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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
aluminium alloy
electrode
proton exchange
fuel cell
exchange membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710929789.2A
Other languages
Chinese (zh)
Other versions
CN107794556A (en
Inventor
徐群杰
万云霄
陈寞静
张徐成
杨灵慧
秦真兰
沈喜训
闵宇霖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai University of Electric Power
Original Assignee
Shanghai University of Electric Power
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai University of Electric Power filed Critical Shanghai University of Electric Power
Priority to CN201710929789.2A priority Critical patent/CN107794556B/en
Publication of CN107794556A publication Critical patent/CN107794556A/en
Application granted granted Critical
Publication of CN107794556B publication Critical patent/CN107794556B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00Electrolytic coating other than with metals
    • C25D9/04Electrolytic coating other than with metals with inorganic materials
    • C25D9/06Electrolytic coating other than with metals with inorganic materials by anodic processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • C25D11/06Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

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

A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates
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
CN201710929789.2A 2017-10-09 2017-10-09 A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates Active CN107794556B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710929789.2A CN107794556B (en) 2017-10-09 2017-10-09 A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710929789.2A CN107794556B (en) 2017-10-09 2017-10-09 A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates

Publications (2)

Publication Number Publication Date
CN107794556A CN107794556A (en) 2018-03-13
CN107794556B true CN107794556B (en) 2019-06-28

Family

ID=61532928

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710929789.2A Active CN107794556B (en) 2017-10-09 2017-10-09 A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates

Country Status (1)

Country Link
CN (1) CN107794556B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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 (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
Title
One-Step In situ Synthesis of SnO2/Graphene Nanocomposites andIts Application As an Anode Material for Li-Ion Batteries;Junfei Liang等;《ACS Applied Materials & Interfaces》;20111221;第4卷;第454-459页
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;万云霄;《中国优秀硕士学位论文全文数据库》;20180715(第7期);第C042-684页

Also Published As

Publication number Publication date
CN107794556A (en) 2018-03-13

Similar Documents

Publication Publication Date Title
Pant et al. Anode and cathode materials characterization for a microbial fuel cell in half cell configuration
Angioni et al. Improving the performances of Nafion™-based membranes for microbial fuel cells with silica-based, organically-functionalized mesostructured fillers
Wang et al. The influence of Ferric ion contamination on the solid polymer electrolyte water electrolysis performance
CN105734606B (en) A kind of SPE water electrolysis structure of ultra-thin membrane electrode and its preparation and application
CN106024416A (en) Nitrogen-doped rod-like titanium oxide/two-dimensional laminated titanium carbide nanometer composite electrode material, and preparation method and application therefor
CN105483751A (en) Efficient Ni-S-Mo hydrogen evolution electrode and preparation method thereof
CN105063721B (en) The method that magnesium alloy anodic oxidation electrolyte and the electrolyte prepare anode oxide film
CN106669739A (en) Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof
CN104611751A (en) Micro-arc oxidation self-assembly composite membrane layer on surface of magnesium alloy and preparation method of micro-arc oxidation self-assembly composite membrane layer
CN106935880A (en) A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates
CN107794556B (en) A kind of surface modifying method of used in proton exchange membrane fuel cell aluminium alloy bipolar plates
CN108411283A (en) A kind of preparation method of metallic matrix/nonmetal basal body carbon composite coating or carbon conductive composite coating
CN103253743A (en) Preparation method and application of Fe-doped PTFE-PbO2/TiO2-NTs/Ti electrode
CN105895385A (en) Titanium oxide columnar array/two-dimensional lamellar titanium carbide electrode material and preparation and application thereof
CN110592616A (en) Method for preparing platinum/titanium dioxide nanotube composite electrode by electroplating method
CN1439742A (en) Metal surface anti-corrosion method based on surface nanometer construct
CN107256975B (en) Method for modifying aluminum alloy bipolar plate for proton exchange membrane fuel cell by using boron nitride nanosheets
Xiang et al. Electrochemical enhancement of carbon paper by indium modification for the positive side of vanadium redox flow battery
CN103296285A (en) Lead dioxide modified graphite felt electrode of all-vanadium redox flow battery and preparation method thereof
CN107317043B (en) Preparation method of graphene/tin dioxide sandwich structure film on surface of aluminum alloy bipolar plate
CN108796583B (en) A kind of preparation method of the super-hydrophobic passivating film of Pure Iron Surface corrosion resistance
CN110938856A (en) Novel anodic oxidation process of nickel-based thin film energy storage material
CN108754580B (en) The surface modified stainless steel of in-situ deposition nanometer pt a kind of and its application
Shul et al. Nafion/graphene oxide layered structure membrane for the vanadium redox flow battery
CN101876068A (en) Method for preparing NiP/TiO2 anticorrosion composite film on surface of carbon steel

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant