CN107794556A - A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates - Google Patents
A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- H01M8/00—Fuel cells; Manufacture thereof
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- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
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Abstract
The invention provides a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, the aluminium alloy after sand paper grinding process is first subjected to electrochemical polish in the ethanol solution of perchloric acid；The aluminium alloy after electrochemical polish is subjected to anodized in phosphate aqueous solution again；Then aluminium alloy is immersed in plant acid solution ultrasonic；Finally aluminium alloy is put into the mixed solution of tin ion and graphene oxide and carries out electro-deposition, so as to prepare one layer of tin ash/graphene oxide composite membrane in aluminum alloy surface.The method of the present invention is a kind of fairly simple, cheap novel processing step easy to control and green, and the used in proton exchange membrane fuel cell aluminium alloy bipolar plates as obtained by the preparation method of the present invention is final have high antiseptic property.
Description
Technical field
The invention belongs to chemical field, is related to a proton exchanging film fuel battery, specifically a kind of proton exchange
The surface modifying method of membrane cell aluminium alloy bipolar plates.
Background technology
With rapid development of economy and the rapid growth of population, the energy resource consumption in the world is also continuously increased, fossil fuel
Great number consumption will deepen world energy sources crisis, while bring the problem of environmental pollution of getting worse.As green energy resource it
One Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cells, PEMFC) has power density
Height, operating temperature is low, starts fast, the advantages such as service life is grown, and is most hopeful to substitute fossil fuel as delivery vehicles such as automobiles
Power source.Bipolar plates are another critical materials outside membrane removal and catalyst in PEMFC, and it occupies battery weight 70%~80%
With the 45% of cost, very important effect is played to the stable operation and popularization and application for ensureing battery.Business is using most at present
Extensive bipolar plates are graphite bi-polar plate, but graphite bi-polar plate density is big, high processing costs, and this aspect increase is that proton is handed over
The weight for changing membrane cell limits its application, and other hand adds the cost of fuel cell, and these factors are common
Limit PEMFC further commercialization popularization and application.
Aluminum alloy materials density is small, cost is low, easy processing, is potential preferable bipolar plate material.However, proton exchange
The working media of membrane cell is harsher, and in faintly acid, its pH value is 3~5, and contains a certain amount of SO4 2-, F-With compared with
A small amount of NO3 -, Cl-Deng corrosive ion, the running temperature of battery is typically at 60~100 DEG C, so wanting to enable aluminum alloy to bipolar
Plate is able to apply etching problem that just must be to solution bipolar plates in PEMFC environment.
In recent years, domestic and foreign scholars have been carried out greatly to solve etching problem of the aluminium alloy bipolar plates in PEMFC environment
Quantifier elimination works.The Chinese invention patent of Application No. 201510937054.5 discloses a kind of graphene doping conducting polymer
Dual polar plates of proton exchange membrane fuel cell and preparation method thereof of thing modification, bipolar plates prepared by this method be
0.01mol/L Na2SO4Tested in+0.01mol/L HCl comparatively gentle simulated solution and corrosion electric current density only reduces
2 quantity, and the aluminium alloy bipolar plates that the method for the present invention is modified are in 0.5mol/L H2SO4It is rotten under+2ppm HF strong acid environment
Erosion current density reduces by 3 order of magnitude protective efficacies and is up to 99.9%.The Chinese invention patent of Application No. 200710014455.9
The preparation method for a kind of bipolar plate for fuel cell announced, using alkalescence and acid double solution system chemical plating nickel-phosphorus alloys pair
Aluminium alloy bipolar plate surfaces are modified, but this method will not only use a large amount of poisonous and hazardous chemical reagent but also prepare work
Skill is extremely complex.The present invention using method of modifying it is simple, green be easy to large-scale industrial production.
The content of the invention
For the problems of the prior art, the invention provides a kind of used in proton exchange membrane fuel cell aluminium alloy bipolar plates
Surface modifying method, the surface modifying method of described this used in proton exchange membrane fuel cell aluminium alloy bipolar plates will solve
Treatment process existing for Proton Exchange Membrane Fuel Cells aluminium alloy bipolar plate surfaces technology of the prior art is complicated, cost is higher
With the technical problem such as environmental pollution.
The invention provides a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, including such as
Lower step：
1) aluminium alloy after sand paper grinding process is subjected to electrochemical polish in the ethanol solution of perchloric acid；
2) aluminium alloy after electrochemical polish is subjected to anodized in phosphate aqueous solution；
3) aluminium alloy after step 2) processing is immersed in plant acid solution ultrasonic；
4) and then the aluminium alloy after step 3) processing is put into the mixed solution of tin ion and graphene oxide and carries out electricity
Deposition, so as to prepare one layer of tin ash/graphene oxide composite membrane in aluminum alloy surface.
Further, the surface modifying method of above-mentioned a kind of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, bag
Include following steps：
1) one carries out electro-chemical polish step to used in proton exchange membrane fuel cell aluminum alloy surface, and it is clear will to pass through polishing
Aluminium alloy after washing carries out electrochemical polish processing in the ethanol solution of perchloric acid；Described perchloric acid is in ethanol solution
Volume fraction be 5vol.%~50vol.%；
2) aluminum alloy surface is carried out anodization step by one, by the aluminium alloy Jing Guo electrochemical polishing treatment in phosphoric acid
Anodized is carried out in the aqueous solution；The concentration of described phosphate aqueous solution is 0.05~0.5mol/L；
3) one carries out processing step using plant acid solution, by the aluminium alloy by above-mentioned steps processing in mass percent
1~60min of ultrasound in the plant acid solution that concentration is 1~10%, it is then standby with drying up；
4) the step of preparation electric depositing solution, described electric depositing solution is by graphene oxide, SnCl2、HNO3、
KNO3, pyrrolidones K-30 and deionized water composition, in described electric depositing solution, the concentration of described graphene oxide is
0.01~0.1mg/mL, described SnCl2Concentration is 5~100mmol/L, described HNO3Concentration be 10~100mmol/L,
Described KNO3Concentration be 10~100mmol/L, described pyrrolidones K-30 concentration is 1~60mg/mL；It will mix equal
Even solution leads to 0.5~3h of oxygen under 40~70 DEG C of water bath condition；
5) electrodeposition step, electro-deposition is carried out using three-electrode system, aluminium alloy is as working electrode, platinum plate electrode
Electric depositing solution is positioned under 40~70 DEG C of water bath condition as reference electrode as to electrode, saturated calomel electrode
Row electro-deposition, the method used prepare one layer of titanium dioxide for cyclic voltammetry or constant voltage or galvanostatic method, in aluminum alloy surface
Tin/graphene oxide composite membrane, complete the surface modification to used in proton exchange membrane fuel cell aluminium alloy bipolar plates.
Further, the aluminium alloy of step 1) is aluminium alloy 5052 or aluminium alloy 6061；Step 1) is using two electrodes
System, aluminium alloy are used as to electrode as working electrode platinum plate electrode, and the voltage of application be 5V~110V, the time for 1~
10min。
Further, step 2) is used as to electricity using two electrode systems, aluminium alloy as working electrode platinum plate electrode
Pole, the voltage of application is 5V~110V, and the time is 1~60min.
Further, bath temperature is during step 5) electro-deposition, 0.1~-10V of its voltage range, current density range 5~
100mA/cm2。
In the modifying process of the present invention, the effect of phytic acid is：Phytic acid has very strong sequestering power, and its 6 negatively charged
Phosphate groups, have huge chelating potential energy between metal cation, therefore phytic acid can not only strengthen the resistance to of aluminum alloy substrate
Corrosion energy and the adhesion between composite film and aluminum alloy substrate can be strengthened.
The electro-deposition SnO of the present invention2Mechanism：
Sn2++O2+2H2O+2e-→Sn4++4OH-
Sn4++4OH-→Sn(OH)4→SnO2+H2O
Electro-deposition GO mechanism：There are a large amount of oxygen-containing functional groups (- COOH ,-OH ,-O-) on GO (graphene oxide), in electric field
Act on and be partially reduced to rGO (redox graphene) on aluminum alloy anode to GO.
Preferably, the volume fraction of step 1) perchloric acid is 25vol.%, voltage 25V, time 4min.
Preferably, step 2) phosphoric acid concentration is 0.3mol/L, voltage 35V, time 30min.
Preferably, step 3) phytic acid mass fraction 3wt.%, ultrasonic time 15min.
Preferably, the optimum proportioning of step 4) electrodeposit liquid is：GO (graphene oxide) concentration is 0.05mg/mL,
SnCl2Concentration is 20mmol/L, HNO3Concentration be 75mmol/L, KNO3Concentration be 100mmol/L, pyrrolidones K-30's
Concentration is 20mg/mL.
Preferably, step 5) bath temperature is 50 DEG C, using cyclic voltammetry, scanning range 0.6V~-1.1V.
The present invention prepares the SnO of gained2The aluminium alloy bipolar plates of the compound membrane modifyings of/GO, it is in 0.5mol/LH2SO4+2ppm
Corrosion electric current density 1.057 × 10 in HF simulated solution-7A/cm23 quantity and corrosion potential are reduced compared with naked aluminium alloy
424mv is shuffled, its inhibition efficiency η has reached 99.9%.
The present invention first prepares equally distributed honeycomb to aluminum alloy surface progress anodic oxidation due to using on its surface
Shape nanometer micropore, then it is surface-treated again with plant acid solution so as to enhance SnO2/ GO composite membranes and aluminum alloy substrate
Adhesive force.The SnO of preparation2The compound film quality of/GO is close and SnO2It is evenly distributed with GO, the composite membrane not only has to aluminum alloy substrate
Extraordinary protective effect and GO presence enhance the electric conductivity of film layer.This method is that one kind is fairly simple, cheap easy
Control and green novel processing step, the Proton Exchange Membrane Fuel Cells as obtained by the preparation method of the present invention is final
There is high antiseptic property with aluminium alloy bipolar plates.
The present invention compares with prior art, and its technological progress is significant.The present invention is to overcome above-mentioned prior art
The defects of existing and provide a kind of green, treatment process is simple, and cost is low, the good Proton Exchange Membrane Fuel Cells of stability
With the surface modifying method of aluminium alloy bipolar plates.
Brief description of the drawings
The SnO that Fig. 1 cyclic voltammetries (0.6~-1.1V of scanning range) deposit on the surface of aluminium alloy 50522/ GO composite membranes
Surface SEM schemes
SnO prepared by Fig. 2 cyclic voltammetries (0.6~-1.1V of scanning range)2The complex film modified aluminium alloys 5052 of/GO try
The cross section SEM figures and distribution diagram of element (mapping) of sample.
SnO prepared by Fig. 3 cyclic voltammetries (0.6~-1.1V of scanning range)2The complex film modified aluminium alloys 5052 of/GO try
The cross section SEM figures of sample and Elemental redistribution linear scan.
The SnO that Fig. 4 cyclic voltammetries (0.6~-1.5V of scanning range) deposit on the surface of aluminium alloy 50522/ GO composite membranes
Surface SEM schemes
Fig. 5 are respectively (1) naked aluminium alloy 5052；(2) 0.6~-1.5V of scanning range prepares SnO2/ GO is complex film modified
Aluminium alloy 5052；(3) 0.6~-1.1V of scanning range prepares SnO2The complex film modified aluminium alloys 5052 of/GO measure in simulated solution
Tafel polarization curves.
Embodiment
The present invention is expanded on further below by case study on implementation and with reference to accompanying drawing, but is not intended to limit the present invention.
The SnO of the present invention2The assay method scanning electron microscopy of the aluminum alloy surface morphology characterization of the compound membrane modifyings of/GO
Mirror (SU-1500, Japanese Hitachi companies) observes the surface topography of sample.
Electrochemical analysis
The measurement of polarization curve is completed in three-electrode system, and test solution is 0.5mol/L H2SO4+ 2ppmHF proton
In exchange film fuel battery simulated solution, working electrode SnO2The aluminum alloy anode or naked aluminum alloy anode of the compound membrane modifyings of/GO,
Auxiliary electrode and reference electrode are respectively Pt plate electrodes and saturated calomel electrode (SCE).Electro-chemical test uses instrument as occasion China
CHI660E electrochemical workstations.AC impedance frequency range is 100kHz-0.01Hz, and ac-excited signal peak is 10mV；Pole
Change curved scanning scope OCP E ± 250mV (vs.SCE), sweep speed 1mV/s.
Inhibition efficiency (η) calculates according to equation below：
Wherein I0It is respectively the corrosion electric current density of the untreated aluminum alloy anode with after processing with I.
Embodiment 1：
A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, comprises the following steps：
(1) aluminum alloy surface electrochemical polish：Using two electrode systems, aluminium alloy is as working electrode platinum plate electrode
(2cm × 2cm) is as to electrode.By the sample of aluminium alloy 5052 after polishing is cleaned in the height that volume fraction is 25vol.%
Anodized is carried out in the ethanol solution of chloric acid, application voltage is 25V, time 4min.
(2) aluminum alloy surface anodic oxidation：Using two electrode systems, tried by the aluminium alloy 5052 of electrochemical polish
Sample is as working electrode platinum plate electrode (2cm × 2cm) as to electrode.Concentration be 0.3mol/L phosphoric acid solutions in carry out sun
Pole aoxidizes, and the voltage of application is 35V, time 30min.
(3) plant acid solution is handled：The sample of aluminium alloy 5052 that process above-mentioned steps are handled is 1wt.% in mass fraction
Plant acid solution in ultrasound (power 50W) 15min, then with warm wind dry up it is standby.
(4) deposit liquid to prepare, wherein GO (graphene oxide) concentration is 0.05mg/mL, SnCl2Concentration be 5~
100mmol/L, HNO3Concentration be 10~100mmol/L, KNO3Concentration be 20mmol/L, pyrrolidones K-30 concentration is
20mg/mL.Well mixed solution is led into oxygen 1h under 50 DEG C of water bath condition.
(5) electro-deposition SnO2/ GO composite membranes：Electro-deposition is carried out using three-electrode system, the sample of aluminium alloy 5052 is as work
Make electrode, platinum plate electrode (2cm × 2cm) is as to electrode, and saturated calomel electrode is as reference electrode.Deposition liquid is positioned over 50 DEG C
Water bath condition under carry out electro-deposition, the method used is cyclic voltammetry, scanning range 0.6V~-1.1V.
Fig. 1 are the SnO prepared with cyclic voltammetry (scanning range 0.6V~-1.1V) on the surface of aluminium alloy 50522/GO
The SEM figures of composite film surface amplification different multiplying (Fig. 1 a~d), the SnO prepared as seen from the figure2It is spherical and arrangement is tight for nanometer
It is close, the GO and SnO on surface2It is brought into close contact.Fig. 2 are SnO prepared by cyclic voltammetry (0.6~-1.1V of scanning range)2/ GO is multiple
Close the cross section SEM figures and element (Al, O, C, Sn) distribution map (mapping) of the film modified sample of aluminium alloy 5052.By cross section
SEM figures can be found, combined closely between composite film and the substrate of aluminium alloy 5052 and matter is close compared with composite film.By Al,
O, C, Sn distribution diagram of element (mapping) understand that O, C, Sn elements are dispersed, i.e. SnO in composite film2/GO
SnO in composite membrane2It is dispersed with GO.Fig. 3 are SnO prepared by cyclic voltammetry (0.6~-1.1V of scanning range)2/GO
The cross section SEM figures and Elemental redistribution linear scan figure of the complex film modified sample of aluminium alloy 5052, following graphical representation
It is change of the different elements along directions of rays cellulose content.Understood with reference to Fig. 2 and Fig. 3, the SnO on the surface of aluminium alloy 50522/ GO is multiple
It is about 100 μm to close film thickness.
Fig. 5 are respectively (1) naked aluminium alloy 5052；(2) 0.6~-1.5V of scanning range prepares SnO2/ GO is complex film modified
Aluminium alloy 5052；(3) 0.6~-1.1V of scanning range prepares SnO2The complex film modified aluminium alloys 5052 of/GO measure in simulated solution
Tafel polarization curves.
Table 1. is the related electrochemical parameter corresponding to Fig. 5
From table 1., (1) naked aluminium alloy 5052；(2) 0.6~-1.5V of scanning range prepares SnO2/ GO is complex film modified
Aluminium alloy 5052；(3) 0.6~-1.1V of scanning range prepares SnO2The complex film modified samples of aluminium alloy 5052 of/GO are in 0.5H2SO4+
Corrosion electric current density in 2ppmHF Proton Exchange Membrane Fuel Cells simulated solution is respectively 1.024 × 10-4A/cm2、3.633×
10-7A/cm2、1.057×10-7A/cm2, corrosion potential is respectively -0.781V, -0.497V, -0.357V.Scanning range 0.6~-
1.1V prepares SnO2The corrosion electric current density of the relatively naked aluminium alloy of the complex film modified samples of aluminium alloy 5052 of/GO reduces by 3 quantity
Level, corrosion potential shuffle 424mV, and inhibition efficiency is up to 99.9%.
Embodiment 2：
A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, comprises the following steps：
(1) aluminum alloy surface electrochemical polish：Using two electrode systems, aluminium alloy 5052 is used as working electrode platinized platinum
Electrode (2cm × 2cm) is as to electrode.In volume fraction it is 25vol.% by the sample of aluminium alloy 5052 after polishing is cleaned
Perchloric acid ethanol solution in carry out anodized, application voltage is 25V, time 4min.
(2) aluminum alloy surface anodic oxidation：Using two electrode systems, tried by the aluminium alloy 5052 of electrochemical polish
Sample is as working electrode platinum plate electrode (2cm × 2cm) as to electrode.Concentration be 0.3mol/L phosphoric acid solutions in carry out sun
Pole aoxidizes, and the voltage of application is 35V, time 30min.
(3) plant acid solution is handled：The sample of aluminium alloy 5052 that process above-mentioned steps are handled is 1wt.% in mass fraction
Plant acid solution in ultrasound (power 50W) 15min, then with warm wind dry up it is standby.
(4) deposit liquid to prepare, wherein GO (graphene oxide) concentration is 0.05mg/mL, SnCl2Concentration be 5~
100mmol/L, HNO3Concentration be 10~100mmol/L, KNO3Concentration be 20mmol/L, pyrrolidones K-30 concentration is
20mg/mL.Well mixed solution is led into oxygen 1h under 50 DEG C of water bath condition.
(5) electro-deposition SnO2/ GO composite membranes：Electro-deposition is carried out using three-electrode system, the sample of aluminium alloy 5052 is as work
Make electrode, platinum plate electrode (2cm × 2cm) is as to electrode, and saturated calomel electrode is as reference electrode.Deposition liquid is positioned over 50 DEG C
Water bath condition under carry out electro-deposition, the method used is cyclic voltammetry, scanning range 0.6V~-1.5V.
Fig. 4 are that cyclic voltammetry (0.6~-1.5V of scanning range) is compound in the SnO2/GO that the surface of aluminium alloy 5052 deposits
Film surface amplification different multiplying (Fig. 4 a~d) SEM figures.As seen from the figure, SnO2/GO is prepared in 0.6~-1.5V scanning range
Scanning range (Fig. 1) preparation film layer of the composite film compared with 0.6~-1.1V is loose and crackle is more.Scanning range is understood by table 1.
0.6~-1.5V prepares PEM of the complex film modified samples of aluminium alloy 5052 of SnO2/GO in 0.5H2SO4+2ppmHF and fired
Expect that the corrosion electric current density in battery simulated solution is 3.633 × 10-7A/cm2, corrosion potential is -0.497V, and corrosion potential is shuffled
284mV, inhibition efficiency are up to 99.65%.The SnO2/GO composite membranes of preparation is anti-corrosion in this explanation 0.6~-1.5V scanning range
Performance is good not as what is prepared in 0.6~-1.1V scanning ranges.
Embodiment 3：
(1) aluminum alloy surface electrochemical polish：Using two electrode systems, aluminium alloy 6061 is used as working electrode platinized platinum
Electrode (2cm × 2cm) is as to electrode.In volume fraction it is 25vol.% by the sample of aluminium alloy 5052 after polishing is cleaned
Perchloric acid ethanol solution in carry out anodized, application voltage is 25V, time 4min.
(2) aluminum alloy surface anodic oxidation：Using two electrode systems, tried by the aluminium alloy 6061 of electrochemical polish
Sample is as working electrode platinum plate electrode (2cm × 2cm) as to electrode.Concentration be 0.3mol/L phosphoric acid solutions in carry out sun
Pole aoxidizes, and the voltage of application is 35V, time 30min.
(3) plant acid solution is handled：The sample of aluminium alloy 6061 that process above-mentioned steps are handled is 1wt.% in mass fraction
Plant acid solution in ultrasound (power 50W) 15min, then with warm wind dry up it is standby.
(4) deposit liquid to prepare, wherein GO (graphene oxide) concentration is 0.05mg/mL, SnCl2Concentration be 5~
100mmol/L, HNO3Concentration be 10~100mmol/L, KNO3Concentration be 20mmol/L, pyrrolidones K-30 concentration is
20mg/mL.Well mixed solution is led into oxygen 1h under 50 DEG C of water bath condition.
(5) electro-deposition SnO2/ GO composite membranes：Electro-deposition is carried out using three-electrode system, the sample of aluminium alloy 6061 is as work
Make electrode, platinum plate electrode (2cm × 2cm) is as to electrode, and saturated calomel electrode is as reference electrode.Deposition liquid is positioned over 50 DEG C
Water bath condition under carry out electro-deposition, the method used is cyclic voltammetry, scanning range 0.6V~-1.1V.
The relevant characterization results such as SEM (SEM), electro-chemical test show with aluminium alloy 6061 as substrate system
It is that substrate prepares SnO2/GO composite membranes without significant difference for SnO2/GO composite membranes and with aluminium alloy 5052, institute also fits in this way
For aluminium alloy 6061.
Above said content is only the basic explanation under present inventive concept, and is appointed according to what technical scheme was made
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (5)
1. a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, it is characterised in that including following step
Suddenly：
1) aluminium alloy after sand paper grinding process is subjected to electrochemical polish in the ethanol solution of perchloric acid；
2) aluminium alloy after electrochemical polish is subjected to anodized in phosphate aqueous solution；
3) aluminium alloy after step 2) processing is immersed in plant acid solution ultrasonic；
4) and then the aluminium alloy after step 3) processing is put into the mixed solution of tin ion and graphene oxide and carries out electro-deposition,
So as to prepare one layer of tin ash/graphene oxide composite membrane in aluminum alloy surface.
2. a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates according to claim 1,
It is characterized in that comprise the following steps：
1) one carries out electro-chemical polish step to used in proton exchange membrane fuel cell aluminum alloy surface, will be after polishing is cleaned
Aluminium alloy electrochemical polish processing is carried out in the ethanol solution of perchloric acid；Body of the described perchloric acid in ethanol solution
Fraction is 5vol.%~50vol.%；
2) aluminum alloy surface is carried out anodization step by one, and the aluminium alloy Jing Guo electrochemical polishing treatment is water-soluble in phosphoric acid
Anodized is carried out in liquid；The concentration of described phosphate aqueous solution is 0.05~0.5mol/L；
3) one carries out processing step using plant acid solution, by the aluminium alloy by above-mentioned steps processing in mass percent concentration
It is then standby with drying up for 1~60min of ultrasound in 1~10% plant acid solution；
4) the step of preparation electric depositing solution, described electric depositing solution is by graphene oxide, SnCl2、HNO3、KNO3, pyrrole
Pyrrolidone K-30 and deionized water composition, in described electric depositing solution, the concentration of described graphene oxide for 0.01~
0.1mg/mL, described SnCl2Concentration is 5~100mmol/L, described HNO3Concentration be 10~100mmol/L, it is described
KNO3Concentration be 10~100mmol/L, described pyrrolidones K-30 concentration is 1~60mg/mL；It is molten by what is be well mixed
Liquid leads to 0.5~3h of oxygen under 40~70 DEG C of water bath condition；
5) electrodeposition step, electro-deposition is carried out using three-electrode system, aluminium alloy is as working electrode, platinum plate electrode conduct
To electrode, electric depositing solution is positioned under 40~70 DEG C of water bath condition as reference electrode and carries out electricity by saturated calomel electrode
Deposition, the method used prepare one layer of tin ash/oxygen for cyclic voltammetry or constant voltage or galvanostatic method, in aluminum alloy surface
Graphite alkene composite membrane, complete the surface modification to used in proton exchange membrane fuel cell aluminium alloy bipolar plates.
3. a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates according to claim 2,
It is characterized in that：The aluminium alloy of step 1) is aluminium alloy 5052 or aluminium alloy 6061；
Step 1) is used as to electrode, the voltage of application using two electrode systems, aluminium alloy as working electrode platinum plate electrode
For 5V~110V, the time is 1~10min.
4. a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates according to claim 2,
It is characterized in that：Step 2) is used as to electrode as working electrode platinum plate electrode, applied using two electrode systems, aluminium alloy
Voltage be 5V~110V, the time is 1~60min.
5. a kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates according to claim 2,
It is characterized in that：Bath temperature is during step 5) electro-deposition, its voltage range 0.1~-10V, 5~100mA/ of current density range
cm2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109985794A (en) * | 2019-03-27 | 2019-07-09 | 上海电力学院 | The method of the modified aluminium alloy of graphene oxide/stannic oxide/silane laminated film |
| CN113215569A (en) * | 2021-06-08 | 2021-08-06 | 湖北欣洁顺幕墙材料有限公司 | Aluminum product surface environment-friendly treatment processing technology for curtain wall material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070003813A1 (en) * | 2005-06-30 | 2007-01-04 | General Motors Corporation | Stable conductive and hydrophilic fuel cell contact element |
| CN101425586A (en) * | 2008-10-11 | 2009-05-06 | 大连海事大学 | Modification method for thin-film aluminum dual polar plates of proton exchange membrane fuel cell |
| CN101654245A (en) * | 2009-10-10 | 2010-02-24 | 天津大学 | Solid-liquid interface self-assembly preparation method for graphene oxide film |
| CN102054989A (en) * | 2010-12-06 | 2011-05-11 | 长沙理工大学 | Bipolar plate for proton exchange membrane fuel cell and manufacture method thereof |
| CN102810400A (en) * | 2011-05-31 | 2012-12-05 | 海洋王照明科技股份有限公司 | Composite solid electrolytic capacitor electrode plate and manufacturing method thereof |
| CN104047043A (en) * | 2014-06-27 | 2014-09-17 | 厦门大学 | Preparation method of TiO2/SnO2 semiconductor two-layer composite film photo anode |
| CN105355438A (en) * | 2015-11-30 | 2016-02-24 | 北京化工大学 | Electrochemistrical preparation method of SnO2 nanorod |
| CN105588864A (en) * | 2015-12-18 | 2016-05-18 | 清华大学深圳研究生院 | Electrode, preparation method thereof, and electrochemical biosensor |
| CN106283139A (en) * | 2016-09-08 | 2017-01-04 | 江西理工大学 | Nickel tungsten Graphene composite plating bath, coating and preparation method thereof |
-
2017
- 2017-10-09 CN CN201710929789.2A patent/CN107794556B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070003813A1 (en) * | 2005-06-30 | 2007-01-04 | General Motors Corporation | Stable conductive and hydrophilic fuel cell contact element |
| CN101425586A (en) * | 2008-10-11 | 2009-05-06 | 大连海事大学 | Modification method for thin-film aluminum dual polar plates of proton exchange membrane fuel cell |
| CN101654245A (en) * | 2009-10-10 | 2010-02-24 | 天津大学 | Solid-liquid interface self-assembly preparation method for graphene oxide film |
| CN102054989A (en) * | 2010-12-06 | 2011-05-11 | 长沙理工大学 | Bipolar plate for proton exchange membrane fuel cell and manufacture method thereof |
| CN102810400A (en) * | 2011-05-31 | 2012-12-05 | 海洋王照明科技股份有限公司 | Composite solid electrolytic capacitor electrode plate and manufacturing method thereof |
| CN104047043A (en) * | 2014-06-27 | 2014-09-17 | 厦门大学 | Preparation method of TiO2/SnO2 semiconductor two-layer composite film photo anode |
| CN105355438A (en) * | 2015-11-30 | 2016-02-24 | 北京化工大学 | Electrochemistrical preparation method of SnO2 nanorod |
| CN105588864A (en) * | 2015-12-18 | 2016-05-18 | 清华大学深圳研究生院 | Electrode, preparation method thereof, and electrochemical biosensor |
| CN106283139A (en) * | 2016-09-08 | 2017-01-04 | 江西理工大学 | Nickel tungsten Graphene composite plating bath, coating and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUNFEI LIANG等: "One-Step In situ Synthesis of SnO2/Graphene Nanocomposites andIts Application As an Anode Material for Li-Ion Batteries", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 万云霄: "质子交换膜燃料电池用铝合金双极板表面改性及其性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109985794A (en) * | 2019-03-27 | 2019-07-09 | 上海电力学院 | The method of the modified aluminium alloy of graphene oxide/stannic oxide/silane laminated film |
| CN113215569A (en) * | 2021-06-08 | 2021-08-06 | 湖北欣洁顺幕墙材料有限公司 | Aluminum product surface environment-friendly treatment processing technology for curtain wall material |
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