New Strategy for Boosting Cathodic Performance of Protonic Ceramic Fuel Cells Through Incorporating a Superior Hydronation Second Phase

For protonic ceramic fuel cells,it is key to develop material with high intrinsic activity for oxygen activation and bulk proton conductivity enabling water formation at entire electrode surface.However,a higher water content which benefitting for the increasing proton conductivity will not only dilute the oxygen in the gas,but also suppress the O_(2)adsorption on the electrode surface.Herein,a new electrode design concept is proposed,that may overcome this dilemma.By introducing a second phase with high-hydrating capability into a conventional cobalt-free perovskite to form a unique nanocomposite electrode,high proton conductivity/concentration can be reached at low water content in atmosphere.In addition,the hydronation creates additional fast proton transport channel along the two-phase interface.As a result,high protonic conductivity is reached,leading to a new breakthrough in performance for proton ceramic fuel cells and electrolysis cells devices among available air electrodes.

Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Effect of 10% Si addition on cathodic arc evaporated TiAlSiN coatings

The effect of 10% Si （mole fraction） addition on TiAlSiN coatings was studied. Ti0.5Al0.5N, Ti0.5Al0.4Si0.1N and Ti0.55Al0.35Si0.1N coatings were deposited on WC？Co substrates by cathodic arc evaporation. The microstructure and mechanical properties were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM）, nano-indentation measurement and scratch test. The mechanisms of how Si affects the properties and failure modes of TiAlSiN coatings were also discussed. The results show that the addition of 10% Si results in the formation of nc-（Ti,Al,Si）N/a-Si3N4 nano-composite structure. The hardness and toughness of TiAlSiN coatings increase, whereas the coating adhesion strength decreases. Compared with Ti0.55Al0.35Si0.1N coating, Ti0.5Al0.4Si0.1N coating has higher hardness but lower toughness. The dominant failure mode of TiAlN coating is wedging spallation due to low toughness and strong interfacial adhesion. The dominant failure mode of TiAlSiN coatings is buckling spallation due to improved toughness and weakened interfacial adhesion.

Pseudo-capacitive Behavior of Cobalt Hydroxide/Carbon Nanotubes Composite Prepared by Cathodic Deposition

A novel type of composite electrode based on nmltiwalled carbon nanotubes coated with sheet-like cobalt hydroxide particles was used in supercapacitors. Cobalt hydroxide cathodlcally deposited fiom Co（NO3）O2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F/g in 1 mol/L KOH. To characterize the cobalt hydroxide nanocomposite electrode, a charge-discharge cycling test, cyclic voltammetry, and an impedance test were done. This cobalt hydroxide composite exhibiting excellent pseudo-capacitive behavior （i.c. high reversibility, high specific capacitance, low impedance）, was demonstrated to be a candidate for the application of electrochemical supercapacitors. A combined capacitor consisting of cobalt hydroxide composite as a cathode and activated carbon fiber as an anode was reported. The electrochemical pcrformance of the combined capacitor was characterized by cyclic voltammetry and a dc charge/discharge test. The combined capacitor showed ideal capacitor behavior with an extended operating voltage of 1.4 V. According to the extended operating voltage, the energy density of the combined capacitor at a current density of 100 mA/cm^2 was found to be 11 Wh/kg. The combined capacitor exhibited high-energy density and stable power characteristics,

CATHODIC PROCESS AND WEAR RESISTANCE OF ELECTRO-DEPOSITED RE-Ni-W-P-SiC COMPOSITE COATING

Cathodic deposition current density of the composite coatings increases when SiC par-ticles and rare earth (RE) were added in the bath, which is profitable for Ni- W-P alloy to deposit in the cathod, forming Ni-W-P-SiC and RE-Ni-W-P-SiC composite coatings. On the contrary, the addition of PTFE in the bath decreases cathodic deposition current density of the coatings. The current density increases a little when the amount of RE is 7-9g/l; however, the current density increases greatly when the amount of RE is increased to 11-13g/l. Bui ij the amount of RE is raised further, the current density decreases. Hardness and wear resistance of RE-Ni-W-P-SiC composite coating have been studied, and the results show that the hardness and wear resistance of RE-Ni-W-P-SiC composite coating increase with increasing heat treatment tempera-ture, which reach peak values at 400℃; while the hardness and wear resistance of the coating decrease with the rise of heat treated temperature continuously.

CREVICE CORROSION BEHAVIOR OF X70 STEEL IN HCO_3^- SOLUTION UNDER CATHODIC POLARIZATION

The crevice corrosion behavior of XTO steel was investigated with a wedge-shaped crevice assembly under -1000 m V （SCE） cathodic polarization in the solutions with various HCO3 concentrations. The potential, current, pH and the oxygen content within the crevice were measured with or without outside coupled specimen. The results indicated that the polarization potential of XTO steel in the crevice dropped with the increase of time under the cathodic polarization. There was a remarkable influence of HCO3 concentration on the potential of XTO steel in the crevice. When HCO3 concentration was up to 0.125%, the surface of the metal was covered with the corrosion products that resulted in the polarization extent of XTO steel decreased. The pH value in the crevice rose and it dropped gradually from the crevice mouth to the bottom under the cathodic polarization. With the increasing of HCO3 concentration, the hydrolyzation reaction of metal in the crevice bottom aggravated. Most of the dissolved oxygen in the crevice was consumed by the cathodic current. The maximum cathodic current on the metal surface was at the crevice mouth and it was much more than that at the crevice bottom.

A review on photoelectrochemical cathodic protection semiconductor thin films for metals

Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for metal to achieve cathodic protection. Comparing with traditional PEC photoanode for water splitting, it requires the photoanode providing a suitable cathodic potential for the metal, instead of pursuit ultimate photon to electric conversion efficiency, thus it is a more possible PEC technology for engineering application. To date, great efforts have been devoted to developing novel n-type semiconductors and advanced modification method to improve the performance on PEC cathodic protection metals. Herein, recent progresses in this field are summarized. We highlight the fabrication process of PEC cathodic protection thin film, various nanostructure controlling, doping, compositing methods and their operation mechanism. Finally, the current challenges and future potential works on improving the PEC cathodic protection performance are discussed.

Cathodic reaction mechanisms in CO2 corrosion of low-Cr steels

The cathodic reaction mechanisms in CO2 corrosion of low-Cr steels were investigated by potentiodynamic polarization and galvanostatic measurements.Distinct but different dominant cathodic reactions were observed at different p H levels.At the higher p H level(p H>~5),H2 CO3 reduction was the dominant cathodic reaction.The reaction was under activation control.At the lower pH level(pH<~3.5),H+reduction became the dominant one and the reaction was under diffusion control.In the intermediate area,there was a transition region leading from one cathodic reaction to another.The measured electrochemical impedance spectrum corresponded to the proposed cathodic reaction mechanisms.

Experience on offshore cathodic protection retrofitting in the northern South China Sea

Platforms I and II are steel structures located in offshore areas southeast of the Zhujiang (Pearl) River Delta, the northern South China Sea,. in about 110 in water depth. The jackets, with aluminum sacrificial anodes for cathodic protection (CP) of the immersed zone, were launched in March 1995. In May 096 a CP survey showed that, after almost one year of service, a low polarization level had been achieved and some extended unprotected zones existed; mainly in the deepest part of the Platform II. Further to this, a joint activity was decided in order to assess the need of a possible retrofitting of the CP systems. The results of the activity carried out are dealt with, including technical and economical comparisons amongst several retrofitting options, both with sacrificial anodes and with impressed current systems. The adopted solution is illustrated and data are reported on the level of protection presently achieved.

Composition demixing effect on cathodic arc ion plating

The composition demixing effect has been found often in alloy coatings deposited by cathodic arc ion plating using various alloy cathode targets. The characteristics of composition demixing phenomena were summarized. Beginning with the ionization zone near the surface of the cathode target, a physical model in terms of the ions generated in the ionization zone and their movement in the plating room modified by bias electric field was proposed. Based on the concept of electric charge state, the simulation calculation of the composition demixing effect was carried out. The percentage of atoms of an element in coating and from the alloy target was demonstrated by direct comparison. The influences of the composition change of the alloy target and the bias electric field on the composition demixing effect were discussed in detail. It is also proposed that the average charge states of the elements may be used to calculate the composition demixing effect and to design the composition of the alloy target.

THE EFFECTS OF NEGATIVE BIAS AND FLUX RATIO ON THE PROPERTIES OF TiN THIN FILMS FORMED BY FILTERED CATHODIC ARC PLASMA TECHNIQUE

The filtered cathodic vacuum-arc (FCVA) technique is a supplementary and alterna tive technique with respect to convendtional physical and chemical vapour deposi tion which can remove macro-particles effectively and make the deposition proces s at ambient temperature. In this work, high quality TiN thin films were deposi ted on silicon substrates at low temperature using the improved filtered cathodi c arc plasma (FCAP) technique. AFM, XRD, TEM were employed to characterize the T iN thin films. The effects of the negative substrate bias on the grain size, pre ferred crystalline orientation, surface roughness of TiN thin films were discuss ed.

Cathodic micro-arc electro-deposition of ZrO_2 coatings in an aqueous solution containing colloidal particles

By a novel technique-cathodic micro-arc electro-deposition (CMED), ZrO_2coatings were deposited on an FeCrAl alloy. Experimental results show that the necessary conditionsfor obtaining ZrO_2 coatings are to apply a pulse peak voltage over a critical value and addmoderate amounts of ZrO_2 colloidal particles and Zr(NO_3)_4 in the aqueous solution. Theas-deposited coatings are porous because hydrogen, water, and other vapors are generated andreleased from the coatings to the solution during the spark reaction. The coatings containmonoclinic and tetragonal crystalline ZrO_2 with certain degree of amorphous structure. Theprocessing parameters and mechanism of CMED were discussed.

Effect of pulsed bias on the properties of ZrN/TiZrN films deposited by a cathodic vacuum arc

ZrN/TiZrN multilayers are deposited by using the cathodic vacuum arc method with different substrate bias（from 0 to 800 V）,using Ti and Zr plasma flows in residual N 2 atmosphere,combined with ion bombardment of sample surfaces.The effect of pulsed bias on the structure and properties of films is investigated.Microstructure of the coating is analyzed by X-ray diffraction（XRD）,and scanning electron microscopy（SEM）.In addition,nanohardness,Young＇s modulus,and scratch tests are performed.The experimental results show that the films exhibit a nanoscale multilayer structure consisting of TiZrN and ZrN phases.Solid solutions are formed for component TiZrN films.The dominant preferred orientation of TiZrN films is（111） and（220）.At a pulsed bias of 200 V,the nanohardness and the adhesion strength of the ZrN/TiZrN multilayer reach a maximum of 38 GPa,and 78 N,respectively.The ZrN/TiZrN multilayer demonstrates an enhanced nanohardness compared with binary TiN and ZrN films deposited under equivalent conditions.

The Effect of Annealing under Non-vacuum on the Optical Properties of TiAlN Non-vacuum Solar Selective Absorbing Coating Prepared by Cathodic Arc Evaporation

TiAIN solar selective absorbing coatings which were deposited on 304L stainless steel using cathodic arc evaporation method were annealed under non-vacuum at different temperatures with different times. The optical properties （absorptance and emittance） of the coatings were measured by a spectrophotometer. It was found that, after being annealed for 2 hours at different temperatures, the absorptance of the coatings reached the highest value of 0.92 at 700 ℃ while the emittance got the lowest value of 0.38 at 800 ℃. When the coatings were annealed at 600 ℃ for 24 hours, the optical properties changed to 0.92/0.44 （absorptance/ emittance）. By measuring the structure, morphology, elements and surface roughness of the coatings, it was found that both the elemental composition and the surface roughness of the coatings changed as a result of annealing, and these changes caused the change of the optical properties of the coatings.

NUMERICAL MODELLING FOR OFFSHORE PLATFORM CATHODIC PROTECTION-LOCAL SYSTEM

This paper discusses numerical methods for modelling cathodic protation (CP) using Boundary ElementMethods(BEM) for CP design analysis in comparision with the traditional methods and presentsseveral mathematical models (for CP design in 3-D infinite area) solvable by using BEM withmicrocomputer.

EFFECT OF CATHODIC PROTECTION ON FRACTURE BEHAVIOUR OF LOWALLOY STEELS IN SEAWATER

Fracture behaviour of low-alloy steels AIST4340,HY100,Welten60,AISIA537 and A131 in artificial seawater under static,cyclic loading and at cathodic protection potential has been investigated by using the techniques of fracture mechanics, electrochemistry and electronfractography.The results reveal that at hydrogen evolution potentials(cathodic pro- tection potential)the critical yield strength required for the occurrance of SCC decreases from 985 at corrosion potential(E_c)to 872 MPa.The effect of cathodic protection on crack propagation of corrosion fatigue(CF)is not simple,it is closely related to the yield strength of steels and their SCC behaviour.For the steels with high yield strength,cathodic protection promotes(da/dN)_Ⅱ evidently,and reduces △K_(th) value.The(da/dN)-△K curves dis- play a plateau at the third stage of CF for steels with medium or low yield strength.It is men- tioned that the cathodic protection potential for oceaneering constructures should be control- led at top level of the protective range.It seems reasonable that the strength of steel for oceaneeing use might be increased by 200 or 300 MPa.

Cathodic Process of Nd and its Dissolution Behavior in Molten Fluoride

The results of linear potential sweep experiments show that, in the molten salt systems of NdF3-LiF-CaF2 and NdF3-LiF-CaF2-Nd2O3, the electrochemical reduction of Nd(III) at Mo cathode takes place in two steps. The dissolution loss of metallic Nd in fluoride melts under different conditions was determined according to the weight difference of Nd before and after experiments.

Synthesis of Lithium-cobalt Oxides by Sol-gel Method and their Cathodical Discharge Behavior at 500 ℃

Three kinds of lithium cobalt oxides with lithium to cobalt atomic ratios of 0.6, 0.8 and 1.0 respectively were prepared using nitrates and citric acid by sol gel process. During the baking of the dry gel powder, two exothermic peaks occur, followed by the formation of Li 2O and Co 3O 4 and then the combination of LiCoO 2, which is testified by DTA and XRD. The powder formed from an alkaline sol is finer than that from the acidic one. There are a single phase intercalation of lithium ion and an electrochemical reduction reaction for higher valence cobalt ion when simulating the discharging process of Li B/LiCl KCl/lithium cobalt oxides at 500 ℃, and the voltage and specific capacity are not sensitive to the initial ratios of lithium to cobalt.

ELECTROCHEMICAL STUDIES ON THE CATHODIC REACTION OF MARINE ATMOSPHERIC CORROSION

Electrochemical studies on the cathodic reaction of marine atmospheric corrosion using Kelvin probeas reference electrode showed that the rate of cathodic reaction-oxygen reduction first increases then de-creases, with the reaction maximizing at a certain thickness as the electrolyte film decreases duringevaporation. It was indicated that with decreasing electrolyte thickness by drying, the oxygen reduction ratewas accelerated by the faster oxygen diffusion due to the thinner electrolyte layer on the metal surface. Theresults also revealed that although the oxygen salting out effect has great influence on the rate of oxygenreduction, it is not the main causative factor for the decrease in cathodic limiting current in the case of avery thin electrolyte layer.

Well-ordered layered LiNi0.8Co0.1Mn0.1O2 submicron sphere with fast electrochemical kinetics for cathodic lithium storage

Nickel-rich layered oxides have drawn sustainable attentions for lithium ion batteries owing to their higher theoretical capacities and lower cost.However,nickel-rich layered oxides also have exposed several defects for commercial application,such as uncontrollable ordered layered structure,which leads to higher energy barrier for Li+diffusion.In addition,suffering from structural mutability,the bulk nickelrich cathode materials likely trigger overall volumetric variation and intergranular cracks,thus obstructing the lithium ion diffusion path and shortening the service life of the whole device.Herein,we report wellordered layered Li Ni0.8Co0.1Mn0.1O2 submicron spheroidal particles via an optimized co-precipitation and investigated as LIBs cathodes for high-performance lithium storage.The as-fabricated Li Ni0.8Co0.1Mn0.1O2 delivers high initial capacity of 228 mAh g–1,remarkable energy density of 866 Wh kg–1,rapid Li ion diffusion coefficient(10–9cm2s–1)and low voltage decay.The remarkable electrochemical performance should be ascribed to the well-ordered layered structure and uniform submicron spheroidal particles,which enhance the structural stability and ameliorate strain relaxation via reducing the parcel size and shortening Li-ion diffusion distance.This work anticipatorily provides an inspiration to better design particle morphology for structural stability and rate capability in electrochemistry energy storage devices.