Air Cathode Research Articles

Many-objective optimization for structural parameters of the fuel cell air compressor based on the Stacking model under multiple operating conditions

As the central element of the cathode air supply system, the centrifugal air compressor is pivotal to the regular and efficient operation of on-board fuel cells. In an attempt to further enhance the overall properties of the air compressor, the computational fluid dynamics (CFD) simulation model and Stacking model are developed and calibrated in this study. On this basis, the Many-Objective Random Walk Gray Wolf Optimizer (MORW-GWO) algorithm is proposed to perform many-objective optimization for compressor structural parameters, and the intrinsic mechanisms of performance improvements are elaborated based on three-dimensional flow analysis. The results indicate that the Stacking model achieves excellent predictive performance and generalization ability through the coupling and mutual error correction of base learners and the meta-learner. The MORW-GWO algorithm demonstrates outstanding many-objective optimization capability, convergence ability and universality. Compared to the original compressor, the optimized air compressor achieves improvements of 2.8%, 2.3%, 9.3% and 16.0% in the pressure ratio, outlet temperature, isentropic efficiency and adiabatic compression work, respectively. Besides, it is found that the internal energy loss, separation loss, friction loss, gas leakage and backflow of the optimized air compressor are reduced through the 3-D flow characteristic analysis. The findings can contribute to the many-objective optimization of compressor structural parameters by giving theoretical guidance, data support and directional evidence.

Synergistic Fe and Co binary single atoms based air cathodes for high performance and ultra-stable Zn-air batteries

Cost-effective highly efficient and stable air cathodes are critical for practical applications of rechargeable Zn-air batteries (ZABs). In this work, air cathodes constructed by loading carbon nanotube supported N-doped carbon anchored Fe and Co binary single atoms, f-Fe1Co1/CNT, in carbon paper composited nickel foams, NF/CP, were developed for ZABs, exhibiting outstanding bifunctional oxygen electrocatalytic activities (ΔE = 0.671 V) with a half-wave potential (E1/2) of 0.880 V (vs. RHE) for oxygen reduction reaction (ORR) and an overpotential of 321 mV at 10 mA cm−2 (η10) for oxygen evolution reaction (OER) in 0.1 M KOH, which outperformed the benchmark (Pt/C+IrO2)-based air cathode (ΔE = 0.773 V, E1/2 = 0.850 V, η10 = 393 mV). With the unique air cathode design of compositing catalyst-loading layer (nickel foam) with gas diffusion layer (carbon paper), the f-Fe1Co1/CNT@NF/CP//Zn ZAB delivered a remarkable discharge peak power density of 282.1 mW cm−2 at an ultra-high current density of 427.7 mA cm−2 and maintained an ultra-small potential gap of 0.75 V after operations at 10 mA cm−2 for 3300 cycles (1100 h), largely outperforming the (Pt/C+IrO2)@NF/CP//Zn ZAB (162.4 mW cm−2 at 247.3 mA cm−2, 0.86 V, 590 cycles). Density functional theory calculations revealed the positive long-range synergy between Fe-N4 and Co-N4 single atoms, significantly reducing the free energies of the rate-determining steps, oxygen protonation for ORR and formation of oxyhydroxides for OER at the main active site Fe-N4, to realize the much enhanced oxygen electrocatalytic activities.

High-Density CoSe2 Sites Embedded within 2D Porous N-Doped Carbon for High-Performance Oxygen Reduction Reaction Electrocatalysis.

Designing and fabricating efficient and stable nonprecious metal-based oxygen reduction reaction (ORR) electrocatalysts is a pressing and challenging task for the pursuit of sustainable new energy devices. Herein, porous P-CoSe2@NC electrocatalysts with high-density carbon-coated CoSe2 sites were successfully fabricated based on a pyridyl-porphyrinic metal-organic framework (Co-TPyP MOF) via a molten salt-assisted synthesis method. The hierarchical pore and N-doping carbon substrate of P-CoSe2@NC promotes mass transfer and electron-transfer efficiency, which is beneficial to maximize CoSe2 site utilization. Well-designed P-CoSe2@NC exhibits efficient ORR catalytic activity with a high half-wave potential of 0.863 V and excellent catalytic stability. Meanwhile, rechargeable aqueous primary/quasi-solid-state ZABs based on a P-CoSe2@NC air cathode show a high peak power density and exceptional operating stability, catering to the demands of practical applications. The qualified performance and structure stability of the electrocatalytic system may be mainly attributed to the protection of the CoSe2 nanoparticle by the coated carbon layer. Given the rational design of the structure and the component of the electrocatalyst with enhanced ORR activity, we believe that this work has provided a reliable pathway to the development of high-performance transition-metal chalcogenides for energy-storage and -conversion devices.

Assessing the Performance of Continuous-Flow Microbial Fuel Cells and Membrane Electrode Assembly with Electrodeposited Mn Oxide Catalyst

Microbial fuel cells (MFCs) are considered promising energy sources whereby chemical energy is converted into electricity via bioelectrochemical reactions utilizing microorganisms. Several factors affect MFC performance, including cathodic reduction of oxygen, electrode materials, cell internal and external resistances, and cell design. This work describes the effect of the catalyst coating in the air-cathode membrane electrode assembly (MEA) for a microbial fuel cell (MFC) prepared via electrodeposition of manganese oxide. The characterization of the synthesized air-cathode MFC, operating in a continuous mode, was made via electrochemical impedance spectroscopy (EIS) analyses for the determination of the intrinsic properties of the electrode that are crucial for scalability purposes. EIS analysis of the MFCs and of the MEA reveals that the anode and cathode contribute to polarization resistance by about 85% and 15%, respectively, confirming the high catalytic activity of the Mn-based air cathode. The maximum power density of the Mn-based cathode is about 20% higher than that recorded using a Pt/C electrode.

Performance of a Fe-N-C Catalyst in Single-chamber MFC Air-cathode at Neutral Media

Performance of a Fe-N-C Catalyst in Single-chamber MFC Air-cathode at Neutral Media

Carbon-coated Fe3O4@cotton fiber biomass carbon for the oxygen reduction reaction in air cathode microbial fuel cells

Iron-based oxide catalysts on biomass carbon fibers can jointly use their respective advantages of chemical composition and structure to develop catalysts for the oxygen reduction reaction (ORR). In this study, carbon-coated Fe3O4@cotton fiber biomass carbon (C@Fe3O4@CFBC) was prepared as an ORR catalyst through hydrothermal growth and calcination treatment for air cathode microbial fuel cells (MFCs). The carbon coating layer enhanced the O2 adsorption energy, decreased the overpotential, and promoted surface activation of the Fe3O4 catalyst. The carbon coating layer can modulate the surface electronic structure of the Fe3O4 catalyst with C–O–Fe bonding and improve the electrical conductivity to accumulate electrons on the Fe3O4 surface to enhance the ORR performance. The CFBC supported Fe3O4 nanoparticles to prevent severe aggregation and expose more effective surface-active sites. The C@Fe3O4@CFBC catalyst achieved a high positive half-wave potential (0.801 V) and low Tafel slope (73.7 mV·dec−1) compared with the Pt/C catalyst (0.877 V and 94.3 mV·dec−1). The assembled air cathode MFCs achieved a desirable maximum power density (1059 ± 16 mW·m−2) based on 1266 ± 94 mW·m−2 of Pt/C MFC devices. This work provides a strategy for designing highly active non-precious metal catalysts for air cathode MFCs.

Intermittent investigations on attenuation mechanism of rechargeable zinc-air batteries during charge/discharge cycles.

Rechargeable zinc-air batteries (RZABs) are an ideal substitute for energy storage, but the short cycle longevity during long-term charge/discharge operation is one of the bottleneck factors that seriously restrict commercial application. Herein, the FeCo alloy/N, S co-doped carbon aerogel (NSCA/FeCo) were prepared as catalysts of cathode for RZABs. We investigated the polarization and impedance on long-term cycles during the battery operation to explore the attenuation mechanism. The results indicated that the roundtrip efficiency of batteries during charge/discharge cycles reduced fast initially and then slow. Besides, the comparative experiment was tested through the replacement of a new electrolyte and a zinc sheet. It is manifested that the failure of the battery is mainly due to the attenuation of the air cathode performance. Therefore, to further disclose the influencing factors and internal mechanisms of air cathode performance degradation, we conducted a series of characterization and testing, including the hydrophilicity, surface morphology, elemental composition, and electrochemical performance of three-electrode systems at different cycle times. This work not only provides a theoretical basis for deeply comprehending the attenuation mechanism of the cathode but also serves a reference for the material design and operating condition optimization of RZABs.

A rechargeable calcium-oxygen battery that operates at room temperature.

Calcium-oxygen (Ca-O2) batteries can theoretically afford high capacity by the reduction of O2 to calcium oxide compounds (CaOx) at low cost1-5. Yet, a rechargeable Ca-O2 battery that operates at room temperature has not been achieved because the CaOx/O2 chemistry typically involves inert discharge products and few electrolytes can accommodate both ahighly reductive Ca metal anode and O2. Here we report a Ca-O2 battery that is rechargeable for 700 cycles at room temperature. Our battery relies on a highly reversible two-electron redox to form chemically reactive calcium peroxide (CaO2) as the discharge product. Using a durable ionic liquid-based electrolyte, this two-electron reaction is enabled by the facilitated Ca plating-stripping in the Ca metal anode at room temperature and improved CaO2/O2 redox in the air cathode. We show the proposed Ca-O2 battery is stable in air and can be made into flexible fibres that are weaved into textile batteries for next-generation wearable systems.

Application of biomimetically synthesized silver nanoparticles as cathode catalyst, quorum-quencher, and anti-biofouling agent for the performance boosting of microbial fuel cell

A microbial fuel cell (MFC) is a cutting-edge bioelectrochemical technology, which demonstrates power and other valuables recovery while treating wastewater by cultivating electroactive microbes. However, rampant biofilm growth over the cathode surface of air cathode MFC exacerbates the oxidation-reduction reaction rate, triggering a dip in the overall performance of MFC. In this sense, biosynthesized silver nanoparticles (AgNPs) have garnered a plethora of potential applications as cathode catalysts as well as anti-biofouling agent for MFCs without harming nature. The MFC equipped with the mixture of aloe vera and algae (@5 mg/cm2) synthesized AgNPs on cathode generated a maximum power density of 66.5 mW/m2 and chemical oxygen demand removal efficiency of 85.2%, which was ca. 5.6 times and 1.2 times higher compared to control MFC operated without any catalyst on cathode. Thus, this investigation paves the way for using eco-amiable, low-cost bioderived organic compounds to assist MFC in achieving high power output and other valuables with minimal reliance on chemicals.

Performance Assessment and Optimization of the Ultra-High Speed Air Compressor in Hydrogen Fuel Cell Vehicles

Air compressors in hydrogen fuel cell vehicles play a crucial role in ensuring the stability of the cathode air system. However, they currently face challenges related to low efficiency and poor stability. To address these issues, the experimental setup for the pneumatic performance of air compressors is established. The effects of operational parameters on energy consumption, efficiency, and mass flow rate of the air compressor are revealed based on a Morris global sensitivity analysis. Considering a higher flow rate, larger efficiency, and lower energy consumption simultaneously, the optimal operating combination of the air compressor is determined based on grey relational multi-objective optimization. The optimal combination of operational parameters consisted of a speed of 80,000 rpm, a pressure ratio of 1.8, and an inlet temperature of 18.3 °C. Compared to the average values, the isentropic efficiency achieved a 48.23% increase, and the mass flow rate rose by 78.88% under the optimal operational combination. These findings hold significant value in guiding the efficient and stable operation of air compressors. The comprehensive methodology employed in this study is applicable further to investigate air compressors for hydrogen fuel cell vehicles.

F Doping-Induced Multicomponent Synergistic Active Site Construction toward High-Efficiency Bifunctional Oxygen Electrocatalysis for Rechargeable Zn-Air Batteries.

The commercialization of rechargeable Zn-air batteries (ZABs) relies on the material innovation to accelerate the sluggish oxygen electrocatalysis kinetics. Due to the differentiated mechanisms of reverse processes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), rationally integrating dual sites for bifunctional oxygen electrocatalysis is prerequisite yet remains challenging. Herein, multicomponent synergistic active sites within highly graphitic carbon substrate are exquisitely constructed, which is accomplished by fluorine (F) modulation strategy. The incorporation of F dopants facilitates pyridinic N formation for anchoring single metal sites, thus guaranteeing the coexistence of sufficient M-Nx sites and metal nanoparticles toward bifunctional oxygen electrocatalysis. As a result, the optimal catalyst, denoted as F NH2-FeNi-800, outperforms commercial Pt/C+RuO2 with smaller gap between Ej = 10 and E1/2 (ΔE) of 0.63V (vs 0.7V for Pt/C+RuO2), demonstrating its superior bifunctionality. Beyond that, its superiority is validated in homemade rechargeable ZABs. ZABs assembled using F NH2-FeNi-800 as the air cathode delivers higher peak power density (123.8mW cm-2) and long-cycle lifetime (over 660 cycles) in comparison with Pt/C@RuO2 (68.8mW cm-2; 300 cycles). The finding not only affords a highly promising oxygen electrocatalyst, but also opens an avenue to constructing multifunctional active sites for heterogeneous catalysts.

Energy harvesting from plants using hybrid microbial fuel cells; potential applications and future exploitation.

Microbial Fuel Cells (MFC) can be fuelled using biomass derived from dead plant material and can operate on plant produced chemicals such as sugars, carbohydrates, polysaccharides and cellulose, as well as being "fed" on a regular diet of primary biomass from plants or algae. An even closer relationship can exist if algae (e.g., prokaryotic microalgae or eukaryotic and unicellular algae) can colonise the open to air cathode chambers of MFCs driving photosynthesis, producing a high redox gradient due to the oxygenic phase of collective algal cells. The hybrid system is symbiotic; the conditions within the cathodic chamber favour the growth of microalgae whilst the increased redox and production of oxygen by the algae, favour a more powerful cathode giving a higher maximum voltage and power to the photo-microbial fuel cell, which can ultimately be harvested for a range of end-user applications. MFCs can utilise a wide range of plant derived materials including detritus, plant composts, rhizodeposits, root exudates, dead or dying macro- or microalgae, via Soil-based Microbial Fuel Cells, Sediment Microbial Fuel Cells, Plant-based microbial fuel cells, floating artificial islands and constructed artificial wetlands. This review provides a perspective on this aspect of the technology as yet another attribute of the benevolent Bioelectrochemical Systems.

Unsaturated cobalt-nitrogen atomic sites in necklace-like hairy fibers towards highly efficient oxygen electrocatalysis for flexible Zn-Air battery

Exploration of single-atom catalysts (SACs) with high activity and efficient utilization efficiency holds great promise in the field of electrocatalysis. However, it is still a challenge to rationally design the SACs due to their properties are greatly influenced by the local electron environment and the effective substrate. Herein, we synchronously realized the modulation of unsaturated cobalt-nitrogen atomic sites (CoN3) and uniformly archoring them on the carbon-nanotube assembled necklace-like fiber (NLF). The unsaturated cobalt-nitrogen atomic sites with asymmetric structure favor the adsorption/desorption features and promote the electrocatalytic reactions of oxygen. Meanwhile, the hairy NLF fiber with the highly conductive and porous matrix guarantees the active sites accessibility and fast kinetics. In addition, the unique necklace-like configuration endows good mechanical strength and high reliability for the CoN3 NLF fiber. Both density functional theoretical (DFT) calculation and the experimental results reveal its superior catalytic properties and good reliability in the oxygen electrocatalytic reactions. Moreover, the finite element analysis (FEA) and the corresponding tests further certify its high pliability and good robustness. Based on the CoN3 NLF fiber air cathode, the aqueous Zn-air battery (ZAB) delivers a high power density (306 mW cm−2) and outstanding cycling stability over 300 h. Furthermore, all-solid-state ZAB based on the freestanding CoN3 NLF air cathode shows considerable flexibility and superior reliability over a wide range of temperatures (-20∼25 °C). Therefore, this work provides an effective catalyst design for the development of metal-air batteries for diverse applications.

Preparation of Co[sbnd]N co-doped carbon nanosheets electrocatalyst for efficient oxygen reduction reaction in zinc-air battery

It is very vital that there be a high-activity and serviceable catalyst for the oxygen reduction reaction (ORR) in the Zn-air Battery. Herein, utilizing g-C3N4 as a self-sacrifice template and Cobalt-His framework as the precursor, a simple strategy was developed to synthesize Co/N co-doped carbon nanosheets (CoNC 800) as a metal electrocatalyst for ORR. Due to the Co/N co-doped CoNX site and large specific surface area, the acquired materials show a preeminent ORR catalytic activity with an initial potential (~0.96 V) and half-wave potential (E1/2) of 0.85 V (vs. RHE) in an alkaline medium. Most importantly, the material has superior long-term stability and methanol tolerance than Pt/C. Furthermore, we assembled the Zn-air battery employing catalyst as an air cathode catalyst, demonstrating maximum power densities of 144 mWcm−2, a specific capacity of 821.50 Wh·kg−1, and charge/discharge cycle stability of more than 140 h. The nanosheet structure electrocatalysts derived from the Cobalt-His framework and g-C3N4 provide an innovative and instructive approach to the design of diverse nanomaterials.

Degradation of cathode in air and its influences on direct recycling

Delamination has been widely used in direct recycling of spent lithium-ion batteries (LIBs) as the first step to harvest cathode materials from cathodes. The variations of the recycling performance have been documented in many studies. The main mechanism of delamination is the inactivation of bonding forces provided by the polyvinylidene fluoride (PVDF) binder. It is believed that the storage environment (air exposure time) will affect the performances of delamination to some extent. Three representative methods (direct calcination, pressure washing, and NMP solvent extraction) for delamination were studied to elucidate the effect of air exposure time on delamination efficiency. The peel-off efficiency (98–99%) of the direct calcination method was barely influenced by air exposure time. The pressure washing system or NMP solvent extraction method also exhibited high peel-off efficiency using samples after a long air exposure time (1 month), however these methods may have problems regarding Al contamination, i.e., 11.5 mg/g of pressure washing system and 134.4 mg/g of NMP solvent extraction. Results suggest that enhanced adhesion (0.11 MPa/month) could be a potential reason why air contact time affects delamination, with O2 and/or H2O acting as contributors. This finding may help to maximum performance of delamination, as it highlights the importance of storage conditions of the spent LIBs prior to direct recycling.

Molecularly engineered potential of d-orbital modulated iron-bridged delaminated MBene for rechargeable Zn–air batteries

An air cathode with high catalytic activity and reversibility toward the OER and ORR is designed by the typical coordinations of iron phthalocyanine molecule crystals on delaminated MoAl1−xB MBene sheets.

Graphitized mango seed as an effective 3D anode in batch and continuous mode microbial fuel cells for sustainable wastewater treatment and power generation.

Herein, we explored the utilization of graphitized mango seeds as 3D-packed anodes in microbial fuel cells (MFCs) powered by sewage wastewater. Mango seeds were graphitized at different temperatures (800 °C, 900 °C, 1000 °C, and 1100 °C) and their effectiveness as anodes was evaluated. Surface morphology analysis indicated that the proposed anode was characterized by layered branches and micro-sized deep holes, facilitating enhanced biofilm formation and microorganism attachment. Maximum power densities achieved in the MFCs utilizing the mango seed-packed anodes graphitized at 1100 °C and 1000 °C were 2170.8 ± 90 and 1350.6 ± 125 mW m-2, respectively. Furthermore, the weight of the graphitized seed anode demonstrated a positive correlation with the generated power density and cell potential. Specifically, MFCs fabricated with 9 g and 6 g anodes achieved maximum power densities of 2170.8 ± 90 and 1800.5 ± 40 mW m-2, respectively. A continuous mode air cathode MFC employing the proposed graphitized mango anode prepared at 1100 °C and operated at a flow rate of 2 L h-1 generated a stable current density of approximately 12 A m-2 after 15 hours of operation, maintaining its stability for 75 hours. Furthermore, a chemical oxygen demand (COD) removal efficiency of 85% was achieved in an assembled continuous mode MFC. Considering that the proposed MFC was driven by sewage wastewater without the addition of external microorganisms, atmospheric oxygen was used as the electron acceptor through an air cathode mode, agricultural biomass waste was employed for the preparation of the anode, and a higher power density was achieved (2170.8 mW m-2) compared to reported values; it is evident that the proposed graphitized mango seed anode exhibits high efficiency for application in MFCs.

Aluminum-air batteries: current advances and promises with future directions.

Owing to their attractive energy density of about 8.1 kW h kg-1 and specific capacity of about 2.9 A h g-1, aluminum-air (Al-air) batteries have become the focus of research. Al-air batteries offer significant advantages in terms of high energy and power density, which can be applied in electric vehicles; however, there are limitations in their design and aluminum corrosion is a main bottleneck. Herein, we aim to provide a detailed overview of Al-air batteries and their reaction mechanism and electrochemical characteristics. This review emphasizes each component/sub-component including the anode, electrolyte, and air cathode together with strategies to modify the electrolyte, air-cathode, and even anode for enhanced performance. The latest advancements focusing on the specific design of Al-air batteries and their rechargeability characteristics are discussed. Finally, the constraints and prospects of their use in mobility applications are also covered in depth. Thus, the present review may pave the way for researchers and developers working in energy storage solutions to look beyond lithium/sodium ion-based storage solutions.

Regulating the frontier orbital of iron phthalocyanine with nitrogen doped carbon nanosheets for improving oxygen reduction activity.

Iron phthalocyanine (FePc) has attracted widespread attention for its tunable electronic structure. However, the Fe-N sites suffer from undesirable oxygen reduction activity due to the symmetric geometries. A suitable substrate was thus needed to induce electron redistribution around Fe-N to improve the activity. Herein, ultrathin nitrogen-doped carbon nanosheets (N-CNSs) were prepared by a simple high temperature pyrolysis. Then iron phthalocyanine was loaded on the ultrathin nitrogen-doped carbon nanosheets (FePc@N-CNSs) by a low-cost and simple solution method. This composite catalyst shows an excellent ORR activity with a half potential of 0.88 V, an onset potential of 0.99 V and durability superior to commercial Pt/C. When used as an air cathode catalyst for rechargeable zinc-air batteries, FePc@N-CNS modified batteries outperform Pt/C + RuO2 modified batteries with higher power density and superior constant current charge-discharge cycling stability of 37 hours. The regulated electronic structure of FePc by the N-CNS substrate was revealed further by DFT calculations, which explained the enhanced adsorption of the active center to the intermediates and the increased ORR performance.

Chemical fabrication and synergistic mechanism of N-doped carbon modified with FeP as catalysts for flexible rechargeable Zn–air batteries

A 3D porous N-doping Paulownia-derived carbon modified with FeP nanoparticles (FeP@NPW) was used as an air cathode for flexible rechargeable Zn–air batteries. The flexible rechargeable ZAB based on FeP@NPW exhibits outstanding cycle stability and durability.