CN110071302A - A kind of titanium-based Asia titanium oxide bipolar plates and preparation method thereof - Google Patents
A kind of titanium-based Asia titanium oxide bipolar plates and preparation method thereof Download PDFInfo
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- CN110071302A CN110071302A CN201910345850.8A CN201910345850A CN110071302A CN 110071302 A CN110071302 A CN 110071302A CN 201910345850 A CN201910345850 A CN 201910345850A CN 110071302 A CN110071302 A CN 110071302A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of Titanium base Asia titanium oxide bipolar plates and preparation method thereof, using micro-arc oxidation process, titanium plate is oxidized to carbon containing titanium dioxide ceramic layer first, then passes through carbo-thermal process for titanium dioxide at conducting function Asia titanium oxide (Ti4O7) ceramic layer.Simple process is easily operated, and the period is short and process stabilizing, repeatability are high.This method can be used for preparing large scale titanium-based Asia titanium oxide bipolar plates, and surface Asia titanium oxide ceramic layer performance is uniform, conductivity can reach 700S/cm or more；With the H of 3M2SO4Corrosion rate can be obtained less than 0.1 μ A/cm using electrochemistry linear polarization method for electrolyte2.Preparation process is generated without noxious material, environmentally protective, high-efficient feature.
Description
Technical field
The invention belongs to engineering material preparation technical field, it is related to the technology of preparing of the bipolar plates in relation to lead flow battery,
More particularly to a kind of titanium-based Asia titanium oxide bipolar plates, the preparation method of the titanium-based Asia titanium oxide bipolar plates is further related to.
Background technique
Titanium dioxide has very high insulation performance, but can improve its electric conductivity by reducing process.Particularly exist
Oxygen vacancies is realized in titanium dioxide lattice, and titania powder is generated into sub- titanium oxide powder powder material, i.e. TinO2n-1(4≤n≤
10).Such as Ti4O7(n=4 is commercialized brand to powder), conductivity can achieve 100~1000S/cm, relatively
In standard hydrogen electrode, oxidizing potential is greater than+2.6V.According to its excellent electric conductivity and electrochemical corrosion resistant, can make
It is had been reported for the anode material of water treatment technology and the bipolar plates of battery.But current main preparation methods are to utilize powder metallurgy
Method and carbon heat or Process of Hydrogen Reduction combine the sub- Titanium oxide electrode plate material of preparation.Specifically, prior art 1: will
Insulating silica titanium powder and water and organic solvent such as isopropanol etc. are uniformly mixed, and powder is tabletted after drying, at high temperature
Titanium dioxide is prepared into electrode plate at sub- titanium oxide using Process of Hydrogen Reduction；Prior art 2: first with carbon heat
Or titanium dioxide powder is reduced into sub- titanium oxide powder by Process of Hydrogen Reduction, then with the heats of mixing such as adhesive such as epoxy resin
It is molded to prepare electrode plate.Research is found to contain porous structure inside the electrode plate prepared using prior art 1, is easy
Sepage, can not be as the bipolar plates (as positive/negative plate, serves as anode on one side, and another side serves as cathode) in battery, can only
As anode or negative electrode material；And prior art 2, using adhesive as matrix, conductivity is low, electrochemical corrosion resistant
Property is poor.And both schemes all use hot press forming technology, and the size of electrode plate is limited by mould specification, increased
Energy consumption, production efficiency are low.
Summary of the invention
The first purpose of the invention is to provide a kind of Titanium base Asia titanium oxide bipolar plates, have high conductivity and resistance to electrification
The characteristics of learning corrosion.
It is a further object to provide the preparation methods of the Titanium base Asia titanium oxide bipolar plates, have raising existing
The characteristics of conductivity and electrochemical corrosion resistant performance of Titanium base Asia titanium oxide bipolar plates.
First technical solution of the present invention is a kind of Titanium base Asia titanium oxide bipolar plates, including matrix with set
It is placed in the coating of matrix surface, matrix is Titanium base, and Titanium base is titanium simple substance or titanium alloy, and coating is sub- titanium oxide ceramics
Layer, sub- titanium oxide ceramics layer is by TinO2n-1Composition, wherein 4≤n≤10, n are integer.
Another technical solution of the present invention is a kind of preparation method of Titanium base Asia titanium oxide bipolar plates, tool
Body follows the steps below to implement:
Titanium base surface is pre-processed；
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent；
Titanium base is placed in the micro-arc oxidation electrolyte and carries out micro-arc oxidation treatment, the carbon containing titanium dioxide of growth in situ
Titanium ceramic layer；
Gained Titanium base after micro-arc oxidation treatment is subjected to carbon thermal reduction processing, until the titanium dioxide ceramic on Titanium base surface
Layer is changed into sub- titanium oxide ceramics layer, obtains titanium-based Asia titanium oxide bipolar plates.
The features of the present invention also characterized in that:
Titanium base surface is pre-processed, while being prepared with deionized water, calgon, polyethylene glycol and film forming agent
Micro-arc oxidation electrolyte follows the steps below to implement:
After Titanium base sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 35%~45%, at 60~100 DEG C
1~3h of lower immersion；
By after immersion Titanium base move into boiling mass percent be 10%~20% oxalic acid solution in impregnate 1~
3h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic in acetone and deionized water to 5~10min,
It is dry.
Micro-arc oxidation electrolyte is prepared specifically according to following with deionized water, calgon, polyethylene glycol and film forming agent
Step is implemented:
Dissolution in deionized water is added in calgon and obtains sodium hexametaphosphate solution；
Polyethylene glycol is added into sodium hexametaphosphate solution, stirring and dissolving obtains mixed solution；
Film forming agent is added in mixed solution and is stirred evenly, pH value is adjusted to 7~8, obtains micro-arc oxidation electrolyte.
The quality of calgon, polyethylene glycol and film forming agent is often upgraded to 5~6:3~5:0.5 in micro-arc oxidation electrolyte
~1.2g.
Film forming agent is made of ethanedioic acid titanium amine and sodium oxalate with the mass ratio of 10:1.
Titanium base is placed in micro-arc oxidation electrolyte and carries out micro-arc oxidation treatment, the carbon containing titanium dioxide pottery of growth in situ
Enamel coating is specifically implemented according to lower step:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, Titanium base connects anode, and cathode is done with two panels stainless steel plate in the Titanium base left and right sides；
It opens mao power source and carries out oxidation processes；
After oxidation processes, Titanium base washing is taken out, is dried.
The spacing of the cathode and anode of Titanium base connection controls between 100~200mm, and oxidation trough electrolyte inside temperature is kept
At 20~30 DEG C.
Differential arc oxidation parameter setting: 1~3A/dm is pressed2Average current is set, 3~20%, frequency is controlled for duty ratio control
In 400~1000Hz, oxide termination voltage is controlled in 500~700V, 15~30min of oxidization time.
Gained Titanium base after micro-arc oxidation treatment is subjected to carbon thermal reduction processing, until the titanium dioxide ceramic on Titanium base surface
Layer is changed into sub- titanium oxide ceramics layer, obtains titanium-based Asia titanium oxide bipolar plates and specifically implements according to lower step:
Titanium base after micro-arc oxidation treatment to be protected using argon gas, heating rate is 10~20 DEG C/min, 1000~
It is calcined at 1100 DEG C, keeps the temperature 120~180 DEG C of min；
Heat preservation terminates, natural cooling room temperature, stops argon gas protection, titanium-based Asia titanium oxide bipolar plates are made.
The beneficial effects of the present invention are:
1, a kind of preparation method of titanium-based Asia titanium oxide bipolar plates of the present invention uses cheap metallic titanium plate for starting
Raw material, cost needed for greatly reducing production, product size are not limited by hot pressing die specification；
2, a kind of preparation method of titanium-based Asia titanium oxide bipolar plates of the present invention is prepared titanium-based using differential arc oxidization technique and is contained
Carbon titanium dioxide plate, method is simple, and formation efficiency is high；And electrolyte used is nontoxic, it is environmentally protective, and component letter
Single, daily no replacement is required, and maintenance cost is low；The present invention uses carbothermic reduction reaction technique, and the titanium-based Asia titanium oxide prepared is double
Pole plate film layer bottom is combined closely with Titanium base, and surface layer is in porous structure, and the negative electrode active material that is positive provides more anti-
Place is answered, to be conducive to improve the efficiency of lead flow battery.
3, the side of the titanium-based Asia titanium oxide bipolar plates of the preparation method preparation of a kind of titanium-based Asia titanium oxide bipolar plates of the present invention
Method simple process is not necessarily to thermoforming process, and plate preparation speed is fast, and low energy consumption.
Detailed description of the invention
Fig. 1 is a kind of titanium-based Asia titanium oxide ceramics of the preparation method embodiment 1 of titanium-based Asia titanium oxide bipolar plates of the present invention
The X ray diffracting spectrum of layer；
Fig. 2 is a kind of titanium-based Asia titanium oxide ceramics of the preparation method embodiment 1 of titanium-based Asia titanium oxide bipolar plates of the present invention
Layer surface shape appearance figure.
Specific embodiment
The present invention is described in detail With reference to embodiment.
A kind of Titanium base Asia titanium oxide bipolar plates, including matrix and the coating for being set to described matrix surface, described matrix
For Titanium base, the Titanium base is titanium simple substance or titanium alloy, and the coating is sub- titanium oxide ceramics layer, the Asia titanium oxide pottery
Enamel coating is by TinO2n-1Composition, wherein 4≤n≤10, n are integer.
A kind of preparation method of Titanium base Asia titanium oxide bipolar plates, is specifically implemented according to the following steps:
Titanium base surface is pre-processed；
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent；
Titanium base is placed in micro-arc oxidation electrolyte and carries out micro-arc oxidation treatment, the carbon containing titanium dioxide pottery of growth in situ
Enamel coating；
Gained Titanium base after micro-arc oxidation treatment is subjected to carbon thermal reduction processing, until the titanium dioxide ceramic on Titanium base surface
Layer is changed into sub- titanium oxide ceramics layer, obtains titanium-based Asia titanium oxide bipolar plates.
The features of the present invention also characterized in that:
Titanium base surface is pre-processed, while being prepared with deionized water, calgon, polyethylene glycol and film forming agent
Micro-arc oxidation electrolyte follows the steps below to implement:
After Titanium base sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 35%~45%, at 60~100 DEG C
1~3h of lower immersion；
By after immersion Titanium base move into boiling mass percent be 10%~20% oxalic acid solution in impregnate 1~
3h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic in acetone and deionized water to 5~10min,
It is dry.
Micro-arc oxidation electrolyte is prepared specifically according to following with deionized water, calgon, polyethylene glycol and film forming agent
Step is implemented:
Dissolution in deionized water is added in calgon and obtains sodium hexametaphosphate solution；
Polyethylene glycol is added into sodium hexametaphosphate solution, stirring and dissolving obtains mixed solution；
Film forming agent is added in mixed solution and is stirred evenly, pH value is adjusted to 7~8, obtains micro-arc oxidation electrolyte.
The quality of calgon, polyethylene glycol and film forming agent is often upgraded to 5~6:3~5:0.5 in micro-arc oxidation electrolyte
~1.2g.
Film forming agent is made of ethanedioic acid titanium amine and sodium oxalate with the mass ratio of 10:1.
Chemicals is that chemistry is pure, and entire configuration process carries out in oxidation trough.
Titanium base is placed in micro-arc oxidation electrolyte and carries out micro-arc oxidation treatment, the carbon containing titanium dioxide pottery of growth in situ
Enamel coating is specifically implemented according to lower step:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, Titanium base connects anode, and cathode is done with two panels stainless steel plate in the Titanium base left and right sides；
It opens mao power source and carries out oxidation processes；
After oxidation processes, Titanium base washing is taken out, is dried.
The spacing of the cathode and anode of Titanium base connection controls between 100~200mm, and oxidation trough electrolyte inside temperature is kept
At 20~30 DEG C.
Stainless steel plate uses 304 stainless steel plates.
Differential arc oxidation parameter setting: 1~3A/dm is pressed2Average current is set, 3~20%, frequency is controlled for duty ratio control
In 400~1000Hz, oxide termination voltage is controlled in 500~700V, 15~30min of oxidization time.
Gained Titanium base after micro-arc oxidation treatment is subjected to carbon thermal reduction processing, until the titanium dioxide ceramic on Titanium base surface
Layer is changed into sub- titanium oxide ceramics layer, obtains titanium-based Asia titanium oxide bipolar plates and specifically implements according to lower step:
Titanium base after micro-arc oxidation treatment to be protected using argon gas, heating rate is 10~20 DEG C/min, 1000~
It is calcined at 1100 DEG C, keeps the temperature 120~180 DEG C of min；
Heat preservation terminates, natural cooling room temperature, stops argon gas protection, titanium-based Asia titanium oxide bipolar plates are made.
Titanium plate is directly prepared sub- titanium oxide bipolar plates using differential arc oxidation and carbo-thermal process by the present invention, specifically,
It uses titanium plate for starting material, is not directed to expensive titanium dioxide or sub- titanium oxide powder material, greatly reduces cost, simultaneously
Powder is avoided to damage human respiratory tract；
Carbon containing titanium dioxide ceramic layer is generated in titanium plate surface in situ using differential arc oxidization technique, bipolar board size not by
The limitation of hot pressing die can prepare large scale bipolar plates；Carbon source agent polyethylene glycol can be carbonized using differential arc oxidization technique
And penetrate into the titanium dioxide layer of growth in situ, without titanium dioxide in powder hot-pressing technique and graphite powder (or carbon black) mixing
Technical process, and electrolyte used is nontoxic, it is environmentally protective, and form simply, daily no replacement is required, maintenance cost
It is low；
Using carbothermic reduction reaction, is calcined in argon gas protection, prepare sub- titanium oxide layer bottom and Titanium base is tight
Close combination, and surface layer is in porous structure, is conducive to provide lead flow battery more positive and negative anodes active materials reacting environment, from
And improve the efficiency of battery.The heat-treatment technology method is easy, and easily operated, process cycle is short.Process stabilizing, repeatability
It is high.It is uniform, electric that this method can be used for preparing large scale titanium-based Asia titanium oxide bipolar plate surfaces Asia titanium oxide ceramic layer performance
Conductance can reach 700S/cm or more；With the H of 3M2SO4Corrosion speed can be obtained using electrochemistry linear polarization method for electrolyte
0.1 μ A/cm of rate <2。
Embodiment 1
Titanium base surface is pre-processed:
Select specification 100mm × 100mm × 1.5mm titanium plate as Titanium base, respectively with the sand paper of 40,500 and 1200 mesh
After sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40%, impregnates 1h at 60 DEG C；
Titanium base after immersion, which moves into the oxalic acid solution that the mass percent of boiling is 15%, impregnates 1h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic 5min in acetone and deionized water, dry.
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent:
Calgon is added in the oxidation trough for filling deionized water by the concentration of 50g/L and is stirred to being completely dissolved, is obtained
To sodium hexametaphosphate solution；
Polyethylene glycol is added by by 30g/L into sodium hexametaphosphate solution, dissolution obtains mixed solution；
Film forming agent is added in mixed solution by 5g/L and is stirred evenly, with salt acid for adjusting pH value to 8, obtains differential arc oxidation electricity
Solve liquid.
Gained Titanium base carries out micro-arc oxidation treatment after will be dry, the carbon containing titanium dioxide ceramic layer of growth in situ:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, make to fly target and Titanium base below liquid level of electrolyte at 100mm, Titanium base connects anode, titanium
Cathode is done with 304 stainless steel plate of two panels at left and right sides of matrix, the spacing of cathode and anode controls between 120mm；
Refrigeration system is opened, oxidation trough electrolyte temperature is maintained at 25 DEG C；
It opens mao power source and carries out oxidation processes, differential arc oxidation parameter setting: press 1A/dm2Average current is set, is accounted for
Than control 3%, frequency control is controlled in 600Hz, oxide termination voltage in 620V, oxidization time 20min sky；
After oxidation processes, Titanium base washing is taken out, is dried.
Gained Titanium base carries out carbon thermal reduction processing after drying, until the titanium dioxide ceramic layer on Titanium base surface is changed into
Sub- titanium oxide ceramics layer:
Titanium plate after micro-arc oxidation treatment is put into Muffle furnace, is protected using argon gas, with the heating of 10 DEG C/min rate
It to 1000 DEG C, is calcined at 1000 DEG C, keeps the temperature 150min；
With furnace temperature natural cooling, when furnace temperature drops to room temperature, titanium-based Asia titanium oxide bipolar plates are made in stopping argon gas protection.
The thickness of the sub- titanium oxide ceramics layer on gained Titanium base surface is about 20 μm；The conductivity of gained bipolar plate material can
To reach 8.9 × 102S/cm, in the H of 3M2SO4For the 0.06 μ A/cm of corrosion rate of electrolyte2。
Embodiment 2
Titanium base surface is pre-processed:
Select specification 200mm × 100mm × 1.5mm titanium plate as Titanium base, respectively with the sand paper of 40,500 and 1200 mesh
After sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40%, impregnates 1.5h at 70 DEG C；
Titanium base after immersion, which moves into the oxalic acid solution that the mass percent of boiling is 15%, impregnates 1.5h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic 7min in acetone and deionized water, dry.
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent:
Calgon is added in the oxidation trough for filling deionized water by the concentration of 55g/L and is stirred to being completely dissolved, is obtained
To sodium hexametaphosphate solution；
Polyethylene glycol is added by by 35g/L into sodium hexametaphosphate solution, dissolution obtains mixed solution；
Film forming agent is added in mixed solution by 5g/L and is stirred evenly, with nitre acid for adjusting pH value to 7.5, obtains differential arc oxidation
Electrolyte.
Gained Titanium base carries out micro-arc oxidation treatment after will be dry, the carbon containing titanium dioxide ceramic layer of growth in situ:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, make to fly target and Titanium base below liquid level of electrolyte at 100mm, Titanium base connects anode, titanium
Cathode is done with 304 stainless steel plate of two panels at left and right sides of matrix, the spacing of cathode and anode controls between 120mm；
Refrigeration system is opened, oxidation trough electrolyte temperature is maintained at 20 DEG C；
It opens mao power source and carries out oxidation processes, differential arc oxidation parameter setting: press 1.5A/dm2Average current is set,
4%, frequency control is controlled in 550Hz, oxide termination voltage in 650V, oxidization time 15min for duty ratio control；
After oxidation processes, Titanium base washing is taken out, is dried.
Gained Titanium base carries out carbon thermal reduction processing after drying, until the titanium dioxide ceramic layer on Titanium base surface is changed into
Sub- titanium oxide ceramics layer:
Titanium plate after micro-arc oxidation treatment is put into Muffle furnace, is protected using argon gas, with the heating of 15 DEG C/min rate
It to 1050 DEG C, is calcined at 1050 DEG C, keeps the temperature 120min；
With furnace temperature natural cooling, when furnace temperature drops to room temperature, titanium-based Asia titanium oxide bipolar plates are made in stopping argon gas protection.
The thickness of the sub- titanium oxide ceramics layer on gained Titanium base surface is about 25 μm；The conductivity of gained bipolar plate material can
To reach 7.8 × 102S/cm, in the H of 3M2SO4For the 0.08 μ A/cm of corrosion rate of electrolyte2。
Embodiment 3
Titanium base surface is pre-processed:
Select specification 200mm × 150mm × 1.5mm titanium plate as Titanium base, respectively with the sand paper of 40,500 and 1200 mesh
After sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40%, impregnates 2.5h at 90 DEG C；
Titanium base after immersion, which moves into the oxalic acid solution that the mass percent of boiling is 15%, impregnates 2h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic 8min in acetone and deionized water, dry.
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent:
Calgon is added in the oxidation trough for filling deionized water by the concentration of 56g/L and is stirred to being completely dissolved, is obtained
To sodium hexametaphosphate solution；
Polyethylene glycol is added by by 40g/L into sodium hexametaphosphate solution, dissolution obtains mixed solution；
Film forming agent is added in mixed solution by 10g/L and is stirred evenly, with salt acid for adjusting pH value to 8, obtains differential arc oxidation
Electrolyte.
Gained Titanium base carries out micro-arc oxidation treatment after will be dry, the carbon containing titanium dioxide ceramic layer of growth in situ:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, make to fly target and Titanium base below liquid level of electrolyte at 100mm, Titanium base connects anode, titanium
Cathode is done with 304 stainless steel plate of two panels at left and right sides of matrix, the spacing of cathode and anode controls between 150mm；
Refrigeration system is opened, oxidation trough electrolyte temperature is maintained at 27 DEG C；
It opens mao power source and carries out oxidation processes, differential arc oxidation parameter setting: press 2.5A/dm2Average current is set,
5%, frequency control is controlled in 670Hz, oxide termination voltage in 620V, oxidization time 18min for duty ratio control；
After oxidation processes, Titanium base washing is taken out, is dried.
Gained Titanium base carries out carbon thermal reduction processing after drying, until the titanium dioxide ceramic layer on Titanium base surface is changed into
Sub- titanium oxide ceramics layer:
Titanium plate after micro-arc oxidation treatment is put into Muffle furnace, is protected using argon gas, with the heating of 12 DEG C/min rate
It to 1080 DEG C, is calcined at 1080 DEG C, keeps the temperature 160min；
With furnace temperature natural cooling, when furnace temperature drops to room temperature, titanium-based Asia titanium oxide bipolar plates are made in stopping argon gas protection.
The thickness of the sub- titanium oxide ceramics layer on gained Titanium base surface is about 28 μm；The conductivity of gained bipolar plate material can
To reach 8.5 × 102S/cm, in the H of 3M2SO4For the 0.07 μ A/cm of corrosion rate of electrolyte2。
Embodiment 4
Titanium base surface is pre-processed:
Select specification 250mm × 200mm × 1.5mm titanium plate as Titanium base, respectively with the sand paper of 40,500 and 1200 mesh
After sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40%, impregnates 1h at 60 DEG C；
Titanium base after immersion, which moves into the oxalic acid solution that the mass percent of boiling is 15%, impregnates 2.5h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic 9min in acetone and deionized water, dry.
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent:
Calgon is added in the oxidation trough for filling deionized water by the concentration of 60g/L and is stirred to being completely dissolved, is obtained
To sodium hexametaphosphate solution；
Polyethylene glycol is added by by 45g/L into sodium hexametaphosphate solution, dissolution obtains mixed solution；
Film forming agent is added in mixed solution by 10g/L and is stirred evenly, with salt acid for adjusting pH value to 8, obtains differential arc oxidation
Electrolyte.
Gained Titanium base carries out micro-arc oxidation treatment after will be dry, the carbon containing titanium dioxide ceramic layer of growth in situ:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, make to fly target and Titanium base below liquid level of electrolyte at 100mm, Titanium base connects anode, titanium
Cathode is done with 304 stainless steel plate of two panels at left and right sides of matrix, the spacing of cathode and anode controls between 170mm；
Refrigeration system is opened, oxidation trough electrolyte temperature is maintained at 25 DEG C；
It opens mao power source and carries out oxidation processes, differential arc oxidation parameter setting: press 3A/dm2Average current is set, is accounted for
Than control 20%, frequency control is controlled in 800Hz, oxide termination voltage in 700V, oxidization time 20min sky；
After oxidation processes, Titanium base washing is taken out, is dried.
Gained Titanium base carries out carbon thermal reduction processing after drying, until the titanium dioxide ceramic layer on Titanium base surface is changed into
Sub- titanium oxide ceramics layer:
Titanium plate after micro-arc oxidation treatment is put into Muffle furnace, is protected using argon gas, with the heating of 20 DEG C/min rate
It to 1100 DEG C, is calcined at 1100 DEG C, keeps the temperature 140min；
With furnace temperature natural cooling, when furnace temperature drops to room temperature, titanium-based Asia titanium oxide bipolar plates are made in stopping argon gas protection.
The thickness of the sub- titanium oxide ceramics layer on gained Titanium base surface is about 26 μm；The conductivity of gained bipolar plate material can
To reach 9.1 × 102S/cm, in the H of 3M2SO4For the 0.05 μ A/cm of corrosion rate of electrolyte2。
Embodiment 5
Titanium base surface is pre-processed:
Select specification 250mm × 100mm × 1.5mm titanium plate as Titanium base, respectively with the sand paper of 40,500 and 1200 mesh
After sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40%, impregnates 3h at 100 DEG C；
Titanium base after immersion, which moves into the oxalic acid solution that the mass percent of boiling is 15%, impregnates 3h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic 10min in acetone and deionized water, dry.
Micro-arc oxidation electrolyte is prepared with deionized water, calgon, polyethylene glycol and film forming agent:
Calgon is added in the oxidation trough for filling deionized water by the concentration of 55g/L and is stirred to being completely dissolved, is obtained
To sodium hexametaphosphate solution；
Polyethylene glycol is added by by 50g/L into sodium hexametaphosphate solution, dissolution obtains mixed solution；
Film forming agent is added in mixed solution by 12g/L and is stirred evenly, with nitre acid for adjusting pH value to 8, obtains differential arc oxidation
Electrolyte.
Gained Titanium base carries out micro-arc oxidation treatment after will be dry, the carbon containing titanium dioxide ceramic layer of growth in situ:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base are placed in
In the micro-arc oxidation electrolyte of configuration, make to fly target and Titanium base below liquid level of electrolyte at 100mm, Titanium base connects anode, titanium
Cathode is done with 304 stainless steel plate of two panels at left and right sides of matrix, the spacing of cathode and anode controls between 200mm；
Refrigeration system is opened, oxidation trough electrolyte temperature is maintained at 27 DEG C；
It opens mao power source and carries out oxidation processes, differential arc oxidation parameter setting: press 2A/dm2Average current is set, is accounted for
Than control 15%, frequency control is controlled in 1000Hz, oxide termination voltage in 500V, oxidization time 30min sky；
After oxidation processes, Titanium base washing is taken out, is dried.
Gained Titanium base carries out carbon thermal reduction processing after drying, until the titanium dioxide ceramic layer on Titanium base surface is changed into
Sub- titanium oxide ceramics layer:
Titanium plate after micro-arc oxidation treatment is put into Muffle furnace, is protected using argon gas, with the heating of 12 DEG C/min rate
It to 1100 DEG C, is calcined at 1100 DEG C, keeps the temperature 180min；
With furnace temperature natural cooling, when furnace temperature drops to room temperature, titanium-based Asia titanium oxide bipolar plates are made in stopping argon gas protection.
The thickness of the sub- titanium oxide ceramics layer on gained Titanium base surface is about 28 μm；The conductivity of gained bipolar plate material can
To reach 8.6 × 102S/cm, in the H of 3M2SO4For the 0.07 μ A/cm of corrosion rate of electrolyte2。
Table 1
As can be seen from Table 1: the conductivity of the positive electrode of embodiment 1-5 and the H in 3M2SO4For the corrosion speed of electrolyte
Rate reaches and is better than U.S. Department of Energy bipolar plates performance standard, i.e. conductivity should be greater than 100S/cm, and corrosion rate should be less than 1 μ A/
cm2。
The sub- titanium oxide ceramics film of 1 Titanium base Asia titanium oxide bipolar plate surfaces of embodiment is by Ti as seen from Figure 14O7Group
At.
The sub- titanium oxide ceramics film of 1 Titanium base Asia titanium oxide bipolar plate surfaces of embodiment is in porous knot as seen from Figure 2
Structure.
Claims (10)
1. a kind of Titanium base Asia titanium oxide bipolar plates, including matrix and the coating for being set to described matrix surface, which is characterized in that
Described matrix is Titanium base, and the Titanium base is titanium simple substance or titanium alloy, and the coating is sub- titanium oxide ceramics layer, the Asia
Titanium oxide ceramics layer is by TinO2n-1Composition, wherein 4≤n≤10, n are integer.
2. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates, which is characterized in that be specifically implemented according to the following steps:
Titanium base surface is pre-processed, while preparing the differential of the arc with deionized water, calgon, polyethylene glycol and film forming agent
Oxidation electrolyte；
The Titanium base is placed in the micro-arc oxidation electrolyte and carries out micro-arc oxidation treatment, the carbon containing titanium dioxide of growth in situ
Titanium ceramic layer；
Gained Titanium base after micro-arc oxidation treatment is subjected to carbon thermal reduction processing, until the titanium dioxide ceramic layer on Titanium base surface turns
Become sub- titanium oxide ceramics layer, obtains titanium-based Asia titanium oxide bipolar plates.
3. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 2, which is characterized in that described right
Titanium base surface is pre-processed, and is followed the steps below to implement:
After Titanium base sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 35%~45%, is soaked at 60~100 DEG C
Steep 1~3h；
Titanium base after immersion is moved into the oxalic acid solution that the mass percent of boiling is 10%~20% and impregnates 1~3h；
Titanium base after oxalic acid solution impregnates successively is cleaned by ultrasonic in acetone and deionized water to 5~10min, is done
It is dry.
4. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 2, which is characterized in that the use
Deionized water, calgon, polyethylene glycol and film forming agent are prepared micro-arc oxidation electrolyte and are specifically implemented according to the following steps:
Dissolution in deionized water is added in calgon and obtains sodium hexametaphosphate solution；
Polyethylene glycol is added into the sodium hexametaphosphate solution, stirring and dissolving obtains mixed solution；
Film forming agent is added in the mixed solution and is stirred evenly, pH value is adjusted to 7~8, obtains the micro-arc oxidation electrolyte.
5. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 4, which is characterized in that described micro-
The quality of calgon, polyethylene glycol and film forming agent is 5~6:3~5:0.5~1.2g in every liter of arc oxidation electrolyte.
6. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 5, which is characterized in that it is described at
Film is made of ethanedioic acid titanium amine and sodium oxalate with the mass ratio of 10:1.
7. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 2, which is characterized in that described to incite somebody to action
The Titanium base, which is placed in the micro-arc oxidation electrolyte, carries out micro-arc oxidation treatment, the carbon containing titanium dioxide ceramic of growth in situ
Layer is specifically implemented according to lower step:
On the winged target for hanging over oxidation trough after Titanium base resulting after drying is clamped, and winged target and Titanium base merging are configured
Micro-arc oxidation electrolyte in, the Titanium base connects anode, does cathode with two panels stainless steel plate at left and right sides of Titanium base；
It opens mao power source and carries out oxidation processes；
After oxidation processes, Titanium base washing is taken out, is dried.
8. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 7, which is characterized in that the titanium
The spacing of the cathode and anode of matrix connection controls between 100~200mm, and the oxidation trough electrolyte inside temperature is maintained at 20~
30℃。
9. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 7, which is characterized in that described micro-
The setting of arc oxygenation parameters: 1~3A/dm is pressed2Set average current, duty ratio control 3~20%, frequency control 400~
1000Hz, oxide termination voltage are controlled in 500~700V, 15~30min of oxidization time.
10. a kind of preparation method of Titanium base Asia titanium oxide bipolar plates according to claim 2, which is characterized in that described
Gained Titanium base after micro-arc oxidation treatment is subjected to carbon thermal reduction processing, until the titanium dioxide ceramic layer on Titanium base surface is changed into
Sub- titanium oxide ceramics layer obtains titanium-based Asia titanium oxide bipolar plates and specifically implements according to lower step:
Titanium base after micro-arc oxidation treatment is protected using argon gas, heating rate is 10~20 DEG C/min, 1000~1100
It is calcined at DEG C, keeps the temperature 120~180 DEG C of min；
Heat preservation terminates, natural cooling room temperature, stops argon gas protection, the titanium-based Asia titanium oxide bipolar plates are made.
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