Preparation and performance of hierarchically porous carbons as oxygen electrodes for lithium oxygen batteries

The hierarchically porous carbons （HPCs） were prepared by sol-gel selassembly technology in different surfactant concentrations and were used as the potential electrode for lithium oxygen batteries. The physical and electrochemical properties of the as-prepared HPCs were investigated by filed emission scanning electron microscopy （FE-SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption isotherm and galvanostatic charge/discharge. The results indicate that all of the HPCs mainly possess mesoporous structure with nearly similar pore size distribution. Using the HPCs as the electrode, a high discharge capacity for lithium oxygen battery can be achieved, and the discharge capacity increases with the specific surface area. Especially, the HPCs-3 oxygen electrode with CTAB concentration of 0.27 mol/L exhibits good capacity retention through controlling discharge depth to 800 mA·h/g and the highest discharge capacity of 2050 mA·h/g at a rate of 0.1 mA/cm2.

Two-dimensional MOF/MOF derivative arrays on nickel foam as efficient bifunctional coupled oxygen electrodes

Oxygen electrocatalysis,exemplified by the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is central to energy storage and conversion technologies such as fuel cells,metal-air batteries,and water electrolysis.However,highly effective and inexpensive earth-abundant materials are sought after to replace the noble metal-based electrocatalysts currently in use.Recently,metal-organic frameworks(MOFs)and carbon-based MOF derivatives have attracted considerable attention as efficient catalysts due to their exceedingly tunable morphologies,structures,compositions,and functionalization.Here,we report two-dimensional(2D)MOF/MOF derivative coupled arrays on nickel foam as binder-free bifunctional ORR/OER catalysts with enhanced electrocatalytic activity and stability.Their remarkable electrochemical properties are primarily attributed to fully exposed active sites and facilitated charge-transfer kinetics.The coupled and hierarchical nanosheet arrays produced via our growth-pyrolysis-regrowth strategy offer promise in the development of highly active electrodes for energy-related electrochemical devices.

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.

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.

Possibility of Using Ni-Co Alloy As Catalyst for Oxygen Electrode of Fuel Cell

In recent years, the scale of use of fuel cells （FCs） has been increasing continuously. One of the essential elements that affect their work is a catalyst. Precious metals （mainly platinum） are known for their high efficiency as FC catalysts. However, their high cost holds back the FCs from application on a large scale. Therefore, catalysts that do not contain precious metals are sought. Studies are focused mainly on the search for fuel electrode catalysts, but for the efficiency of FCs also the oxygen electrode catalyst is of great significance. The paper presents an analysis of the possibilitiesof using Ni-Co alloy as a catalyst for the oxygen electrode of the FC.

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.

Robust tantalum tuned perovskite oxygen electrode for reversible protonic ceramic electrochemical cells

Perovskite oxides with diverse composition and structure have exhibited grand advances in boosting the oxygen reduction and evolution reaction(ORR/OER),which are essential for the reversible protonic ceramic electrochemical cell(R-PCEC)toward the sustainable hydrogen production and utilization.However,enhancement of their activity and stability remains challenging.Herein,we develop the Ta-regulated BaCo_(0.7)Fe_(0.3)O_(3-δ)perovskite oxygen electrode(Ba(Co_(0.7)Fe_(0.3))_(1-x)Ta_xO_(3-δ))with abundant oxygen defects and achieve the simultaneous enhancement in the electrocatalytic activity and stability toward ORR and OER.As-fabricated R-PCEC with(Ba(Co_(0.7)Fe_(0.3))_(0.9)Ta_(0.1)O_(3-δ))(BCFT10)oxygen electrode performs high power density of 1.47 W·cm^(-2)at 650℃in fuel cell mode,and the current density is up to-2.11 A·cm^(-2)at 1.4 V at 650℃in electrolysis mode,as well as the good stability in both the fuel cell and electrolysis modes.Importantly,the cell also demonstrates a stable cycling operation between fuel cell and electrolysis mode,suggesting a great potential of BCFT10 as oxygen electrode material for R-PCECs.

Electrochemical performance of La_(2)NiO_(4+δ)-Ce_(0.55)La_(0.45)O_(2−δ)as a promising bifunctional oxygen electrode for reversible solid oxide cells

In this work,La_(2)NiO_(4+δ)-Ce_(0.55)La_(0.45)O_(2−δ)(denoted as LNO-xLDC)with various LDC contents(x=0,10,20,30,and 40 wt%)were prepared and evaluated as bifunctional oxygen electrodes for reversible solid oxide cells(RSOCs).Compared with the pure LNO,the optimum composition of LNO-30LDC exhibited the lowest polarization resistance(Rp)of 0.53 and 0.12Ω·cm^(2)in air at 650 and 750℃,respectively.The enhanced electrochemical performance of LNO-30LDC oxygen electrode was mainly attributed to the extended triple phase boundary and more oxygen ionic transfer channels.The hydrogen electrode supported single cell with LNO-30LDC oxygen electrode displayed peak power densities of 276,401,and 521 mW·cm^(−2)at 700,750,and 800℃,respectively.Moreover,the electrolysis current density of the single cell demonstrated 526.39 mA·cm^(−2) under 1.5 V at 800℃,and the corresponding hydrogen production rate was 220.03 mL·cm^(−2)·h^(−1).The encouraging results indicated that LNO-30LDC was a promising bifunctional oxygen electrode material for RSOCs.

Pd-La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)composite as active and stable oxygen electrode for reversible solid oxide cells

To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used to prepare the Pd-LSCF composite oxygen electrode.The cell with Pd-LSCF|GDC|YSZ|Ni-YSZ configuration shows perfect electrochemical performance in both solid oxide fuel cell(SOFC)mode and solid oxide electrolysis cell(SOEC)mode.In the SOFC mode,the cell achieves a power density of 1.73 W/cm^(2)at800℃higher than that of the LSCF oxygen electrode with 1.38 W/cm^(2).In the SOEC mode,the current density at 1.5 V is 1.67 A/cm^(2)at 800℃under 50 vol%steam concentration.Moreover,the reversibility and stability of the RSOCs were tested during 192 h long-term reversible operation.The degradation rate of the cell is only 2.2%/100 h and 2.5%/100 h in the SOEC and the SOFC modes,respectively.These results confirm that compositing Pd with the LSCF oxygen electrode can considerably boost the electrochemical performance of LSCF electrode in RSOCs field.

Mn-doped perovskite-type oxide LaFeO3 as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

Perovskite oxides based on the alkaline earth metal lanthanum for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)in alkaline electrolytes are promising catalysts,but their catalytic activity and stability remain unsatisfactory.Here,we synthesized a series of LaFe1-xMn2O3(x=0,0.1,0.3,0.5,0.7,0.9 and 1)perovskite oxides by doping Mn into LaFeO3(LF).The results show that the doping amount of Mn has a significant effect on the catalytic performance.When x=0.5,the catalyst LaFeo.sMno.sO3(LFM)exhibits the best performance.The limiting current density in 0.1 mol·L^-1 KOH solution is 7 mA·cm^-2,much larger than that of the commercial Pt/C catalyst(5.5 mA·cm^-2).Meanwhile,the performance of the doped catalyst is also superior to that of commercial Pt/C in terms of the long-term durability.The excellent catalytic performance of LFM may be ascribed to its abundant 0^2-/0^-species and low charge transfer resistance after doping the Mn element.

Surface carboxyl groups enhance the capacities of carbonaceous oxygen electrodes for aprotic lithiumoxygen batteries: A direct observation on binder-free electrodes

In order to achieve the high capacities of carbonaceous oxygen diffusion electrodes for aprotic lithiumoxygen batteries(Li-O2 batteries),most efforts currently focus on the design of rational porous architectures.Only few works study the surface chemistry effect that might be a critical factor influencing the capacities of carbonaceous electrodes.In addition,the surface chemistry effect is very difficult to be studied in composite electrodes due to the influences of binders and additives.Herein,we propose chemically activated carbon cloth(CACC) as an ideal model to investigate the effect of surface functional groups on the discharge capacities of carbonaceous oxygen electrodes for Li-O2 batteries.The intrinsic surface chemistry effect on the performance of carbonaceous cathode is directly observed for the first time without the influences of binders and additives.Results indicate that the surface carboxyl groups introduced by the chemical treatment not only function as the appropriate nucleation sites for Li2 O2 but also induce the formation of toroid-like Li2 O2.Thus,the surface carboxyl modification enhances the discharge capacities from 0.48 mAh/cm^2 of pristine carbon cloth to 1.23 mAh/cm^2 of CACC.This work presents an effective way to further optimize the carbonaceous oxygen electrodes via surface functional group engineering.

Preparation and application of perovskite-type oxides for electrocatalysis in oxygen/air electrodes

Recent advances in the preparation and application of perovskite-type oxides as bifunctional electrocatalysts for oxygen reaction and oxygen evolution reaction in rechargeable metal-air batteries are presented in this review.Various fabrication methods of these oxides are introduced in detail,and their advantages and disadvantages are analyzed.Different preparation methods adopted have great influence on the morphologies and physicochemical properties of perovskite-type oxides.As a bifunctional electrocatalyst,perovskite-type oxides are widely used in rechargeable metal-air batteries.The relationship between the preparation methods and the performances of oxygen/air electrodes are summarized.This work is concentrated on the structural stability,the phase compositions,and catalytic performance of perovskite-type oxides in oxygen/air electrodes.The main problems existing in the practical application of perovskite-type oxides as bifunctional electrocatalysts are pointed out and possible research directions in the future are recommended.

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.

Nano-LaCoO_(3)infiltrated BaZr_(0.8)Y_(0.2)O_(3)−δelectrodes for steam splitting in protonic ceramic electrolysis cells

Protonic ceramic electrolysis cell(PCEC)is a promising technology for production of pure dry hydrogen due to the low operating temperature and high efficiency.One of the obstacles for commercialization of PCEC technology is the poor performance and insufficient long-term durability of the oxygen electrode.In this study,we address the above challenge by designing a LaCoO_(3)(LC)catalyst infiltrated porous BaZr_(0.8)Y_(0.2)O_(3)−δ(BZY20)backbone electrode(LC-BZY20).The performance and durability of the LC-BZY20 electrode are investigated on symmetrical cells using electrochemical impedance spectroscopy(EIS).The total electrode polarization resistance(RP)values of the electrode are 0.56,1.24,2.18,and 2.90Ωcm2 in 3​vol%humidified synthetic air at 600,550,500,and 450​℃,respectively,indicating good electrochemical performance of the LC-BZY20 electrode.Furthermore,the LC-BZY20 electrode displays good stability,without significant performance degradation when tested at 600​℃ in 10​vol%humidified air for 900​h.We further study the influence of oxygen partial pressure(PO_(2))and steam partial pressure(P_(H_(2)O))on the response of the EIS data,and propose a set of chemical and electrochemical processes involved in the steam splitting reaction in the LC-BZY20 electrode.

Effects of Temperature and Light on Growth Rate and Photosynthetic Characteristics of Sargassum horneri

The changing environmental factors exerted great influences on coastal macroalgal communities.To study the responses of the brown seaweed Sargassum horneri to temperature and light,S.horneri was cultured under three temperatures(20,25 and 30℃)and three light intensities(30,60,and 120μmol photons m-2 s-1)for seven days.The growth rate,chlorophyll a(Chl a)and carotenoids(Car)contents,chlorophyll fluorescence,and photosynthetic oxygen evolution rate were measured.The results show that the highest relative growth rate(RGR),maximal electron transport rate(rETRmax);the net photosynthetic rate(Pn)were observed at the lowest temperature(20℃)and highest light intensity(120μmol photons m-2 s-1);and the RGR and Pn were significantly inhibited by the highest temperature(30℃),especially at the lowest light intensity(30μmol photons m-2 s-1)(P<0.05).Additionally,the highest light intensity enhanced the non-photochemical quenching(NPQ)even under the highest temperature(30℃),indicating that the higher light intensity could induce photo-protection reaction of thalli.These results suggest that the higher temperature and lower light intensity exerted negative influences on S.horneri.

In-situ growth of CoNi bimetal anchored on carbon nanoparticle/nanotube hybrid for boosting rechargeable Zn-air battery

Exploring highly efficient non-precious metal based catalysts for bifunctional oxygen electrode is crucial for rechargeable metal-air batteries.In this study,with MOFs as precursors,a facile coprecipitation method is designed to realize in-situ growth of the CoNi anchored carbon nanoparticle/nanotube(CoNi/N-CNN)hybrid,which can achieve the simultaneous maximum exposure of both oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)active centers.Benefiting from the unique structure,the CoNi/N-CNN catalyst exhibits excellent electrocatalytic performance for ORR(E_(onset)=1.183 V,E_(1/2)=0.819 V)and a low operating voltage of 1.718 V at 10 mA cm^(−2)(Ej=10)for OER.Delightfully,the home-made rechargeable Zn-air battery with CoNi/N-CNN delivers a high discharge power density up to 209 mW cm^(−2),and an outstanding charge–discharge cycling stability.The boosted bifunctional electrocatalytic activity can be ascribed to the strong coupling effect between Co/Ni center sites and defect-rich N-anchored carbon featured with porous and nanotube structure,which can introduce uniformly dispersed active sites,tailored electronic configuration,superb conductivity and convenient charge transfer process.The hybrid non-precious bimetal based electrocatalyst provides the possibility to develop the low-cost and high-efficient ORR/OER bifunctional electrocatalysts in rechargeable metal-air battery.

An oxygen reduction sensor based on a novel type of porous carbon composite membrane electrode

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using a novel type of porous carbon composite membrane/glassy carbon electrode based on the low-cost common filter paper by a simple method. The resulting device exhibited excellent electrocatalytic activities toward the oxygen reduction reaction. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements demonstrated that the porous morphology and uniformly dispersed Fe;C nanoparticles of the PCCM play an important role in the oxygen reduction reaction. A linear response range from 2mmol/L up to 110 mmol/L and a detection limit of 1.4 mmol/L was obtained with this sensor. The repeatability of the proposed sensor,evaluated in terms of relative standard deviation, was 3.0%. The successful fabrication of PCCM/GC electrode may promote the development of new porous carbon oxygen reduction reaction material for the oxygen reduction sensor.

A Novel Composite Electrode of Photocatalyst-TiO_2/C Loading on the Surface of the Air (Oxygen) Electrode

The methods for preparing the H_2O_2 generating air (oxygen) electrode andthe composite electrode of photocatalyst-TiO_2/C loading on the surface of the air (oxygen)electrode were introduced. In the case of the composite electrode, the current efficiency ofelectro-generated H_2O_2 is higher than 80% (J ≤ 15 mA/cm^2). The degradation of aniline was usedas an example to measure the influence of the composite electrode and compared with the system inwhich the air (oxygen) electrode and the photocatalyst-TiO_2 were separated. The results confirmedthat the composite electrode played an active role on accelerating the degradation rate of aniline.According to the measurement of the polarization curves of composite electrode and TiO_2 photoanode, and of the adsorbing amount of aniline on the surface of the composite electrode, theprinciple of descending the recombination rate of photo-generated electron and hole and of enhancingthe oxidation rate of organic molecule was described. The mechanism about the degradation ofaniline was also discussed.

An Effective Novel ReactionSystem For The Photo Degradation of Aqueous Organic Pollutants

A novel reaction system consisted of a supported TiO2 film electrode, a Ru?Ti oxide film electrode and air (oxygen) electrode is reported. The air (oxygen) electrode can provide H2O2 continuously for homogeneous photochemical oxidation reaction on the spot. In this reactor, degradation reaction of aniline occur from interface of TiO2 film to all solution which is irradiated by ultraviolet ray. The degradation rate of aniline was characterized by measuring the change of chemical oxygen demand (COD) in solution under different conditions. It was found that the degradation rate of aniline in the novel system increased apparently as compared with single heterogeneous photocatalysis and homogeneous photochemistry system. It can be explained in terms of combining acts of heterogeneous photocatalysis and homogeneous photochemistry.

Thin layer gas electrode and its application to measurement of dissolved oxygen

A novel thin layer cell equipped with thin layer gas electrode(TLGE)was studied as electrochemical gas sensor for the measurement of dissolved oxygen in water or aqueous solutions. The working electrode(TLGE)is a hydrophohic gas diffusing electrode placed between the cell electrolyte and the solution to be tested.The hydrophobic pores in TLGE serve as a gas chamber. After the sampling period,in which the partial pressure of dissolved oxygen in test solution becomes in equilibrium with that in the gas chamber,the TLGE is polarized with square wave or linear potential signal.Then the Faradaic charge (Q) consumed in depletion of the oxygen contained in pores of TLGE is measured.The main merits of this system are good linearity between the partial pressure of dissolved oxygen in test solution and Q,low zero-reading,negligible liquid-gas difference,con- venient calibration and very low temperature coefficient(ca.0.5%/℃).This technique can also be applied to the measurement of oxygen partial pressure in gas phases.