions with higher DNs (43.3) form stable complexes, inhibiting zinc ion activity and causing the formation of film-like discharge products, which reduces ZAB performance. The Zn(OTF)₂-DMF electrolyte also enables a battery lifespan of over 200 h, more than fivefold compared to the acetate-based system.

Consolidating the Oxygen Reduction with Sub-Polarized Graphitic Fe-N4 Atomic Sites for an Efficient Flexible Zinc-Air Battery.

The effectuation of the Zn-air battery (ZAB) is appealing for active and durable catalysts to kinetically drive the sluggish cathodic oxygen reduction reaction (ORR). Atomic metal-Nx-C sites are widely witnessed with Pt-like activity, but their demetalations still severely restrict the durability in ORR. Here we have profiled an ordered hierarchical porous carbon supported Fe-N4 single-atom (FeNC) catalyst by a template derivation method for efficient ORR and flexible ZAB studies. The FeNC structure is observed with a sub-polarized graphitic Fe-N4 coordination with a shortened Fe-N bond for potentially consolidating the ORR, together with the hierarchical porous matrix for kinetical mass transfer. Resultantly, the optimized FeNC catalyst showcases Pt-beyond alkaline ORR activity (E1/2 = 0.95 V) with long-term durability for 100 h, delivering the flexible ZAB device with high power density (251 mW cm-2) and durable cycle life (80 h). This research underscores the criterion in rationalizing active and robust ORR catalysts through metal-nitrogen bond modulation.

Comparative study of the performance of α-MnO2 and amorphous manganese dioxide air electrodes for zinc-air batteries

Comparative study of the performance of α-MnO2 and amorphous manganese dioxide air electrodes for zinc-air batteries

Optimizing cobalt/nickle sulfide heterojunction interface with ordered porous framework for efficient rechargeable zinc-air batteries

Developing efficient oxygen evolution/reduction reaction (OER/ORR) bifunctional catalysts is essential to improve zinc-air batteries (ZABs) performance. In this study, an OER/ORR bifunctional catalyst consists of cobalt and nickel sulfide heterojunction with three-dimensional ordered mesoporous structure is fabricated (3DOM Co9S8/Ni3S4). In-situ attenuated total reflection Fourier transform infrared tests and theoretical calculations reveal that the heterojunction structure promotes electrons transfer from Co9S8 to Ni3S4 and modulates the d-band center, thus optimizing the adsorption/desorption of *OH, *O and *OOH oxygen-containing intermediates and contributing to the improvement of the reactivity of the catalyst. In-situ Raman analysis shows that 3DOM Co9S8/Ni3S4 undergoes surface reconstruction to form highly reactive NiOOH species during the OER process. Meanwhile, the 3DOM framework structure also increases the catalyst specific surface area and benefits the mass transfer process during the reactions. As a result, 3DOM Co9S8/Ni3S4 exhibits a low OER overpotential (334 mV) at 10 mA cm−2 and the ORR half-wave potential is 0.77 V vs. RHE. The rechargeable ZABs with 3DOM Co9S8/Ni3S4 cathode deliver an energy density of 760.73 mAh g−1 at 10 mA cm−2 and stable cycling performance for 100 hours. This study provides guidance for developing efficient heterojunction bifunctional catalysts for ZABs.

DFT-guided synthesis of N, B dual-doped porous carbon from saccharina japonica for enhanced oxygen reduction catalysis

IntroductionThe oxygen reduction reaction (ORR) is a crucial determinant of the energy transformation capacity of fuel cells. This study investigates the performance of N and B dual-doped carbon in ORR.MethodsSix models using density functional theory (DFT) are developed to compare the performance of different doping strategies. A highly efficient dual-doped carbon ORR catalyst (S-850-1) is synthesized from Saccharina japonica, containing 4.54 at% N and 1.05 at% B atom.ResultsElectrochemical analysis reveals that S-850-1 significantly outperforms the nitrogen mono-doped carbon S-850, exhibiting a higher half-wave potential of 0.861 V and a greater limited current density of −5.60 mA cm⁻2, compared to S-850’s 0.838 V and −5.24 mA cm⁻2. Furthermore, S-850-1 surpasses the performance of 20% Pt/C, demonstrating enhanced durability and exceptional resistance to CO and methanol. The 1.40 V open circuit voltage produced by S-850-1 when integrated into a Zn-air battery can power an LED light.DiscussionBoth theoretical and practical evaluations validate the excellent ORR performance of nitrogen and boron dual-doped carbon, as evidenced by the agreement between the electrochemical results and DFT calculations. This work not only extends the range of ORR catalysts derived from biomass but also provides guidance on creating and producing affordable, effective catalysts that utilize natural resources.