CN103345958A - Composite electrode material containing reactive plasma spraying nanometer TiN middle layer and preparation method thereof - Google Patents

Composite electrode material containing reactive plasma spraying nanometer TiN middle layer and preparation method thereof Download PDF

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CN103345958A
CN103345958A CN2013102274618A CN201310227461A CN103345958A CN 103345958 A CN103345958 A CN 103345958A CN 2013102274618 A CN2013102274618 A CN 2013102274618A CN 201310227461 A CN201310227461 A CN 201310227461A CN 103345958 A CN103345958 A CN 103345958A
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intermediate layer
matrix
plasma spraying
tin
layer
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CN103345958B (en
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董艳春
张建新
杨勇
陈学广
阎殿然
刘哲
褚振华
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Hebei University of Technology
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Abstract

The invention discloses a composite electrode material containing a reactive plasma spraying nanometer TiN middle layer. The material comprises a base body, a bonding bottom layer arranged on the base body, the reactive plasma spraying nanometer TiN middle layer arranged on the bonding bottom layer and an oxide catalytic layer arranged on the middle layer. The base body is an iron-based or Ti-based base body, the bonding bottom layer is a nickel aluminum self-fluxing alloy layer containing Ni 95wt. % or an iron aluminum self-fluxing alloy layer containing Fe 50 wt. %, the thickness of the bonding bottom layer is 30-70 micrometers, the thickness of the reactive plasma spraying nanometer TiN middle layer is 300-500 micrometers, and the thickness of the oxide catalytic layer is 10-30 micrometers. Compared with a conventional Ti-based and iron-based electrode, a composite electrode is remarkably improved by 20%-25% in oxygen evolution potential, the fortified life of a Ti/TiN/Sb-SnO2 composite electrode is 3 times as long as that of the conventional electrode without the middle layer, and the fortified life of a Fe/TiN/PbO2 composite electrode is 360 times as long as that of the Ti/TiN/Sb-SnO2 composite electrode.

Description

Contain the combination electrode material in reaction and plasma spraying nano TiN intermediate layer and preparation method thereof
Technical field
The invention belongs to technical field of electrochemistry, relate to a kind of titanium base and ferrous metals oxide combination electrode material and manufacture method thereof that has reaction and plasma spraying nano TiN intermediate layer, this electrode is applicable to fields such as electrochemical industry, electrometallurgy industry, dirty waste water treatment, new forms of energy.
Background technology
The titanium-based metal oxide electrode has good electro catalytic activity, high electrolytic efficiency and higher job stability, and therefore, since coming out the sixties in 20th century, the titanium-based metal oxide electrode is used widely in electrochemical field.The stability of titanium-based metal oxide electrode and useful life is except outside the Pass the constituent structure with the metal oxide electro-catalytic coating has, and depends on interface and combination degree between surface state, coating of metal oxides and the matrix of electrode matrix to a great extent.At present, the failure cause of titanium-based metal oxide electrode is thought three kinds: the one, and the loss of metal oxide oxidation catalyst active coating; The 2nd, between catalyst coatings and titanium matrix, form passivating film; The 3rd, between catalyst coatings and the titanium matrix adhesion a little less than, catalyst coatings easily comes off gradually.Wherein passivating film formation and coming off of electro-catalytic coating are considered to cause the one of the main reasons of electrode failure.
Between titanium matrix and catalyst coatings, add the intermediate layer, can improve the stability of electrode, improve the useful life of electrode.The early stage intermediate layer material that uses is the strong precious metals of corrosion resistance such as Au, Pt, Ta, though the performance of the titanium-based metal oxide coating electrode that contains the intermediate layer that makes like this increases, cost performance is low, is difficult to apply.People forwarded research direction to conductivity and the same good oxide intermediate layer material of corrosion resistance afterwards, as Ir-Ta oxide, Sn-Sb oxide, Sn-Sb-Mn oxide, Sn-Ru-Mn oxide etc.Thermal decomposition method, sol-gel process etc. are used in the preparation in oxide intermediate layer always, the institutional framework in the intermediate layer of making and with the matrix bond situation with do not have the catalyst coatings in intermediate layer basic identical, the more weak situation of intermediate layer and titanium matrix bond is not significantly improved, difference just has more an intermediate layer, has played the effect that delays the oxide etch of titanium matrix.TiN intermediate layer film by the preparation of physical deposition method is good electrode intermediate layer material, but this preparation method's cost height, complex process is unsuitable for broad-area electrode, and is difficult to prepare the bigger intermediate layer film of thickness.
Summary of the invention
Purpose of the present invention is the problem that exists at above-mentioned existing titanium-based metal oxide electrode, designing a kind of is matrix with Ti and ferroalloy (mild steel, stainless steel etc.), nano TiN coating with the preparation of the reaction and plasma spraying micron order Ti powder of high spray efficiency is the intermediate layer, is combination electrode material of metal oxide oxidation catalyst coating and preparation method thereof on it.The present invention has improved stability and the useful life of existing electrode.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of combination electrode material that contains reaction and plasma spraying nano TiN intermediate layer, this material is formed and is comprised matrix, the bond coating of substrates, the reaction and plasma spraying nano TiN intermediate layer above the bond coating, and the oxide Catalytic Layer above the intermediate layer;
Wherein, matrix is iron-based or titanium base; Bond coating is the iron aluminium self-fluxing alloy layer that contains the nickel aluminium self-fluxing alloy of Ni95wt.% or contain Fe50wt.%, and thickness is 30-70 μ m; Reaction and plasma spraying nano TiN layer intermediate layer thickness is 300-500 μ m; Oxide Catalytic Layer thickness 10-30 μ m.
Described matrix is mild steel, stainless steel or Titanium.
Described oxide is Sb-SnO 2, PbO 2, IrO 2, Ta 2O 5, MnO 2, RuO 2, V 2O 5And Cr 2O 3In one or both.
The described preparation method who contains the combination electrode material in reaction and plasma spraying nano TiN intermediate layer may further comprise the steps:
(1) preliminary treatment of matrix: matrix surfaces such as titanium and low-carbon (LC) steel or stainless steel are removed greasy dirt, carry out blasting treatment, make surface coarsening;
(2) the bonding bottom of plasma spraying self-fluxing alloy: the matrix after the sandblast is placed on the plasma spraying operating desk, add Nickel Aluminium Alloy Powder or ferroaluminium powder in the powder feeder, preparation thickness is the bond coating of 30-70 μ m, and spraying parameter is spray power 20～30KW, Ar gas 60～80L/min, N 2Gas 50～70L/min, spray distance 110～130mm, powder feeding N 2Gas 8～12L/min obtains being coated with the matrix of bond coating;
(3) preparation in TiN intermediate layer: be that the titanium valve of 30～50 μ m is raw material with purity 〉=99%, granularity, adopt the reaction and plasma spraying device to obtain being coated with that coating thickness is the TiN intermediate layer of 300-500 μ m on the matrix of bond coating in previous step, spraying parameter is spray power 21～40KW, Ar gas 60～90L/min, N 2Gas 65～100L/min, spray distance 90～110mm, powder feeding N 2Gas 8～15L/min obtains being coated with the matrix in bond coating and intermediate layer;
(4) densification in TiN intermediate layer: the matrix that is coated with bond coating and intermediate layer that previous step is obtained is heated to 480～500 ℃, is incubated 1～3h, obtains being coated with the matrix in bond coating and dense intermediate layer;
(5) metal oxide oxidation catalyst layer preparation: the matrix that is coated with bond coating and dense intermediate layer of selecting for use thermal decomposition method or electrodeposition process to obtain in previous step prepares the metal oxide oxidation catalyst layer on combination electrode surface, and described metal oxide is Sb-SnO 2Or PbO 2, thickness 10-30 μ m.
Beneficial effect of the present invention is: the nano TiN coatings applications that the present invention reaches the corrosion resistance of 300-500 μ m and good conductivity to the thickness of reaction and plasma spraying preparation is prepared combination electrode material in conventional electrodes.TiN intermediate layer corrosion resistance and the good conductivity of combination electrode, and thickness can reach 500 μ m, and catalyst coatings has high oxygen evolution potential, and entire electrode has good stable and long useful life.Compare with the electrode of conventional titanium base and iron-based, the oxygen evolution potential of combination electrode obviously improves (improving 20%-25%), Ti/TiN/Sb-SnO 2The reinforcing life of combination electrode is 3 times of no intermediate layer conventional electrodes, Fe/TiN/PbO 2The reinforcing life of combination electrode is Ti/PbO 2360 times.
Description of drawings
Fig. 1 is the surface topography in reaction and plasma spraying nano TiN intermediate layer among the embodiment 1;
Fig. 2 is the TEM photo in reaction and plasma spraying nano TiN intermediate layer among the embodiment 1
Fig. 3 is the stereoscan photograph in TiN intermediate layer after the densification among the embodiment 1
Ti/TiN/Sb-SnO among Fig. 4 embodiment 1 2The combination electrode surface topography
Ti/TiN/Sb-SnO among Fig. 5 embodiment 1 2The surperficial XRD collection of illustrative plates of combination electrode
Ti/TiN/Sb-SnO among Fig. 6 embodiment 1 2Combination electrode and Ti/Sb-SnO 2The comparison of the oxygen evolution potential of electrode
Ti/TiN/Sb-SnO among Fig. 7 embodiment 1 2Combination electrode and Ti/Sb-SnO 2The comparison of the reinforcing life curve of electrode
The surface topography in TiN intermediate layer after the densification among Fig. 8 embodiment 2
The TEM photo in reaction and plasma spraying nano TiN intermediate layer among Fig. 9 embodiment 2
The cross section pattern in TiN intermediate layer after the densification among Figure 10 embodiment 2
Fe/TiN/PbO among Figure 11 embodiment 2 2The surface topography of combination electrode
Fe/TiN/PbO among Figure 12 embodiment 2 2Combination electrode surface XRD spectral line
Fe/TiN/PbO among Figure 13 embodiment 2 2, Ti/TiN/PbO 2, Ti/PbO 2The comparison of the oxygen evolution potential of electrode
1.0mol/L H among Figure 14 embodiment 2 2SO 4, 4.0A.cm -2Under the condition, Fe/TiN/PbO 2And Ti/PbO 2The reinforcing life curve of electrode
Specific embodiment
The raw material that the present invention prepares combination electrode all is commercially available.
Embodiment 1-Ti/TiN/Sb-SnO 2Combination electrode
(1) getting the thick trade mark of 3mm is that the Ti plate of TA1 is done matrix, and the dry blasting machine carries out sandblast (corundum) to be handled, and removes surface and oil contaminant, makes surface coarsening, and roughness reaches Rz25～100 μ m.
(2) matrix after the sandblast is placed on the plasma spraying operating desk, adopt 80KWGP-80 type plasma spraying equipment, BT-1 type spray gun, (composition is seen 1 table to add Nickel Aluminium Alloy Powder in the powder feeder, granularity 30～60 μ m powder), open the spraying control cubicle, spray the thick nickel alclad alloy bonding bottom of 40 μ m.Spraying parameter is power 20KW, ion A r gas 65L/min, ion N 2Gas 50L/min, spray distance 120mm, powder feeding N 2Gas 10L/min.
Table 1 sprays nickel aluminium and bronze composition
Figure BDA00003316058700031
(3) powder in the powder feeder changes micron metal T into iPowder (granularity 30～50 μ m, composition sees Table 2), preparation TiN intermediate layer, spraying parameter is power 24KW, ion A r throughput 60L/min, ion N 2Throughput 80L/min, spray distance 100mm, powder feeding N 2Throughput 12L/min, thickness are 500 μ m.
Table 2 test Ti meal component
(4) sample after will spraying is put into resistance furnace and is heated to 480 ℃ of insulation 1h, carries out densification.
(5) get 8gSnCl 45H 2O, 0.5gSbCl 3, 1g citric acid and 5ml ethylene glycol, be dissolved in the 100ml deionized water, the water-bath heating is prepared into collosol and gel, is applied to the TiN interlayer surfaces after the densification, is heated to 480 ℃ then and keeps 2h, obtaining thickness is the surperficial Sb-SnO of 14 μ m 2Catalytic Layer.
Accompanying drawing 1 is the surface topography in reaction and plasma spraying nano TiN intermediate layer, and wherein, Fig. 1 a and Fig. 1 b are respectively the stereoscan photographs that amplifies 500 times and 1000 times; By surface topography as can be seen, TiN is formed by the drop deposition, illustrates that TiN is in complete molten state in flame stream.Accompanying drawing 2 is the transmission electron microscope photo in TiN intermediate layer, and the TiN crystallite dimension is about 100nm as can be seen, and explanation is nanoscale.Accompanying drawing 3 is the cross-sectional scans photos in TiN intermediate layer after the densification, and coating is very fine and close after the coating densification as can be seen, with the combination enhancing of bond coating.Adding the Ti/TiN/Sb-SnO for preparing behind the TiN intermediate layer 2The surface catalytic layer of electrode is smooth, fine and close, even, does not have tangible hole and crackle (accompanying drawing 4), and visible TiN intermediate layer is conducive to apply sprawling of colloid, is beneficial to the preparation of Catalytic Layer.
Accompanying drawing 5 is to contain combination electrode surface, TiN intermediate layer XRD collection of illustrative plates, and as can be seen, the Catalytic Layer principal phase is SnO 2, but containing the TiN phase simultaneously, reason is SnO 2Thinner, detected the TiN intermediate layer, the main component that the intermediate layer also is described is TiN, rather than Ti.
Accompanying drawing 6 is Ti/Sb-SnO 2And Ti/TiN/Sb-SnO 2The oxygen evolution potential of electrode compares, and the oxygen evolution potential of Ti/Sb-SnO2 and Ti/TiN/Sb-SnO2 electrode is respectively 2.1V and 2.6V as can be seen, and the adding in visible TiN intermediate layer has improved the overpotential for oxygen evolution of electrode.
Accompanying drawing 7 is Ti/Sb-SnO 2And Ti/TiN/Sb-SnO 2The reinforcing life of electrode relatively.As can be seen, the starting voltage of two electrodes is about 6V, when the testing time reaches 40 minutes, and Ti/Sb-SnO 2The test voltage of electrode sharply raises, and electrode lost efficacy.TiN has played in the intermediate layer mechanical barrier effect from the Ti/TiN/Sb-SnO2 electrode, has slowed down the oxidation rate of Ti matrix, and voltage raise when the testing time was 120 minutes, and its reinforcing life is Ti/Sb-SnO 23 times of electrode.
Embodiment 2-Fe (Q235)/TiN/PbO 2Combination electrode
(1) (carbon containing 0.05～0.038wt.%) is done matrix, and the matrix surface oil removal is clean, carries out blasting treatment to get the thick Q235 steel of 3mm.
(2) matrix after the sandblast is placed on the plasma spraying operating desk, adds Nickel Aluminium Alloy Powder (95%Ni+5% aluminium, granularity 30～60 μ m) in the powder feeder, opens the spraying control cubicle, sprays the thick nickel alclad alloy bonding bottom of 70 μ m.Spraying parameter: power 25KW, ion A r gas 70L/min, ion N 2Gas 60L/min, spray distance 120mm, powder feeding N 2Gas 8L/min.
(3) powder in the powder feeder changes micron metal Ti powder into, and spraying level Ti prepares the TiN intermediate layer, and spraying parameter is spray power 28KW, ion A r gas 70L/min, ion N 2Gas 90L/min, spray distance 110mm, powder feeding N 2Gas 10L/min, intermediate layer thickness are 350 μ m.
(4) the TiN intermediate layer is heated to 500 ℃ of insulation 1.5h densification in heat-treatment furnace.
(5) adopt prepared by electrodeposition PbO 2Catalytic Layer, solution composition are 0.1mol/L Pb (NO 3) 2Add the 1.5g/LNaF additive in the aqueous solution, use HNO 3The pH value of regulator solution between 1.5～2.5,60 ℃ of bath temperatures, electric current 15mA/cm 2, sedimentation time 1h, obtaining thickness is the surperficial PbO of 28 μ m 2Catalytic Layer.
Accompanying drawing 8 is the surface topographies in TiN intermediate layer after the densification among the embodiment 2, densification is described after, interlayer surfaces crackle and hole reduce.The TEM photo in reaction and plasma spraying nano TiN intermediate layer among Fig. 9 embodiment 2 illustrates that the intermediate layer is nanoscale.Figure 10 is the cross section pattern in intermediate layer after the densification, on the direction of cross section as can be seen in the intermediate layer microdefect few.Figure 11 is Fe/TiN/PbO among the embodiment 2 2The surface topography of combination electrode, wherein, Figure 11 a amplifies 5000 times stereoscan photograph for 2000 times of amplifications, Figure 11 b, and electrode top layer particle is tiny and fine and close as can be seen, the kind electrode structure can increase the electro-chemical activity of electrode, can stop the infiltration of electrolyte again.Figure 12 is Fe/TiN/PbO among the embodiment 2 2Combination electrode surface XRD spectral line illustrates that pole catalyze layer is β-PbO 2Figure 13 is Fe/TiN/PbO among the embodiment 2 2, Ti/TiN/PbO 2, Ti/PbO 2The comparison of the oxygen evolution potential of electrode, the oxygen evolution potential of the electrode in interpolation intermediate layer is apparently higher than the electrode in no intermediate layer.1.0mol/L H among Figure 14 embodiment 2 2SO 4, 4.0A.cm -2Under the condition, Fe/TiN/PbO 2And Ti/PbO 2The reinforcing life curve, having the electrode in intermediate layer to strengthen electrode life is 180 hours, have only 0.5 hour the electrode life in no intermediate layer.
Embodiment 3
(1) with embodiment 2
(2) matrix after the sandblast is placed on the plasma spraying operating desk, adds ferroaluminium powder (contain Fe50wt.%, all the other are Al, granularity 30～60 μ m) in the powder feeder, opens the spraying control cubicle, sprays the thick ferroaluminium powder bond coating of 50 μ m.Spraying parameter: power 28KW, ion A r gas 75L/min, ion N 2Gas 70L/min, spray distance 110mm, powder feeding N 2Gas 8L/min.
(3)～(5) with embodiment 2
The oxygen evolution potential of gained combination electrode is than the high 0.4V of oxygen evolution potential of the electrode in no TiN intermediate layer, and the reinforcing life of electrode is 120 hours.
Embodiment 4
(1)～(4) with embodiment 1
(5) RuCl of employing mass fraction 36.9%Ru 33H 2O is raw material with the tantalic chloride butanol solution that contains tantalum 100g/L, gets ethanol, each 200ml of isopropyl alcohol as solvent.By ruthenium: the tantalum ion mol ratio is 1:1 preparation masking liquid, and total concentration of metal ions control is about 0.25mol/L in the masking liquid.The precursor masking liquid is coated on TiN matrix surface after the densification, and oven dry is sent into after the oven dry and is carried out thermal oxidation 10min in the Muffle furnace then, and oxidizing temperature is 300 ℃.Repeating above-mentioned steps, is 0.1mol/m up to the carrying capacity of titanium substrate surface metal ion 2Annealed 1 hour down at 300 ℃ at last.Obtaining thickness is the surperficial RuO of 18 μ m 2-Ta 2O 5Catalytic Layer.
After tested, Ti/TiN/RuO 2-Ta 2O 5The oxygen evolution potential of combination electrode is 2.3V, and the reinforcing life of electrode is 157 hours.
Unaccomplished matter of the present invention is known technology.

Claims (4)

1. combination electrode material that contains reaction and plasma spraying nano TiN intermediate layer, it is characterized by this material composition and comprise matrix, the bond coating of substrates, the reaction and plasma spraying nano TiN intermediate layer above the bond coating, and the oxide Catalytic Layer above the intermediate layer;
Wherein, matrix is iron-based or titanium base; Bond coating is the iron aluminium self-fluxing alloy layer that contains the nickel aluminium self-fluxing alloy of Ni95wt.% or contain Fe50wt.%, and thickness is 30-70 μ m; Reaction and plasma spraying nano TiN layer intermediate layer thickness is 300-500 μ m; Oxide Catalytic Layer thickness 10-30 μ m.
2. the combination electrode material that contains reaction and plasma spraying nano TiN intermediate layer as claimed in claim 1, it is characterized by described matrix is mild steel, stainless steel or Titanium.
3. the combination electrode material that contains reaction and plasma spraying nano TiN intermediate layer as claimed in claim 1, it is characterized by described oxide is Sb-SnO 2, PbO 2, IrO 2, Ta 2O 5, MnO 2, RuO 2, V 2O 5And Cr 2O 3In one or both.
4. the preparation method who contains the combination electrode material in reaction and plasma spraying nano TiN intermediate layer according to claim 1 is characterized by and may further comprise the steps:
(1) preliminary treatment of matrix: matrix surfaces such as titanium and low-carbon (LC) steel or stainless steel are removed greasy dirt, carry out blasting treatment, make surface coarsening;
(2) the bonding bottom of plasma spraying self-fluxing alloy: the matrix after the sandblast is placed on the plasma spraying operating desk, adopt and add Nickel Aluminium Alloy Powder or ferroaluminium powder in the plasma spraying equipment powder feeder, preparation thickness is the bond coating of 30-70 μ m, and spraying parameter is spray power 20～30KW, Ar gas 60～80L/min, N 2Gas 50～70L/min, spray distance 110～130mm, powder feeding N 2Gas 8～12L/min obtains being coated with the matrix of bond coating;
(3) preparation in TiN intermediate layer: be that the titanium valve of 30～50 μ m is raw material with purity 〉=99%, granularity, adopting reaction and plasma spraying device coating thickness on the matrix that is coated with bond coating that previous step obtains is 300-500 μ mTiN intermediate layer, and spraying parameter is spray power 21～40KW, Ar gas 60～90L/min, N 2Gas 65～100L/min, spray distance 90～110mm, powder feeding N 2Gas 8～15L/min obtains being coated with the matrix in bond coating and intermediate layer;
(4) densification in TiN intermediate layer: the matrix that is coated with bond coating and intermediate layer that previous step is obtained is heated to 480～500 ℃, is incubated 1～3h, obtains being coated with the matrix in bond coating and dense intermediate layer;
(5) metal oxide oxidation catalyst layer preparation: the matrix that is coated with bond coating and dense intermediate layer of selecting for use thermal decomposition method or electrodeposition process to obtain in previous step prepares the metal oxide 10-30 μ m Catalytic Layer on combination electrode surface, and described metal oxide is Sb-SnO 2, PbO 2, IrO 2, Ta 2O 5, MnO 2, RuO 2, V 2O 5And Cr 2O 3In one or both.
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CN104846398A (en) * 2015-05-29 2015-08-19 华北水利水电大学 Titanium-based TiNx/IrO2-Ta2O5 coating anode
CN107090572A (en) * 2017-04-07 2017-08-25 国网天津市电力公司 A kind of preparation method of TiN coatings
CN109778100A (en) * 2019-04-01 2019-05-21 西安建筑科技大学 One kind is lengthened the life the steady PbO of energy saving shape2The electric-arc thermal spray coating preparation method of anode middle layer
CN110184558A (en) * 2019-07-05 2019-08-30 河北工业大学 A kind of method that reaction and plasma spraying prepares nanocrystalline TiVN coating
CN112030188A (en) * 2020-09-08 2020-12-04 华北水利水电大学 IrO2 nano-coating anode with TiN nanotube intermediate layer
CN115125594A (en) * 2022-07-22 2022-09-30 西安泰金工业电化学技术有限公司 Lead dioxide anode for zinc electrodeposition and rapid preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104846398A (en) * 2015-05-29 2015-08-19 华北水利水电大学 Titanium-based TiNx/IrO2-Ta2O5 coating anode
CN107090572A (en) * 2017-04-07 2017-08-25 国网天津市电力公司 A kind of preparation method of TiN coatings
CN109778100A (en) * 2019-04-01 2019-05-21 西安建筑科技大学 One kind is lengthened the life the steady PbO of energy saving shape2The electric-arc thermal spray coating preparation method of anode middle layer
CN110184558A (en) * 2019-07-05 2019-08-30 河北工业大学 A kind of method that reaction and plasma spraying prepares nanocrystalline TiVN coating
CN112030188A (en) * 2020-09-08 2020-12-04 华北水利水电大学 IrO2 nano-coating anode with TiN nanotube intermediate layer
CN112030188B (en) * 2020-09-08 2023-06-09 华北水利水电大学 IrO2 nano-coating anode with TiN nano-tube intermediate layer
CN115125594A (en) * 2022-07-22 2022-09-30 西安泰金工业电化学技术有限公司 Lead dioxide anode for zinc electrodeposition and rapid preparation method thereof

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