CN107794556B - 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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- CN107794556B CN107794556B CN201710929789.2A CN201710929789A CN107794556B CN 107794556 B CN107794556 B CN 107794556B CN 201710929789 A CN201710929789 A CN 201710929789A CN 107794556 B CN107794556 B CN 107794556B
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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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
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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
- C25D11/04—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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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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
- H01M8/0258—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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 present invention provides a kind of surface modifying methods of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, and the aluminium alloy after sand paper grinding process is first carried out 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, to prepare one layer of stannic oxide/graphene oxide composite membrane in aluminum alloy surface.Method of the invention is a kind of fairly simple, cheap novel processing step easy to control and environmentally protective, and finally resulting used in proton exchange membrane fuel cell aluminium alloy bipolar plates have high antiseptic property to preparation method through the invention.
Description
Technical field
The invention belongs to chemical fields, are 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 technique
With the rapid growth of rapid development of economy and population, the energy consumption in the world is also continuously increased, fossil fuel
Great number consumption will deepen world energy sources crisis, while bringing the problem of environmental pollution got 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, and starting is fast, the advantages such as long service life, is most hopeful that fossil fuel is replaced to become the delivery vehicles such as automobile
Power source.Bipolar plates are another critical materials in PEMFC outside membrane removal and catalyst, it occupies battery weight 70%~80%
With the 45% of cost, very important effect is played to the stable operation and popularization and application that ensure battery.Business is using most at present
Extensive bipolar plates are graphite bi-polar plate, but graphite bi-polar plate density is big, processing cost is high, and this aspect increase is that proton is handed over
The weight for changing membrane cell limits its scope of application, and other hand increases the cost of fuel cell, these factors are common
The further commercialization for limiting PEMFC promotes and applies.
Aluminum alloy materials density is small, at low cost, easy processing, is potential ideal bipolar plate material.However, proton exchange
The working media of membrane cell is harsher, weakly acidic, and pH value is 3~5, and contains a certain amount of SO4 2-, F-With compared with
A small amount of NO3 -, Cl-Equal corrosive ions, the running temperature of battery is generally at 60~100 DEG C, so bipolar to enable aluminum alloy to
Plate, which is able to apply, must just give etching problem of the solution bipolar plates in PEMFC environment.
In recent years, domestic and foreign scholars have carried out greatly to solve etching problem of the aluminium alloy bipolar plates in PEMFC environment
Quantifier elimination work.Application No. is 201510937054.5 Chinese invention patents to disclose a kind of graphene doping conducting polymer
The dual polar plates of proton exchange membrane fuel cell and preparation method thereof of object modification, the bipolar plates of this method preparation be
0.01mol/L Na2SO4Test in the comparatively gentle simulated solution of+0.01mol/L HCl and corrosion electric current density only reduces
2 quantity, and the aluminium alloy bipolar plates that method of the invention is modified are in 0.5mol/L H2SO4It is rotten under the strong acid environment of+2ppm HF
Erosion current density reduces by 3 order of magnitude protection efficiencies and is up to 99.9%.Application No. is 200710014455.9 Chinese invention patents
The preparation method for a kind of bipolar plate for fuel cell announced, using alkalinity 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 preparation work
Skill is extremely complex.The present invention is simple using method of modifying, environmentally protective convenient for large-scale industrial production.
Summary of the invention
For the problems of the prior art, the present invention provides a kind of used in proton exchange membrane fuel cell aluminium alloy bipolar plates
Surface modifying method, the surface modifying method of this used in proton exchange membrane fuel cell aluminium alloy bipolar plates will solve
The complexity for the treatment of process existing for Proton Exchange Membrane Fuel Cells aluminium alloy bipolar plate surfaces technology in the prior art, higher cost
With the technical problems such as environmental pollution.
The present invention provides a kind of surface modifying methods 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) by step 2), treated that aluminium alloy is immersed in is ultrasonic in plant acid solution；
4) then by step 3), treated that aluminium alloy is put into that electricity is carried out in the mixed solution of tin ion and graphene oxide
Deposition, to prepare one layer of stannic oxide/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, packet
Include following steps:
1) one carries out electro-chemical polish step to used in proton exchange membrane fuel cell aluminum alloy surface, will be clear by polishing
Aluminium alloy after washing carries out electrochemical polish processing in the ethanol solution of perchloric acid；The 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 aqueous solution；The concentration of the 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 spare with drying up；
4) the step of preparation electric depositing solution, the electric depositing solution is by graphene oxide, SnCl2、HNO3、
KNO3, pyrrolidones K-30 and deionized water composition, in the electric depositing solution, the concentration of the graphene oxide is
0.01~0.1mg/mL, the SnCl2Concentration is 5~100mmol/L, the HNO3Concentration be 10~100mmol/L,
The KNO3Concentration be 10~100mmol/L, the concentration of the pyrrolidones K-30 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 carries out electro-deposition using three-electrode system, and aluminium alloy is as working electrode, platinum plate electrode
As to electrode, saturated calomel electrode as reference electrode, electric depositing solution is placed under 40~70 DEG C of water bath condition into
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 is completed modified to the surface of 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 working electrode platinum plate electrode to electrode, and the voltage of application is 5V~110V, and the time is 1~
10min。
Further, step 2) is used as working electrode platinum plate electrode to electricity using two electrode systems, aluminium alloy
Pole, the voltage of application are 5V~110V, and the time is 1~60min.
Further, bath temperature is when step 5) electro-deposition, 0.1~-10V of voltage range, current density range 5~
100mA/cm2。
In modifying process of the invention, the effect of phytic acid is: phytic acid has very strong sequestering power, and 6 negatively charged
Phosphate groups, have huge chelating potential energy between metal cation, therefore phytic acid can not only enhance the resistance to of aluminum alloy substrate
Corrosion energy and the binding force between composite film and aluminum alloy substrate can be enhanced.
Electro-deposition SnO of the invention2Mechanism:
Sn2++O2+2H2O+2e-→Sn4++4OH-
Sn4++4OH-→Sn(OH)4→SnO2+H2O
Electro-deposition GO mechanism: there is a large amount of oxygen-containing functional groups (- COOH ,-OH ,-O-) on GO (graphene oxide), in electric field
It acts on and is 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 are as follows: the concentration of GO (graphene oxide) 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 resulting SnO2The aluminium alloy bipolar plates of the compound membrane modifying of/GO, in 0.5mol/LH2SO4+2ppm
Corrosion electric current density 1.057 × 10 in the simulated solution of HF-7A/cm23 quantity and corrosion potential are reduced compared with naked aluminium alloy
424mv is shuffled, inhibition efficiency η has reached 99.9%.
Equally distributed honeycomb first is prepared on its surface out to aluminum alloy surface progress anodic oxidation due to using in the present invention
Then shape nanometer micropore carries out surface treatment with plant acid solution again to enhance SnO2/ GO composite membrane and aluminum alloy substrate
Adhesive force.The SnO of preparation2The compound film quality of/GO is close and SnO2It is evenly distributed with GO, which not only has aluminum alloy substrate
The extraordinary protective effect and presence of GO enhances the electric conductivity of film layer.This method is that one kind is fairly simple, cheap easy
Control and environmentally protective novel processing step, the final resulting Proton Exchange Membrane Fuel Cells of preparation method through the invention
There is high antiseptic property with aluminium alloy bipolar plates.
The present invention is compared with prior art, and technological progress is significant.The present invention is to overcome the above-mentioned prior art
Existing defect and provide a kind of environmentally protective, treatment process is simple, at low cost, the good Proton Exchange Membrane Fuel Cells of stability
With the surface modifying method of aluminium alloy bipolar plates.
Detailed description of the invention
The SnO that Fig. 1 cyclic voltammetry (0.6~-1.1V of scanning range) deposits on 5052 surface of aluminium alloy2/ GO composite membrane
Surface SEM figure
The SnO of Fig. 2 cyclic voltammetry (0.6~-1.1V of scanning range) preparation2The complex film modified aluminium alloy 5052 of/GO tries
The cross section SEM of sample schemes and distribution diagram of element (mapping).
The SnO of Fig. 3 cyclic voltammetry (0.6~-1.1V of scanning range) preparation2The complex film modified aluminium alloy 5052 of/GO tries
The cross section SEM of sample schemes and Elemental redistribution linear scan.
The SnO that Fig. 4 cyclic voltammetry (0.6~-1.5V of scanning range) deposits on 5052 surface of aluminium alloy2/ GO composite membrane
Surface SEM figure
Fig. 5 is 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 alloy 5052 of/GO measures in simulated solution
Tafel polarization curve.
Specific embodiment
The present invention is further described below by case study on implementation and in conjunction with attached drawing, but is not intended to limit the present invention.
SnO of the invention2The measuring method scanning electron microscopy of the aluminum alloy surface morphology characterization of the compound membrane modifying of/GO
The surface topography of mirror (SU-1500, Japanese Hitachi company) observation sample.
Electrochemical analysis
The measurement of polarization curve is completed in three-electrode system, and test solution is 0.5mol/L H2SO4The proton of+2ppmHF
In exchange film fuel battery simulated solution, working electrode SnO2The aluminum alloy anode or naked aluminum alloy anode of the compound membrane modifying of/GO,
Auxiliary electrode and reference electrode are respectively Pt plate electrode and saturated calomel electrode (SCE).Electro-chemical test uses instrument for occasion China
CHI660E electrochemical workstation.AC impedance frequency range is 100kHz-0.01Hz, and ac-excited signal peak is 10mV；Pole
Change curved scanning range open circuit potential E ± 250mV (vs.SCE), scanning speed 1mV/s.
Inhibition efficiency (η) is calculated according to following formula:
Wherein I0It is respectively untreated and the corrosion electric current density of treated aluminum alloy anode with I.
Embodiment 1:
A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates, includes 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 5052 sample of aluminium alloy after polishing cleaning 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) it aluminum alloy surface anodic oxidation: using two electrode systems, is 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 solution in carry out sun
Pole oxidation, the voltage of application are 35V, time 30min.
(3) plant acid solution handle: by by above-mentioned steps processing 5052 sample of aluminium alloy mass fraction be 1wt.%
Plant acid solution in ultrasound (power 50W) 15min, then with warm wind dry up it is spare.
(4) deposition liquid is prepared, and wherein the concentration of GO (graphene oxide) is 0.05mg/mL, SnCl2Concentration be 5~
100mmol/L, HNO3Concentration be 10~100mmol/L, KNO3Concentration be 20mmol/L, the concentration of pyrrolidones K-30 is
20mg/mL.Uniformly mixed solution is led into oxygen 1h under 50 DEG C of water bath condition.
(5) electro-deposition SnO2/ GO composite membrane: electro-deposition is carried out using three-electrode system, 5052 sample of aluminium alloy 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 placed in 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 is the SnO prepared with cyclic voltammetry (scanning range 0.6V~-1.1V) on 5052 surface of aluminium alloy2/GO
Composite film surface amplifies the SEM figure of 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 fits closely.Fig. 2 is the SnO of cyclic voltammetry (0.6~-1.1V of scanning range) preparation2/ GO is multiple
Close the cross section SEM figure and element (Al, O, C, Sn) distribution map (mapping) of film modified 5052 sample of aluminium alloy.By cross section
SEM figure can be found, in conjunction with closely and compared with composite film matter is close between composite film and 5052 substrate of aluminium alloy.By Al,
The distribution diagram of element (mapping) of O, C, Sn are it is found that O, C, Sn element are evenly dispersed, i.e. SnO in composite film2/GO
SnO in composite membrane2It is evenly dispersed with GO.Fig. 3 is the SnO of cyclic voltammetry (0.6~-1.1V of scanning range) preparation2/GO
The cross section SEM of complex film modified 5052 sample of aluminium alloy schemes and Elemental redistribution linear scan figure, following graphical representation
It is variation of the different elements along directions of rays cellulose content.In conjunction with Fig. 2 and Fig. 3 it is found that the SnO on 5052 surface of aluminium alloy2/ GO is multiple
Closing film thickness is about 100 μm.
Fig. 5 is 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 alloy 5052 of/GO measures in simulated solution
Tafel polarization curve.
Table 1. is the related electrochemical parameter corresponding to Fig. 5
By table 1. it is found that (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 SnO2Complex film modified 5052 sample of aluminium alloy of/GO is in 0.5H2SO4+
Corrosion electric current density in the Proton Exchange Membrane Fuel Cells simulated solution of 2ppmHF 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 complex film modified relatively naked aluminium alloy of 5052 sample of aluminium alloy of/GO reduces by 3 quantity
Grade, 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, includes 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.By by polishing cleaning after 5052 sample of aluminium alloy volume fraction be 25vol.%
Perchloric acid ethanol solution in carry out anodized, application voltage is 25V, time 4min.
(2) it aluminum alloy surface anodic oxidation: using two electrode systems, is 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 solution in carry out sun
Pole oxidation, the voltage of application are 35V, time 30min.
(3) plant acid solution handle: by by above-mentioned steps processing 5052 sample of aluminium alloy mass fraction be 1wt.%
Plant acid solution in ultrasound (power 50W) 15min, then with warm wind dry up it is spare.
(4) deposition liquid is prepared, and wherein the concentration of GO (graphene oxide) is 0.05mg/mL, SnCl2Concentration be 5~
100mmol/L, HNO3Concentration be 10~100mmol/L, KNO3Concentration be 20mmol/L, the concentration of pyrrolidones K-30 is
20mg/mL.Uniformly mixed solution is led into oxygen 1h under 50 DEG C of water bath condition.
(5) electro-deposition SnO2/ GO composite membrane: electro-deposition is carried out using three-electrode system, 5052 sample of aluminium alloy 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 placed in 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 is that the SnO2/GO that cyclic voltammetry (0.6~-1.5V of scanning range) is deposited on 5052 surface of aluminium alloy is compound
Film surface amplifies different multiplying (Fig. 4 a~d) SEM figure.As seen from the figure, SnO2/GO is prepared in the scanning range of 0.6~-1.5V
Composite film is loose compared with the scanning range of 0.6~-1.1V (Fig. 1) preparation film layer and crackle is more.The scanning range known to table 1.
0.6~-1.5V prepares proton exchange membrane of complex film modified 5052 sample of aluminium alloy of SnO2/GO in 0.5H2SO4+2ppmHF and fires
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 membrane of preparation is anti-corrosion in this explanation 0.6~-1.5V scanning range
Performance is good not as good as what is prepared in 0.6~-1.1V scanning range.
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.By by polishing cleaning after 5052 sample of aluminium alloy volume fraction be 25vol.%
Perchloric acid ethanol solution in carry out anodized, application voltage is 25V, time 4min.
(2) it aluminum alloy surface anodic oxidation: using two electrode systems, is 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 solution in carry out sun
Pole oxidation, the voltage of application are 35V, time 30min.
(3) plant acid solution handle: by by above-mentioned steps processing 6061 sample of aluminium alloy mass fraction be 1wt.%
Plant acid solution in ultrasound (power 50W) 15min, then with warm wind dry up it is spare.
(4) deposition liquid is prepared, and wherein the concentration of GO (graphene oxide) is 0.05mg/mL, SnCl2Concentration be 5~
100mmol/L, HNO3Concentration be 10~100mmol/L, KNO3Concentration be 20mmol/L, the concentration of pyrrolidones K-30 is
20mg/mL.Uniformly mixed solution is led into oxygen 1h under 50 DEG C of water bath condition.
(5) electro-deposition SnO2/ GO composite membrane: electro-deposition is carried out using three-electrode system, 6061 sample of aluminium alloy 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 placed in 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 characterizations such as scanning electron microscope (SEM), electro-chemical test are the result shows that with aluminium alloy 6061 for substrate system
It is that substrate prepares SnO2/GO composite membrane without significant difference for SnO2/GO composite membrane 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 made by technical solution according to the present invention
What equivalent transformation, is within the scope of protection of the invention.
Claims (4)
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
It is rapid:
1) one carries out electro-chemical polish step to used in proton exchange membrane fuel cell aluminum alloy surface, will be after polishing cleaning
Aluminium alloy electrochemical polish processing is carried out in the ethanol solution of perchloric acid；Body of the 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 the 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 spare with drying up for 1~60min of ultrasound in 1~10% plant acid solution；
4) the step of preparation electric depositing solution, the electric depositing solution is by graphene oxide, SnCl2、HNO3、KNO3, pyrrole
Pyrrolidone K-30 and deionized water composition, in the electric depositing solution, the concentration of the graphene oxide is 0.01~
0.1mg/mL, the SnCl2Concentration is 5~100mmol/L, the HNO3Concentration be 10~100mmol/L, it is described
KNO3Concentration be 10~100mmol/L, the concentration of the pyrrolidones K-30 is 1~60mg/mL；It is molten by what is be uniformly mixed
Liquid leads to 0.5~3h of oxygen under 40~70 DEG C of water bath condition；
5) electrodeposition step carries out electro-deposition using three-electrode system, and aluminium alloy is as working electrode, platinum plate electrode conduct
To electrode, electric depositing solution is placed 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 stannic oxide/oxygen for cyclic voltammetry or constant voltage or galvanostatic method, in aluminum alloy surface
Graphite alkene composite membrane is completed modified to the surface of used in proton exchange membrane fuel cell aluminium alloy bipolar plates.
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 by: the aluminium alloy of step 1) is aluminium alloy 5052 or aluminium alloy 6061；Step 1) is using two electrode systems, aluminium
Alloy is used as working electrode platinum plate electrode to electrode, and the voltage of application is 5V~110V, and the time is 1~10min.
3. 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 by: step 2), using two electrode systems, aluminium alloy is used as to electrode as working electrode platinum plate electrode, applies
Voltage be 5V~110V, the time be 1~60min.
4. 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 by: bath temperature is 40~70 DEG C, 0.1~-10V of voltage range, current density range when step 5) electro-deposition
5~100mA/cm2。
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| 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 |
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