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.

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.

Cathodic micro-arc electrodeposition of yttrium stabilized zirconia (YSZ) coatings on FeCrAl alloy

The formation of ceramic coatings on metal substrate by cathodic electrolytic deposition (CELD) has received more attention in recent years. But only thin filmscan be prepared via CELD. Yttrium stabilized zirconia (YSZ) ceramic coatings were deposited on FeCrAI alloy by a novel technique--cathodic micro-arc electrodeposition (CMED).The result shows that, when a high pulse electric field is applied to the cathode which was pre-deposited with a thin YSZ film, dielectric breakdown occurs and micro-arc discharges appear. Coatings with reasonably thickness of-300μm and crystalline structure can be deposited on the cathode by utilizing the energy of the micro-arc. The thickness of the as-deposited coating is dominated by the voltage and the frequency. Y2O3 is co-deposited with ZrO2 when Y(NO3)3 was added to the electrolyte, which stabilize t-phase, t′-phase and c-phase of ZrO2 at room temperature. The amount of the m-ZrO2 in the coating is diminished by increasing the concentration of Y(NO3)3 in the electrolyte.This report describes the processing of CMED and studies the microstructure of the deposited YSZ coatings.

A functional cathode sodium compensation agent for stable sodium-ion batteries

Hard carbon(HC)is widely used in sodium-ion batteries(SIBs),but its performance has always been limited by lowinitial Coulombic efficiency(ICE)and cycling stability.Cathode compensation agent is a favorable strategy to make up for the loss of active sodium ions consumed byHCanode.Yet it lacks agent that effectively decomposes to increase the active sodium ions as well as regulate carbon defects for decreasing the irreversible sodium ions consumption.Here,we propose 1,2-dihydroxybenzene Na salt(NaDB)as a cathode compensation agent with high specific capacity(347.9 mAh g^(-1)),lower desodiation potential(2.4–2.8 V)and high utilization(99%).Meanwhile,its byproduct could functionalize HC with more C=O groups and promote its reversible capacity.Consequently,the presodiation hard carbon(pHC)anode exhibits highly reversible capacity of 204.7 mAh g^(-1) with 98%retention at 5 C rate over 1000 cycles.Moreover,with 5 wt%NaDB initially coated on the Na3V2(PO4)3(NVP)cathode,the capacity retention of NVP + NaDB|HC cell could increase from 22%to 89%after 1000 cycles at 1 C rate.This work provides a new avenue to improve reversible capacity and cycling performance of SIBs through designing functional cathode compensation agent.

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.

Sc-doped strontium iron molybdenum cathode for high-efficiency CO_(2)electrolysis in solid oxide electrolysis cell

Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.

Improved rate and cycling performances of Na_(3)V_(2)(PO_(4))_(2)F_(2)O by Ti^(3+/4+)doping with two oxidation states for sodium cathodes

Ti at the oxidation states of Ti^(3+)and Ti^(4+),was used to enhance the performance of Na_(3)V_(2)(PO_(4))_(2)F_(2)O by partially substituting vanadium.After doping Ti,the crystallographic volume is decreased due to the less radii of Ti^(3+/4+),and the valence of Ti is demonstrated identical to V.During sodium insertion in Ti-doped Na_(3)V_(2)(PO_(4))_(2)F_(2)O,the two discharge plateaus split into three because of the rearrangement of local redox environment.Consequently,the optimized Na_(3)V_(0.96)Ti_(0.04)(PO_(4))_(2)F_(2)O shows a specific capacity of 123 and 63 mA·h/g at 0.1C and 20C,respectively.After 350 cycles at 0.5C,the capacity is gradually reduced corresponding to a retention of 71.05%.The significantly improved performance is attributed to the rapid electrochemical kinetics,and showcases the strategy of replacing V^(3+/4+)with Ti^(3+/4+)for high-performance vanadium-based oxyfluorophosphates.

Optimization Strategies of Na_(3)V_(2)(PO_(4))_(3) Cathode Materials for Sodium‑Ion Batteries

Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.

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.

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.