Recent progress of self-supported air electrodes for flexible Zn-air batteries

Smart wearable devices are regarded to be the next prevailing technology product after smartphones and smart homes,and thus there has recently been rapid development in flexible electronic energy storage devices.Among them,flexible solid-state zinc-air batteries have received widespread attention because of their high energy density,good safety,and stability.Efficient bifunctional oxygen electrocatalysts are the primary consideration in the development of flexible solid-state zinc-air batteries,and self-supported air cathodes are strong candidates because of their advantages including simplified fabrication process,reduced interfacial resistance,accelerated electron transfer,and good flexibility.This review outlines the research progress in the design and construction of nanoarray bifunctional oxygen electrocatalysts.Starting from the configuration and basic principles of zinc-air batteries and the strategies for the design of bifunctional oxygen electrocatalysts,a detailed discussion of self-supported air cathodes on carbon and metal substrates and their uses in flexible zinc-air batteries will follow.Finally,the challenges and opportunities in the development of flexible zinc-air batteries will be discussed.

Bulk preparation of free-standing single-iron-atom catalysts directly as the air electrodes for high-performance zinc-air batteries

The keen interest in fuel cells and metal-air batteries stimulates a great deal of research on the development of a cost-efficient and high-performance catalyst as an alternative to traditional Pt to boost the sluggish oxygen reduction reaction(ORR)at the cathode.Herein,we report a facile and scalable strategy for the large-scale preparation of a free-standing and flexible porous atomically dispersed Fe-N-doped carbon microtube(FeSAC/PCMT)sponge.Benefiting from its unique structure that greatly facilitates the catalytic kinetics,mass transport,and electron transfer,our FeSAC/PCMT electrode exhibits excellent performance with an ORR potential of 0.942 V at^(-3) mA cm^(-2).When the FeSAC/PCMT sponge was directly used as an oxygen electrode for liquid-state and flexible solid-state zinc-air batteries,high peak power densities of 183.1 and 58.0 mW cm^(-2) were respectively achieved,better than its powdery counterpart and commercial Pt/C catalyst.Experimental and theoretical investigation results demonstrate that such ultrahigh ORR performance can be attributed to atomically dispersed Fe-N_(5) species in FeSAC/PCMT.This study presents a cost-effective and scalable strategy for the fabrication of highly efficient and flexible oxygen electrodes,provides a significant new insight into the catalytic mechanisms,and helps to realize significant advances in energy devices.

High quality Sb-doped SnO2 electrodes with high oxygen evolution potential prepared by in situ hydrothermal synthesis method

High quality Sb-doped SnO2 electrode, with high oxygen evolution potential of 3.0 V, was successfully synthesized on the Ti substrates by in situ hydrothermal synthesis method.

Fabrication and study of supercapacitor electrodes based on oxygen plasma functionalized carbon nanotube fibers

Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron microscopy(SEM),Raman spectroscopy,and X-ray Photoelectron Spectroscopy(XPS).It was found from the conducted electrochemical measurements that the functionalized fibers showed a 132.8% increase in specific capacitance compared to non-functionalized fibers.Dye-adsorption test and the obtained Randles-Sevcik plot demonstrated that the oxygen plasma functionalized fibers exhibited increased surface area.It was further established by Brunauer-Emmett-Teller(BET)measurements that the surface area of the CNT fibers was increased from 168.22 m^2/g to 208.01 m^2/g after plasma functionalization.The pore size distribution of the fibers was also altered by this processing.The improved electrochemical data was attributed to enhanced wettability,increased surface area,and the presence of oxygen functional groups,which promoted the capacitance of the fibers.Fiber supercapacitors were fabricated from the oxygen plasma functionalized CNT fiber electrodes using different electrolyte systems.The devices with functionalized electrodes exhibited excellent cyclic stability(93.2% after 4000 cycles),flexibility,bendability,and good energy densities.At 0.5 m A/cm^2,the EMIMBF4 device revealed a specific capacitance,which is 27% and 65%greater than the specific capacitances of devices using EMIMTFSI and H2SO4 electrolytes,respectively.The practiced in this work plasma surface processing can be employed in other applications where fibers,yarns,ribbons,and sheets need to be chemically modified.

Cobalt-Free BaFe_(0.6)Zr_(0.1)Y_(0.3)O_(3−δ)Oxygen Electrode for Reversible Protonic Ceramic Electrochemical Cells

Reversible protonic ceramic electrochemical cells(R-PCECs)are ideal,high-effi ciency devices that are environmentally friendly and have a modular design.This paper studies BaFe_(0.6)Zr_(0.1)Y_(0.3)O_(3−δ)(BFZY3)as a cobalt-free perovskite oxygen electrode for high-performance R-PCECs where Y ions doping can increase the concentration of oxygen vacancies with a remarkable increase in catalytic performance.The cell with confi guration of Ni-BZCYYb/BZCYYb/BFZY3 demonstrated promising performance in dual modes of fuel cells(FCs)and electrolysis cells(ECs)at 650℃with low polarization resistance of 0.13Ωcm^(2),peak power density of 546.59 mW/cm^(2)in FC mode,and current density of−1.03 A/cm^(2)at 1.3 V in EC mode.The alternative operation between FC and EC modes for up to eight cycles with a total of 80 h suggests that the cell with BFZY3 is exceptionally stable and reversible over the long term.The results indicated that BFZY3 has considerable potential as an air electrode material for R-PCECs,permitting effi cient oxygen reduction and water splitting.

Oxygen Evolution Efficiency and Chlorine Evolution Efficiency for Electrocatalytic Properties of MnO_2-based Electrodes in Seawater

To improve both oxygen evolution efficiency and stability at high temperatures, Mn, Mn+Mo, Mn+Mo+V, and Mn+Fe+V oxide electrodes were prepared on a Ti substrate, with an intermediate layer of IrO_2, by an anodic deposition method. The crystal structure, surface morphology, pore size distribution, specific surface area, and voltammetric charge were then characterized for each electrode. The results demonstrated that for Mn-O electrodes, the preferential orientation of the(100) crystal plane and the mesopore structure played negative roles in the oxygen evolution reaction. On the basis of the electrocatalytic properties of MnO2-based electrodes in seawater, the outer surface voltammetric charge at a scan rate of 500 mV·s-1 was shown to effectively indicate whether oxygen evolution reactions were preferred over chlorine evolution reactions. The Mn-O electrode exhibited oxygen evolution efficiency of only 47.27%, whereas the Mn+Mo, Mn+Mo+V and Mn+Fe+V oxide electrodes displayed oxygen evolution efficiency of nearly 100%. This means that adding Mo, V, and Fe elements to the electrode can improve its crystal structure and morphology as well as further enhancing its oxygen evolution efficiency.

Handily etching nickel foams into catalyst-substrate fusion self‐stabilized electrodes toward industrial‐level water electrolysis

The key challenge of industrial water electrolysis is to design catalytic electrodes that can stabilize high current density with low power consumption(i.e.,overpotential),while industrial harsh conditions make the balance between electrode activity and stability more difficult.Here,we develop an efficient and durable electrode for water oxidation reaction(WOR),which yields a high current density of 1000 mA cm−2 at an overpotential of only 284 mV in 1M KOH at 25°C and shows robust stability even in 6M KOH strong alkali with an elevated temperature up to 80°C.This electrode is fabricated from a cheap nickel foam(NF)substrate through a simple one-step solution etching method,resulting in the growth of ultrafine phosphorus doped nickel-iron(oxy)hydroxide[P-(Ni,Fe)O_(x)H_(y)]nanoparticles embedded into abundant micropores on the surface,featured as a self-stabilized catalyst–substrate fusion electrode.Such self-stabilizing effect fastens highly active P-(Ni,Fe)O_(x)H_(y)species on conductive NF substrates with significant contribution to catalyst fixation and charge transfer,realizing a win–win tactics for WOR activity and durability at high current densities in harsh environments.This work affords a cost-effective WOR electrode that can well work at large current densities,suggestive of the rational design of catalyst electrodes toward industrial-scale water electrolysis.

Rational Design of Ruddlesden-Popper Perovskite Ferrites as Air Electrode for Highly Active and Durable Reversible Protonic Ceramic Cells

Reversible protonic ceramic cells(RePCCs)hold promise for efficient energy storage,but their practicality is hindered by a lack of high-performance air electrode materials.Ruddlesden-Popper perovskite Sr_(3)Fe_(2)O_(7−δ)(SF)exhibits superior proton uptake and rapid ionic conduction,boosting activity.However,excessive proton uptake during RePCC operation degrades SF’s crystal structure,impacting durability.This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes,incorporating Sr-deficiency and Nb-substitution to create Sr_(2.8)Fe_(1.8)Nb_(0.2)O_(7−δ)(D-SFN).Nb stabilizes SF’s crystal,curbing excessive phase formation,and Sr-deficiency boosts oxygen vacancy concentration,optimizing oxygen transport.The D-SFN electrode demonstrates outstanding activity and durability,achieving a peak power density of 596 mW cm^(−2)in fuel cell mode and a current density of−1.19 A cm^(−2)in electrolysis mode at 1.3 V,650℃,with excellent cycling durability.This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.

Reaction of erythromycin with dissolved oxygen on gold nanoparticle-modified glassy carbon electrodes

Cyclic voltammetry was used to investigate the reaction of erythromycin (EM) with dissolved oxygen on gold nanoparticle-modified electrodes prepared via electrodeposition. A well-defined reduction peak at -0.420 V and a reoxidation peak at -0.055 V were observed. With the addition of EM into the NaOH solution containing dissolved oxygen, the oxidation peak at -0.055 V was still indiscernible. However, a new oxidation peak at 0.200 V appeared, which suggests the interaction between EM and dissolved oxygen. Therefore, this method can be used for the analysis of EM in tablets. The present method is simple, reproducible, and does not require complex analytical instruments.

Carbon nanotube-supported mixed-valence Mn_(3)O_(4) electrodes for high-performance lithium-oxygen batteries

Lithium-oxygen batteries(LOBs)have extensive applications because of their ultra-high energy densities.However,the practical application of LOBs is limited by several factors,such as a high overpotential,poor cycle stability,and limited rate capacity.In this paper,we describe the successful uniform loading of Mn_(3)O_(4) nanoparticles onto multi-walled carbon nanotubes(Mn_(3)O_(4)@CNT).CNTs form a conductive network and expose numerous catalytically active sites,and the one-dimensional porous structure provides a convenient channel for the transmission of Li+and O2 in LOBs.The electronic conductivity and electrocatalytic activity of Mn_(3)O_(4)@CNT are significantly better than those of MnO@CNT because of the inherent driving force facilitating charge transfer between different valence metal ions.Therefore,the Mn_(3)O_(4)@CNT cathode obtains a low overpotential(0.76 V at a limited capacity of 1000 mAh g^(-1)),high initial discharge capacity(16895 mAh g^(-1) at 200 mA g^(-1)),and long cycle life(97 cycles at 200 mA g^(-1)).This study provides evidence that transition metal oxides with mixed-valence states are suitable for application as efficient cathodes for LOBs.

Solid Reference Electrode of Metallurgical Oxygen Sensor

The thermal equilibrium state of the reference electrode was investigated. The results show that the temperature difference between the inside and the outside of zirconia tube was very small and the Seebeck effect can be ignored after the sensor was dipped into liquid steel for more than 2 s. A special sensor was designed to test the relation between the EMF （electromotive force） of sensor and the thermal equilibrium state of the reference elec- trode. Based on these results, it is suggested that the peak in EMF curve was caused by the change of oxygen potential in reference electrode before the thermal equilibrium was reached. If NiO was added by 2 M- 5 M to the Cr/Cr2O3 reference electrode, the peak in EMF curve could be eliminated.

Amorphous iron-nickel phosphide nanocone arrays as efficient bifunctional electrodes for overall water splitting

The synthesis of low-cost and highly active electrodes for both oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is very important for water splitting.In this work,the novel amorphous iron-nickel phosphide(FeP-Ni)nanocone arrays as efficient bifunctional electrodes for overall water splitting have been in-situ assembled on conductive three-dimensional(3D)Ni foam via a facile and mild liquid deposition process.It is found that the FeP-Ni electrode demonstrates highly efficient electrocatalytic performance toward overall water splitting.In 1 M KOH electrolyte,the optimal FeP-Ni electrode drives a current density of 10 mA cm^(-2) at overpotential of 218 mV for the OER and120 mV for the HER,and can attain such current density for 25 h without performance regression.Moreover,a two-electrode electrolyzer comprising the FeP-Ni electrodes can afford 10 mA cm^(-2) electrolysis current at a low cell voltage of 1.62 V and maintain long-term stability,as well as superior to that of the coupled RuO_(2)/NFk Pt/C/NF cell.Detailed characterizations confirm that the excellent electrocatalytic performances for water splitting are attributed to the unique 3D morphology of nanocone arrays,which could expose more surface active sites,facilitate electrolyte diffusion,and benefit charge transfer and also favorable bubble detachment behavior.Our work presents a facile and cost-effective pathway to design and develop active self-supported electrodes with novel 3D morphology for water electrolysis.

3D hollow sphere Co_3O_4/MnO_2-CNTs:Its high-performance bi-functional cathode catalysis and application in rechargeable zinc-air battery

There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.

Discharge Characteristics of an Atmospheric Pressure Argon Plasma Jet Generated with Screw Ring-Ring Electrodes in Surface Dielectric Barrier Discharge

An atmospheric-pressure argon plasma jet with screw ring-ring electrodes in surface dielectric barrier discharge is generated by a sinusoidal excitation voltage at 8 kHz. The discharge characteristics, such as rotational and vibrational temperature of nitrogen, electronic excitation temperature, oxygen atomic density, nitrogen molecular density, and average electron density, are estimated. It is found that the rotational temperature of nitrogen is in the range of 352 ～ 392 K by comparing the simulated spectrum with the measured spectrum at the C3Πu → B3Πg （△ν = 2） band transition, the electronic excitation temperature is found to be in the range of 3127 ～ 3230 K by using the Boltzmann plot method, the oxygen atomic and nitrogen molecular density are of the order of magnitude of 1016 cm-3 by the actinometry method, and the average electron density is of the order of magnitude of 1012 cm-3 by the energy balance equation. Besides, the effective power, conduction, and displacement current are measured during the discharge.

A novel bifunctional oxygen electrode architecture enabled by heterostructures self-scaffolding for lithium–oxygen batteries

In recent years, as one of the most promising chemical power sources for future society, lithium–oxygen (Li–O2) battery receives great attention due to its extremely high theoretical energy density of 3505 Wh kg^(–1)[1–4]. In practice, large polarization and consequent low energy efficiency currently still hinder the application of Li–O2batteries, which mainly results from the sluggish electrochemical reaction kinetics of oxygen diffusion electrodes in aprotic electrolytes [5]. On one hand, oxygen reduction reaction (ORR)in aprotic electrolytes is intrinsically sluggish due to the difficult charge transfer, the low solubility of oxygen.

Hybrid architecture design enhances the areal capacity and cycling life of low-overpotential nanoarray oxygen electrode for lithium–oxygen batteries

Transition metal oxide(TMO)nanoarrays are promising architecture designs for self-supporting oxygen electrodes to achieve high catalytic activities in lithium-oxygen(Li-O2)batteries.However,the poor conductive nature of TMOs and the confined growth of nanostructures on the limited surfaces of electrode substrates result in the low areal capacities of TMO nanoarray electrodes,which seriously deteriorates the intrinsically high energy densities of Li-O2 batteries.Herein,we propose a hybrid nanoarray architecture design that integrates the high electronic conductivity of carbon nanoflakes(CNFs)and the high catalytic activity of Co3 O4 nanosheets on carbon cloth(CC).Due to the synergistic effect of two differently featured components,the hybrid nanoarrays(Co3 O4-CNF@CC)achieve a high reversible capacity of3.14 mA h cm-2 that cannot be achieved by only single components.Further,CNFs grown on CC induce the three-dimensionally distributed growth of ultrafine Co3 O4 nanosheets to enable the efficient utilization of catalysts.Thus,with the high catalytic efficiency,hybrid Co3 O4-CNF@CC also achieves a more prolonged cycling life than pristine TMO nanoarrays.The present work provides a new strategy for improving the performance of nanoarray oxygen electrodes via the hybrid architecture design that integrates the intrinsic properties of each component and induces the three-dimensional distribution of catalysts.

Oxygen reduction on teflon-bonded carbon electrode

Oxygen reduction on Teflon-bonded carbon gas diffusion electrode without cataly st in 6 mol/L KOH solution was investigated with acimpedance spectroscopy and o ther electrochemical techniques. The kinetic parameters were measured with an ex change current density of J0=3.44×10-9 and a Tafel slope of 46 mV/ dec in low overpotential range （-0.05-0.14 V vs SCE）,which are compara ble with those reported on carbon supported platinum electrode. The reaction mec hanism of OR and the active effect of carbon black were examined.

Electro-catalytic effect of manganese oxide on oxygen reduction at teflonbonded carbon electrode

Oxygen reduction(OR)on Teflon-bonded carbon electrodes with manganese oxide as catalyst in 6 mol/L KOH solution was investigated using AC impedance spectroscopy combined with other techniques. For OR at this electrode, the Tafel slope is –0.084 V/dec and the apparent exchange current density is (1.02-3.0)×10-7 A/cm2. In the presence of manganese oxide on carbon electrode, the couple Mn3+/Mn4+ reacts with the O2 adsorbed on carbon sites forming O ?2 radicals and acceletes the dismutation of O 2?, which contributes to the catalytic effect of manganese oxide for OR reaction.

Progress and perspective of single-atom catalysts for membrane electrode assembly of fuel cells

A fuel cell is an energy conversion device that can continuously input fuel and oxidant into the device through an electrochemical reaction to release electrical energy.Although noble metals show good activity in fuel cell-related electrochemical reactions,their ever-increasing price considerably hinders their industrial application.Improvement of atom utilization efficiency is considered one of the most effective strategies to improve the mass activity of catalysts,and this allows for the use of fewer catalysts,saving greatly on the cost.Thus,single-atom catalysts(SACs)with an atom utilization efficiency of 100%have been widely developed,which show remarkable performance in fuel cells.In this review,we will describe recent progress on the development of SACs for membrane electrode assembly of fuel cell applications.First,we will introduce several effective routes for the synthesis of SACs.The reaction mechanism of the involved reactions will also be introduced as it is highly determinant of the final activity.Then,we will systematically summarize the application of Pt group metal(PGM)and nonprecious group metal(non-PGM)catalysts in membrane electrode assembly of fuel cells.This review will offer numerous experiences for developing potential industrialized fuel cell catalysts in the future.

Progress on direct assembly approach for in situ fabrication of electrodes of reversible solid oxide cells

Reversible solid oxide cells(SOCs)are very efficient and clean for storage and regeneration of renewable electrical energy by switching between electrolysis and fuel cell modes.One of the most critical factors governing the efficiency and durability of SOCs technology is the stability of the interface between oxygen electrode and electrolyte,which is conventionally formed by sintering at a high temperature of~1000–1250℃,and which suffers from delamination problem,particularly for reversibly operated SOCs.On the other hand,our recent studies have shown that the electrode/electrolyte interface can be in situ formed by a direct assembly approach under the electrochemical polarization conditions at 800℃and lower.The direct assembly approach provides opportunities for significantly simplifying the cell fabrication procedures without the doped ceria barrier layer,enabling the utilization of a variety of high-performance oxygen electrode materials on barrier layer–free yttria-stabilized zirconia(YSZ)electrolyte.Most importantly,the in situ polarization induced interface shows a promising potential as highly active and durable interface for reversible SOCs.The objective of this progress report is to take an overview of the origin and research progress of in situ fabrication of oxygen electrodes based on the direct assembly approach.The prospect of direct assembly approach in the development of effective SOCs and in the fundamental studies of electrode/electrolyte interface reactions is discussed.