CN109023312A - A kind of method of laser assisted prepares coating Ti electrode - Google Patents
A kind of method of laser assisted prepares coating Ti electrode Download PDFInfo
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- CN109023312A CN109023312A CN201811029523.3A CN201811029523A CN109023312A CN 109023312 A CN109023312 A CN 109023312A CN 201811029523 A CN201811029523 A CN 201811029523A CN 109023312 A CN109023312 A CN 109023312A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
The invention discloses a kind of methods of laser assisted prepares coating Ti electrode, comprising the following steps: pre-processes to Ti matrix；Prepare precursor solution；In the uniform brushing precursor solution of Ti matrix surface；It uses a laser as heat source to heat Ti matrix, is formed on its surface the coating with electro catalytic activity；Method using laser assisted prepares coating Ti electrode proposed by the invention, can shorten the preparation time of electrode, keep the geomery of prepared electrode unrestricted, and have good chemical property using the coating Ti electrode of this method preparation.
Description
Technical field
The present invention relates to Surface Engineering field, the method for specifically a kind of laser assisted prepares coating Ti electrode.
Background technique
Coating Ti electrode is using metal Ti as matrix, and surface has the electricity of the platinum-group metal oxide coatings of electro catalytic activity
Pole material.Compared with traditional graphite and lead-based anode, coating Ti electrode is had the advantage that
1, the dimensionally stable of electrode.Using metal Ti as electrode matrix, in the use process of electrode, Ti matrix will not
Excessive consumption, the dimensionally stable of electrode, pole constant gap, decomposition voltage are stablized, and the quality of electrolysate can be improved.
2, operating voltage is low when Ti electrode uses, and can reduce energy consumption.
3, machining property is good, can arbitrarily be processed into required shape.
4, the good corrosion resistance of coating Ti electrode, service life are longer compared with traditional electrode.
Coating Ti electrode is widely used in the fields such as chlorine industry, plating, cathodic protection, pollutant process.But by
In thermal decomposition method prepares coating Ti electrode, time-consuming, and production efficiency is lower, and traditional production method has been difficult to meet each neck
Therefore demand of the domain to coating Ti electrode need to improve the production efficiency of coating Ti electrode.Utilize laser assisted prepares coating Ti electricity
Pole can flexibly control heat input according to actual state in preparation process, realize different heating temperatures, reach improve matrix with
Apply the purpose of interlayer bond quality；It can choose the region heated, keep the geomery for preparing sample unrestricted；Heating
Rate is fast, can effectively shorten preparation time using laser assisted prepares coating Ti electrode, improve efficiency.
In the selection of coating Ti electrode coating material, IrO2It is special because it is with good electro catalytic activity and electric conductivity
It is not the IrO under with corrosive operating condition2There is better corrosion resistance compared with Ru series metal oxide, become most often
Coating composition, but since it is easily segregated in coating surface, cause the service life of electrode relatively short；Ta2O5As inertia
Ingredient is added, and can alleviate IrO2Segregation, extend the service life of electrode；SnO is added in the coating2, can reduce coating and split
The width and depth of line, delay the infiltration of oxygen, prevent matrix from oxidation occurs and generate nonconducting TiO2, extend electrode uses the longevity
Life.
Therefore, it can use laser auxiliary heating and prepare IrO in Ti matrix surface2-Ta2O5-SnO2Mixed oxide electricity is urged
Change active coating.Laser assisted prepares coating Ti electrode can shorten the preparation time of electrode, and prepared sample shape size is more
It is versatile and flexible, and use the research of laser assisted prepares coating Ti electrode correlation technique less, therefore study and use laser auxiliary
Prepares coating Ti electrode is helped to have great importance.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of laser assisted prepares coating Ti electrode, to solve above-mentioned background skill
The problem of being proposed in art.
To achieve the above object, the invention provides the following technical scheme:
A kind of method of laser assisted prepares coating Ti electrode, which is characterized in that the described method comprises the following steps:
The surface preparation of S1, Ti matrix；
S2, precursor solution is prepared；
S3, precursor solution is uniformly brushed to Ti matrix surface after the pre-treatment, and is dried；
S4, using laser as heat source, Ti matrix is heated, its Surface Creation have electro catalytic activity oxidation
Object coating obtains sample；
S5, after sample is cooled to room temperature, repeat S3, S4 step.
Further, the step S1 the following steps are included:
S11, Ti matrix of being polished using sand paper, are removed its oxide on surface and spot and make surface roughness Ra6.3；
It S12, is that 37wt.%HCl solution carries out acid etch to the Ti matrix after polishing using concentration, to be uniformly distributed
Etch pit surface；
S13, the Ti matrix after acid etch is rinsed well with the dehydrated alcohol of 99.7wt.%.
Further, in the presoma masking liquid, the weight percent of each component is configured that 69-75%H2IrCl6·
xH2O, 20-24%TaCl5, surplus 1-11%SnCl2·2H2O。
Further, the specific preparation method of the precursor solution is, by H2IrCl6·xH2O is dissolved in (CH3)2CHOH
In obtain solution A, then by TaCl5、8nCl2·2H2O is dissolved in (CH3) respectively2Solution B is obtained in CHOH, finally by solution A and
Solution B is mixed, and precursor solution is obtained.
Further, the H2IrCl6·xH2The content of Ir is 35wt.%, the TaCl in O5Purity be
98wt.%, the 8nCl2·2H2The purity of O is the 98wt.%, (CH3)2The concentration of CHOH is 99.7wt.%.
Further, in the step S3, the brushing method of precursor solution is to dip precursor solution using hairbrush,
The even Ti matrix surface brushed after the pre-treatment.
Further, in the step S3, the Ti matrix for being painted with precursor solution is placed in baking oven, is dried at 90 DEG C
It is 5 minutes dry, remove organic solvent in precursor solution.
Further, it in the step S5, repeats S3, S4 step 8-12 times.
Further, the laser assisted device includes laser, numerical control table, NC table, and the laser is semiconductor optical fibre
Laser, spot diameter 3mm, overlapping rate 20%；The numerical control table, NC table is for fixing Ti matrix；Laser and numerical control work
Platform cooperative movement makes the movement speed of matrix heating region within the scope of 10-20mm/s.
Further, the specific method of laser assisted preparation is that use power be the laser of 100-200W to Ti base
Body surface face is heated, and the oxide coating with electro catalytic activity is obtained on its surface.
Compared with prior art, the beneficial effects of the present invention are:
The present invention uses a laser as heat source, is prepared for IrO in Ti matrix surface2-Ta2O5-SnO2Mixed oxide electricity is urged
Change active coating.The present invention uses laser assisted prepares coating Ti electrode, effectively shortens the preparation time of electrode, preparation electricity
The geomery of pole is unrestricted, has practical application value.
Detailed description of the invention
Fig. 1 is the process schematic representation of the embodiment of the present invention 1；
Fig. 2 is the X-ray diffractogram of the coating composition of the embodiment of the present invention 1；
Fig. 3 is the volt-ampere cyclic curve of the coating Ti electrode of the embodiment of the present invention 1；
Fig. 4 is the electrochemical impedance spectroscopy of the coating Ti electrode of the embodiment of the present invention 1；
Fig. 5 is the process schematic representation of the embodiment of the present invention 3.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, implements below
Example for explaining only the invention, is not intended to limit the scope of the present invention..
Embodiment 1:
A kind of method of laser assisted prepares coating Ti electrode, comprising the following steps:
Ti matrix is pre-processed, the size of Ti matrix is 50mm × 40mm × 3mm, is beaten Ti matrix surface
Mill, controlling its surface roughness is Ra6.3, removes the spot and oxide on its surface, the Ti matrix polished is put into
It is impregnated 1 hour in the HCl of 37wt.%, carries out acid etch, with the etch pit surface being evenly distributed, then use C2H5OH is by Ti matrix
Surface washing is clean.
69%H is taken by weight2IrCl6·xH2O crystal, 24%TaCl5And 7%SnCl2·2H2O is dissolved in respectively
(CH3)2In CHOH, then each solution mixed, obtains precursor solution.Precursor solution is dipped with hairbrush uniformly to brush
On Ti matrix, the Ti matrix for being painted with precursor solution is put into baking oven, 90 DEG C dry 5 minutes.Finally use a laser as
Heat source, auxiliary prepare electro catalytic activity coating.
The laser assisted device chosen in the present embodiment includes semiconductor light fibre laser, numerical control table, NC table, by Ti matrix
It is fixed on numerical control table, NC table, the scanning speed of laser is 15mm/s, power setting 160W, overlapping rate 20%.Using swash
Light heats Ti matrix, makes Ti matrix surface heating and oxidation, obtains the oxide coating with electro catalytic activity.
Every time after heating, it is cooled to room temperature to sample, repeats and is brushed, dried and heated, be repeated 8
It is secondary, obtain IrO2-Ta2O5-SnO2Mixed oxidization coating Ti electrode.
Fig. 1 is the XRD diagram of sample, it is seen that coating Ti electrode surface has IrO2Generation；Due to Ta2O5From it is noncrystal to
The transition temperature of crystal is 800 DEG C, prepares the temperature of the sample about at 500 DEG C, so inspection does not measure Ta in XRD diagram2O5Peak
In the presence of；Due to generating SnO2Amount it is seldom, so inspection do not measure SnO2The presence at peak.
Fig. 2 is the volt-ampere cyclic curve of sample, it is seen that the sample has good electro catalytic activity.
Fig. 3 is the electrochemical impedance spectroscopy of sample, it is seen that semicircle is presented in curve, and semicircular diameter is activation polarization electricity
The measurement of resistance can be obtained by the data analysis of electrochemical impedance spectroscopy, which has lesser polarization resistance, and electro catalytic activity is high.
Embodiment 2:
A kind of method of laser assisted prepares coating Ti electrode, comprising the following steps:
Ti matrix is pre-processed, the size of Ti matrix is 100mm × 80mm × 3mm, is beaten Ti matrix surface
Mill, controlling its surface roughness is Ra6.3, removes the spot and oxide on its surface, the Ti matrix polished is put into concentration
To be impregnated 1 hour in the HCl of 37wt.%, acid etch is carried out, with the etch pit surface being evenly distributed, then uses C2H5OH is by Ti base
It rinses well in body surface face.
75%H is taken by weight2IrCl6·xH2O crystal, 20%TaCl5And 5%SnCl2·2H2O is dissolved in respectively
(CH3)2In CHOH, then each solution mixed, obtains precursor solution.Precursor solution is dipped with hairbrush uniformly to brush
On Ti matrix, the Ti matrix for being painted with precursor solution is put into baking oven, 90 DEG C dry 5 minutes.Finally use a laser as
Heat source, auxiliary prepare electro catalytic activity coating.
The laser assisted device chosen in the present embodiment includes semiconductor light fibre laser, numerical control table, NC table, by Ti matrix
It is fixed on numerical control table, NC table, the scanning speed of laser is 10mm/s, power setting 100W, overlapping rate 20%.Using swash
Light heats Ti matrix, makes Ti matrix surface heating and oxidation, obtains the oxide coating with electro catalytic activity.
Every time after heating, it is cooled to room temperature to sample, repeats and is brushed, dried and heated, be repeated 10
It is secondary, obtain IrO2-Ta2O5-SnO2Mixed oxidization coating Ti electrode.
Embodiment 3:
A kind of method of laser assisted prepares coating Ti electrode, comprising the following steps:
Ti matrix is pre-processed, it is 10mm that Ti matrix, which selects diameter, and length is the circular bar of 50mm, to Ti matrix
Surface is polished, and controlling its surface roughness is Ra6.3, removes the spot and oxide on its surface, the Ti base that will be polished
Body, which is put into the HCl that concentration is 37wt.%, to be impregnated 1 hour, is carried out acid etch, with the etch pit surface being evenly distributed, then is used
C2H5OH rinses Ti matrix surface well.
72%H is taken by weight2IrCl6·xH2O, 22%TaCl5And 6%SnCl2·2H2O is dissolved in (CH respectively3)2In CHOH, then each solution mixed, obtains precursor solution.Precursor solution is dipped with hairbrush uniformly to brush in Ti base
On body, the Ti matrix for being painted with precursor solution is put into baking oven, 90 DEG C dry 5 minutes.Heat source is finally used a laser as,
Auxiliary prepares electro catalytic activity coating.
The laser assisted device chosen in the present embodiment includes semiconductor light fibre laser, numerical control table, NC table, by Ti matrix
It is fixed on numerical control table, NC table, it is 20mm/s that numerical control table, NC table shaft, which rotates linear velocity, and the scanning speed of laser is 2mm/s, function
Rate is set as 200W, overlapping rate 20%.Ti matrix is heated using laser, makes Ti matrix surface heating and oxidation, is obtained
Oxide coating with electro catalytic activity.
Every time after heating, it is cooled to room temperature to sample, repeats and is brushed, dried and heated, be repeated 12
It is secondary, obtain IrO2-Ta2O5-SnO2Mixed oxidization coating Ti electrode.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of method of laser assisted prepares coating Ti electrode, which is characterized in that the described method comprises the following steps:
The surface preparation of S1, Ti matrix；
S2, precursor solution is prepared；
S3, precursor solution is uniformly brushed to Ti matrix surface after the pre-treatment, and is dried；
S4, using laser as heat source, Ti matrix is heated, its Surface Creation have electro catalytic activity oxide apply
Layer obtains sample；
S5, after sample is cooled to room temperature, repeat S3, S4 step.
2. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the step
S1 the following steps are included:
S11, Ti matrix of being polished using sand paper, are removed its oxide on surface and spot and make surface roughness Ra6.3；
It S12, is that 37wt.%HCl solution carries out acid etch to the Ti matrix after polishing using concentration, to obtain equally distributed erosion
Cheat surface；
S13, the Ti matrix after acid etch is rinsed well with the dehydrated alcohol of 99.7wt.%.
3. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the forerunner
In body masking liquid, the weight percent of each component is configured that 69-75%H2IrCl6·xH2O, 20-24%TaCl5, surplus 1-
11%SnCl2·2H2O。
4. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the forerunner
The specific preparation method of liquid solution is, by H2IrCl6·xH2O is dissolved in (CH3)2Obtain solution A in CHOH, then by TaCl5、
SnCl2·2H2O is dissolved in (CH3) respectively2Solution B is obtained in CHOH, finally mixes solution A and solution B, obtains forerunner
Liquid solution.
5. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that described
H2IrCl6·xH2The content of Ir is 35wt.%, the TaCl in O5Purity be 98wt.%, the 8nCl2·2H2The purity of O
For the 98wt.%, (CH3)2The concentration of CHOH is 99.7wt.%.
6. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the step
In S3, the brushing method of precursor solution is to dip precursor solution using hairbrush, the uniform Ti base brushed after the pre-treatment
Body surface face.
7. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the step
In S3, the Ti matrix for being painted with precursor solution is placed in baking oven, is dried 5 minutes at 90 DEG C, is removed in precursor solution
Organic solvent.
8. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the step
In S5, repeat S3, S4 step 8-12 times.
9. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that the laser
Auxiliary device includes laser, numerical control table, NC table, and the laser is semiconductor light fibre laser, spot diameter 3mm, overlap joint
Rate is 20%；The numerical control table, NC table is for fixing Ti matrix；Laser and numerical control table, NC table cooperative movement, make matrix heating region
Movement speed within the scope of 10-20mm/s.
10. a kind of method of laser assisted prepares coating Ti electrode according to claim 1, which is characterized in that described to swash
The specific method of light auxiliary preparation is that power is used to heat for the laser of 100-200W to Ti matrix surface, on its surface
Obtain the oxide coating with electro catalytic activity.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565834A (en) * | 2009-05-26 | 2009-10-28 | 北京科技大学 | Method for surface pre-treatment of titanium electrode substrate |
| CN101665948A (en) * | 2009-09-18 | 2010-03-10 | 天津大学 | Dinitrogen pentoxide electrode on electrochemistry synthesis and preparation method thereof |
| CN102505127A (en) * | 2011-12-29 | 2012-06-20 | 文广 | Preparation method for noble metal modified titanium anode materials |
| CN106745557A (en) * | 2017-03-13 | 2017-05-31 | 盐城工学院 | A kind of titanium-based tin iridium oxide electrode and preparation method thereof |
-
2018
- 2018-09-05 CN CN201811029523.3A patent/CN109023312B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565834A (en) * | 2009-05-26 | 2009-10-28 | 北京科技大学 | Method for surface pre-treatment of titanium electrode substrate |
| CN101665948A (en) * | 2009-09-18 | 2010-03-10 | 天津大学 | Dinitrogen pentoxide electrode on electrochemistry synthesis and preparation method thereof |
| CN102505127A (en) * | 2011-12-29 | 2012-06-20 | 文广 | Preparation method for noble metal modified titanium anode materials |
| CN106745557A (en) * | 2017-03-13 | 2017-05-31 | 盐城工学院 | A kind of titanium-based tin iridium oxide electrode and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周生刚等: "《金属基层状复合功能材料的研制与性能》", 31 May 2015, 冶金工业出版社 * |
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