CN107317043A - A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film - Google Patents
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film Download PDFInfo
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- CN107317043A CN107317043A CN201710311105.2A CN201710311105A CN107317043A CN 107317043 A CN107317043 A CN 107317043A CN 201710311105 A CN201710311105 A CN 201710311105A CN 107317043 A CN107317043 A CN 107317043A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
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- H01M8/0228—Composites in the form of layered or coated products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film, comprise the following steps：(1) remove ionized water to mix with absolute ethyl alcohol, add two hydrated stannous chlorides, pH is to 9~10 for regulation, obtains hydrothermal precursor solution；(2) take pretreated aluminium alloy bipolar plates to be placed in NaOH solution, carry out chemical etching, clean, dry；(3) the aluminium alloy bipolar plates samsara after chemical etching is circulated to self assembly in the PDDA aqueous solution and graphene oxide water solution one or many, takes out and be cleaned and dried；(4) the aluminium alloy bipolar plates after the completion of step (3) self assembly are placed in the hydrothermal precursor solution of step (1) configuration again, hydro-thermal reaction, cleaned, dried, that is, complete.Compared with prior art, simple to operate, cost of the invention is low, anti-corrosion effect is good etc..
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells technical field, more particularly, to a kind of aluminium alloy bipolar plate surfaces stone
The preparation method of black alkene/tin ash Sandwich film.
Background technology
The problems such as continuing to develop and improving with society, lack of energy, environmental pollution, is also following.In 21 century
Today, people's having recognized due to the seriousness of a series of problems that the development of the mankind is caused further.Nowadays, fossil energy
Reserves are fewer and fewer, develop the reproducible cleanliness without any pollution energy and cause global concern, fuel cell is exactly the mankind's
One of wisdom crystallization.Wherein Proton Exchange Membrane Fuel Cells (PEMFC, also known as polymer dielectric film fuel cell) is newest one
Replacing fuel battery, the chemical energy that it is mainly produced using hydrogen and oxygen reaction is changed into electric energy, and discharge is vapor, no
Carbonated isothermal chamber gas, has the advantages that efficient, energy-saving and environmental protection, startup are fast and operating temperature is low (60~80 DEG C).It is double
Pole plate not only accounts for 70~80% and most volume of whole battery pile quality as PEMFC important composition component, and
And sizable ratio is also taken up in the production cost of battery pile, so the selection for bipolar plate material is extremely important.
The bipolar plate material mainly applied at present has：Graphite, composite, metal material.With other bipolar plate material phases
Have that thermal conductivity is good, electric conductivity is strong, high mechanical strength, processability are good than, metal material, the low feature of cost and cause
Extensive concern.Aluminium and its alloy greatly, are considered in terms of its conductance, mechanical strength and density, can also used due to reserves
Make PEMFC bipolar plate material.Easily it is passivated because of its chemical property nonreactive surfaces again simultaneously, and the defect such as is easily corroded,
Using being restricted.In order to which it can be widely applied, surface modification is carried out to it with improve its electric conductivity and
Corrosion resistance turns into a necessary job.
In recent years, the research on modified proton exchanging film fuel battery bipolar plate material has a lot, but these methods
Generally all there is the shortcomings of complex treatment process, cost are higher, stability is poor.The China of Application No. 200810202639.2 is specially
Profit has issued a kind of surface modifying method of the dual polar plates of proton exchange membrane fuel cell of energy technology field, this bipolar
Plate is made up of surface reforming layer and matrix stainless steel, using the method for ion implanting by copper ion implantation stainless sheet steel,
Implanted layer is formed in the nanometer range of Thin Stainless Steel plate surface tens, modified bipolar plate of stainless steel is obtained.This method is modified
The corrosion resistance of stainless steel be not greatly improved, the corrosion electric current density of naked stainless steel is 11.76 μ Acm-2, it is modified
Corrosion electric current density be only 7 μ Acm-2, inhibition efficiency is only 40.48%, and the preparation condition of this method is extremely harsh,
High voltage is needed to need to carry out at high temperature again.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of aluminium alloy bipolar plates
The preparation method of surface graphene/tin ash Sandwich film.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film, including it is following
Step：
(1) remove ionized water to mix with absolute ethyl alcohol, add two hydrated stannous chlorides, pH is to 9~10 for regulation, obtains hydro-thermal
Precursor solution；
(2) take pretreated aluminium alloy bipolar plates to be placed in NaOH solution, carry out chemical etching, clean, dry；
(3) the aluminium alloy bipolar plates samsara after chemical etching is circulated in the PDDA aqueous solution and graphene oxide water solution
Self assembly is one or many, takes out and is cleaned and dried；
(4) hydrothermal precursor for the aluminium alloy bipolar plates after the completion of step (3) self assembly being placed in into step (1) configuration again is molten
In liquid, hydro-thermal reaction is cleaned, and is dried, i.e., it is thin to obtain graphene/tin ash sandwich structure in aluminium alloy bipolar plate surfaces
Film.
It is preferred that, the ratio between addition of deionized water, absolute ethyl alcohol and two hydrated stannous chlorides is 20- in step (1)
40mL：10mL：0.1-0.3g.
It is preferred that, the NaOH solution that the solution in step (1) used in regulation pH is 1M.
It is preferred that, the concentration of NaOH solution is 0.8-1.2M in step (2), and the process conditions of chemical etching are：In 50-70
20-40s is etched under the conditions of DEG C.
It is preferred that, in step (2), pretreatment is specially：
By aluminium alloy bipolar plates after grinding process, it is placed in acetone and is cleaned by ultrasonic, then uses absolute ethyl alcohol, deionization successively
Water is rinsed, to remove aluminum alloy surface greasy dirt and grease.
It is furthermore preferred that grinding process is concretely comprised the following steps：Sequentially pass through 600#, 1000#, 1500#, 2000# water milling
Paper is polished, then is polished with W3.5 abrasive paper for metallograph.
It is preferred that, in step (3), the self-assembly process condition in the PDDA aqueous solution is：Volume fraction 0.8-1.2%'s
PDDA aqueous solution self assemblies 8-15min；
The process conditions of self assembly are in graphene oxide water solution：In the oxidation stone that mass fraction is 0.8-1.2wt%
Self assembly 8-15min in black aqueous solution.
It is preferred that, the number of times of step (3) samsara circulation assembling is 10 times.
It is preferred that, the condition of hydro-thermal reaction is in step (4)：The hydro-thermal reaction 4-8h in 110-130 DEG C.
It is preferred that, in step (4), the condition being cleaned and dried after hydro-thermal reaction is：Dried the whole night at 60 DEG C after cleaning.
Used in the present invention mechanism of NaOH solution chemical etching for：
2Al+2NaOH+6H2O→2Na[Al(OH)4]+3H2↑
In hydrothermal reaction process, graphene oxide is reduced to the reduction-oxidation graphite of excellent performance using thermal reduction
Alkene；Generation tin ash mechanism be：
Graphene/tin ash Sandwich film surface obtained by present invention preparation is in simulation pem fuel
Simulated solution (the 0.5M H of battery2SO4+ 2ppm HF) middle immersion, after film layer reaches stabilization, corrosion potential has shuffled 496mV, rotten
Erosion current density has reached 3.457 × 10-7A·cm-2And corrosion inhibition rate can reach 99.59%, extraordinary corrosion resistance is shown
Energy.
The present invention is performed etching using NaOH solution as etching liquid to aluminum alloy surface, so that aluminum alloy surface obtains hydroxyl
Base.The PDDA aqueous solution carries positive charge, can be combined together with hydroxylated aluminum alloy surface by electrostatic attraction.Aoxidize stone
The aqueous solution of black alkene carries negative electrical charge, can be combined again with the surface with positive charge of PDDA modifieds by electrostatic attraction one
Rise.So samsara circulation carries out self assembly 10 times in the aqueous solution of PDDA and graphene oxide respectively, you can obtain oxidation stone
Black alkene layer.Hydrothermal treatment again, graphene oxide forms redox graphene by thermal reduction, and the stannous chloride of water then turns
The tin ash with excellent stability is turned to, so as to prepare graphene/tin ash Sandwich film surface.Should
Method has the advantages that simple to operate, cost is low, anti-corrosion effect is good.Graphite as obtained by the preparation method of the present invention is final
Alkene/tin ash Sandwich film surface has higher antiseptic property.
Compared with prior art, the present invention has advantages below：
1) surface of PDDA/ graphene oxides modification is obtained in aluminum alloy surface using self-assembly method, and eventually through heat
Reduction, obtains redox graphene.
2) method being combined by self-assembly method and hydro-thermal method, a kind of table of sandwich structure is prepared in aluminum alloy surface
Face film, is directed to corrosion proof research of the enhancing aluminum alloy materials under PEMFC environment and belongs to a kind of innovation
3) preparation technology is simple, and mild condition, cost is relatively low, and stability is higher, environmental protection, the graphite obtained by preparation
Alkene/tin ash Sandwich film surface, inhibition efficiency is up to 99.59%, with excellent corrosion resisting property.
Brief description of the drawings
Fig. 1 is the aluminium alloy on different disposal surface in 0.5M H2SO4Potentiodynamic polarization in+2ppm HF simulated solution is bent
Line chart；
Fig. 2 is the aluminium alloy on different disposal surface in 0.5M H2SO4Potentiodynamic polarization in+2ppm HF simulated solution is bent
The corresponding relevant chemical parameters list of line chart；
Fig. 3 is blank aluminum alloy surface shape appearance figure under 1000 multiplying powers；
Fig. 4 is the aluminum alloy surface shape appearance figure after being etched under 1000 multiplying powers with NaOH solution；
Fig. 5 is the surface topography map of pure zirconia graphene under 4000 multiplying powers；
Fig. 6 is the surface topography map of pure tin ash under 5000 multiplying powers；
Fig. 7 is the surface topography map of graphene/tin ash Sandwich film under 5000 multiplying powers.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
A kind of graphene/tin ash Sandwich film table of aluminum alloy surface with corrosion resisting property of the present invention
The assay method of face morphology characterization observes the surface shape of sample with SEM (SU-1500, Japanese Hitachi companies)
Looks.
Electrochemical analysis
The measurement of ac impedance measurement and polarization curve is completed all in three-electrode system, and working electrode is to have built graphite
The aluminum alloy anode of alkene/tin ash Sandwich film, auxiliary electrode and reference electrode are respectively that Pt electrodes and saturation are sweet
Mercury electrode (SCE).Electro-chemical test uses instrument for occasion China CHI660E electrochemical workstations.Its impedance frequency scope is
100kHz-0.05Hz, ac-excited signal peak is 5mV；Polarization curve scanning range E ± 200mV (vs.SCE), sweep speed
For 1mV/s.
Inhibition efficiency (η %) is calculated according to equation below：
Wherein I0It is respectively the corrosion electric current density of untreated and treated aluminum alloy anode with I.
Embodiment 1
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film, including it is as follows
Step：
(1), the preparation of etching liquid
Compound concentration is 1M NaOH solution, is used as etching liquid；
(2), the preparation of the PDDA aqueous solution
The PDDA aqueous solution that volume ratio is 1% is configured, for self assembly；
(3), the preparation of graphene oxide water solution
Configuration quality fraction is 1wt% graphene oxide water solution, for self assembly；
(4) preparation of hydro-thermal precursor solution
It is 3 according to deionized water and absolute ethyl alcohol volume ratio：1, take 30mL deionized waters and 10mL absolute ethyl alcohols mixed respectively
Close, add 0.15g two hydrated stannous chlorides, after being well mixed, pH=9~10 of solution are adjusted with 1M NaOH；
(5), the pretreatment of aluminium alloy
By 5 (1,2,3,4,5) aluminium alloys successively through first sequentially passing through 600#, 1000#, 1500#, 2000# water milling
Paper is polished, then is polished with W3.5 abrasive paper for metallograph.Cleaned again in acetone solution with supersonic wave cleaning machine after 15min or so,
Absolute ethyl alcohol, deionized water rinsing are used successively again, to remove surface and oil contaminant and grease；
(6), chemical etching
Pretreated wherein 4 (2,3, the 4,5) aluminium alloys of step (5) are taken out to the etching being immersed in obtained by step (1)
In liquid, 5min is cleaned with deionized water and EtOH Sonicate respectively after carving 30s, etching under conditions of 60 DEG C of water-bath；
(7), self assembly is handled
Will step (6) etch after obtained wherein 2 (3,5) aluminium alloys, be respectively put into step (2), molten made from (3)
10min is soaked in liquid, samsara circulates 10 self assemblies.
(8), hydro-thermal process
It is etched by wherein 1 (5) aluminium alloy after the PDDA/ graphene oxides modification of step (7) acquisition and by step (6)
Wherein 1 (4) aluminium alloy obtained afterwards, the step of being put into reactor, and add 10mL wherein presoma made from (4) is molten
Liquid, carries out 120 DEG C, 6h hydro-thermal reaction；Wherein 1 (3) are put into after the PDDA/ graphene oxides modification that step (7) is obtained
Reactor, adds 10mL deionized waters, carries out 120 DEG C, 6h hydro-thermal reaction.
Fig. 1 and Fig. 2 is respectively naked aluminium alloy (1), the obtained aluminium alloy after etching obtained after above-mentioned steps are handled
(2), pure graphene film is modified aluminium alloy (3), pure tin dioxide film and is modified aluminium alloy (4) and graphene/tin ash sandwich
Structural membrane is modified aluminium alloy (5) in 0.5M H2SO4Test and obtain in+2ppm HF Proton Exchange Membrane Fuel Cells simulated solution
Dynamic potential polarization curve figure and AC impedance figure.Table 1 is the list of Fig. 1 relevant chemical parameters, and naked aluminium alloy is known by table 1
(1), etch after obtain aluminium alloy (2), pure graphene film be modified aluminium alloy (3), pure tin dioxide film be modified aluminium alloy (4),
The corrosion electric current density that graphene/tin ash Sandwich film is modified aluminium alloy (5) is respectively 8.356 × 10-5A/
cm2、2.161×10-5A/cm2、4.924×10-6A/cm2、2.851×10-6A/cm2、3.457×10-7A/cm2, corrosion potential
Respectively：-710mV、-521mV、-419mV、-406mV、-234mV.Graphene/tin ash Sandwich film modified aluminium
For the relatively naked aluminium alloy of alloy, corrosion potential has shuffled 496mV, and inhibition efficiency is up to 99.59%.As shown in Figure 2, graphite
The impedance value that alkene/tin ash Sandwich film is modified aluminium alloy is maximum, is desirably also corresponding with its corrosion resisting property.
Fig. 3 is blank aluminum alloy surface shape appearance figure under 1000 multiplying powers, and surface is homogeneous cut.Fig. 4 is under 1000 multiplying power
Aluminum alloy surface after aluminum alloy surface shape appearance figure after being etched with NaOH solution, etching has the pattern of similar cell shape, together
When surface obtain hydroxyl.Fig. 5 is the surface topography map of pure zirconia graphene under 4000 multiplying powers, and the pattern has graphene oxide
The characteristic feature of accordion, because graphene can be used for anti-corrosion, therefore can play certain protection work to aluminum alloy surface
With.Fig. 6 is the surface topography map of pure tin ash under 5000 multiplying powers, and the diameter of the pattern of the spherical assembling is about 1~2 μm,
Aluminum alloy surface is uniformly covered on, simultaneously because the superior stability of tin ash, preferably can protect aluminium alloy rotten
Erosion, Fig. 7 be 5000 multiplying powers under graphene/tin ash Sandwich film surface topography map, be combined after pattern than
The surface topography of pure tin ash there occurs that some change, but the lamellar structure of bead becomes more slim, in addition with graphite
The collective effect of alkene, serves the protective effect to aluminum alloy substrate.
Embodiment 2：
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film of the present embodiment,
Specifically include following steps：
(1), the preparation of etching liquid
Compound concentration is 1M NaOH solution, is used as etching liquid；
(2), the preparation of the PDDA aqueous solution
The PDDA aqueous solution that volume ratio is 1% is configured, for self assembly；
(3), the preparation of graphene oxide water solution
Configuration quality fraction is 1wt% graphene oxide water solution, for self assembly；
(4) preparation of hydro-thermal precursor solution
It is 1 according to deionized water and absolute ethyl alcohol volume ratio：3, take 10mL deionized waters and 30mL absolute ethyl alcohols mixed respectively
Close, add 0.15g two hydrated stannous chlorides, after being well mixed, pH=9~10 of solution are adjusted with 1M NaOH；
(5), the pretreatment of aluminium alloy
Aluminium alloy is polished through first sequentially passing through 600#, 1000#, 1500#, 2000# silicon carbide paper successively, then uses W3.5
Abrasive paper for metallograph polished.Cleaned again in acetone solution with supersonic wave cleaning machine after 15min or so, then use anhydrous second successively
Alcohol, deionized water rinsing, to remove surface and oil contaminant and grease；
(6), chemical etching
The pretreated aluminium alloy of step (5) is taken out in the etching liquid being immersed in obtained by step (1), in 60 DEG C of water-bath
Under the conditions of carve and clean 5min with deionized water and EtOH Sonicate respectively after 30s, etching；
(7), self assembly is handled
Will step (6) etch after obtained aluminium alloy, be respectively put into step (2), soak in solution made from (3)
10min, samsara circulates 10 self assemblies.
(8), hydro-thermal process
Aluminium alloy after the PDDA/ graphene oxides modification that step (7) is obtained, is put into reactor, and add wherein
Precursor solution made from the step of 10mL (4), carries out 120 DEG C, 6h hydro-thermal reaction, you can obtaining has graphene/dioxy
Change tin Sandwich film surface.
Embodiment 3：
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film of the present embodiment,
Specifically include following steps：
(1), the preparation of etching liquid
Compound concentration is 1M NaOH solution, is used as etching liquid；
(2), the preparation of the PDDA aqueous solution
The PDDA aqueous solution that volume ratio is 1% is configured, for self assembly；
(3), the preparation of graphene oxide water solution
Configuration quality fraction is 1wt% graphene oxide water solution, for self assembly；
(4) preparation of hydro-thermal precursor solution
It is 3 according to deionized water and absolute ethyl alcohol volume ratio：1, take 30mL deionized waters and 10mL absolute ethyl alcohols mixed respectively
Close, add 0.15g two hydrated stannous chlorides, after being well mixed, pH=9~10 of solution are adjusted with 1M NaOH；
(5), the pretreatment of aluminium alloy
Aluminium alloy is polished through first sequentially passing through 600#, 1000#, 1500#, 2000# silicon carbide paper successively, then uses W3.5
Abrasive paper for metallograph polished.Cleaned again in acetone solution with supersonic wave cleaning machine after 15min or so, then use anhydrous second successively
Alcohol, deionized water rinsing, to remove surface and oil contaminant and grease；
(6), chemical etching
The pretreated aluminium alloy of step (5) is taken out in the etching liquid being immersed in obtained by step (1), in 60 DEG C of water-bath
Under the conditions of carve and clean 5min with deionized water and EtOH Sonicate respectively after 30s, etching；
(7), self assembly is handled
Will step (6) etch after obtained aluminium alloy, be respectively put into step (2), soak in solution made from (3)
10min, samsara circulates 5 self assemblies.
(8), hydro-thermal process
Aluminium alloy after the PDDA/ graphene oxides modification that step (7) is obtained, is put into reactor, and add wherein
Precursor solution made from the step of 10mL (4), carries out 120 DEG C, 6h hydro-thermal reaction, you can obtaining has graphene/dioxy
Change tin Sandwich film surface.
Embodiment 4：
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film of the present embodiment,
Specifically include following steps：
(1), the preparation of etching liquid
Compound concentration is 1M NaOH solution, is used as etching liquid；
(2), the preparation of the PDDA aqueous solution
The PDDA aqueous solution that volume ratio is 1% is configured, for self assembly；
(3), the preparation of graphene oxide water solution
Configuration quality fraction is 1wt% graphene oxide water solution, for self assembly；
(4) preparation of hydro-thermal precursor solution
It is 3 according to deionized water and absolute ethyl alcohol volume ratio：1, take 30mL deionized waters and 10mL absolute ethyl alcohols mixed respectively
Close, add 0.15g two hydrated stannous chlorides, after being well mixed, pH=9~10 of solution are adjusted with 1M NaOH；
(5), the pretreatment of aluminium alloy
Aluminium alloy is polished through first sequentially passing through 600#, 1000#, 1500#, 2000# silicon carbide paper successively, then uses W3.5
Abrasive paper for metallograph polished.Cleaned again in acetone solution with supersonic wave cleaning machine after 15min or so, then use anhydrous second successively
Alcohol, deionized water rinsing, to remove surface and oil contaminant and grease；
(6), chemical etching
The pretreated aluminium alloy of step (5) is taken out in the etching liquid being immersed in obtained by step (1), in 60 DEG C of water-bath
Under the conditions of carve and clean 5min with deionized water and EtOH Sonicate respectively after 30s, etching；
(7), self assembly is handled
Will step (6) etch after obtained aluminium alloy, be respectively put into step (2), soak in solution made from (3)
10min, samsara circulates 10 self assemblies.
(8), hydro-thermal process
Aluminium alloy after the PDDA/ graphene oxides modification that step (7) is obtained, is put into reactor, and add wherein
Precursor solution made from the step of 10mL (4), carries out 150 DEG C, 6h hydro-thermal reaction, you can obtaining has graphene/dioxy
Change tin Sandwich film surface.
Embodiment 5
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film of the present embodiment,
Specifically include following steps：
(1), the preparation of etching liquid
Compound concentration is 0.8M NaOH solution, is used as etching liquid；
(2), the preparation of the PDDA aqueous solution
The PDDA aqueous solution that volume ratio is 0.8% is configured, for self assembly；
(3), the preparation of graphene oxide water solution
Configuration quality fraction is 0.8wt% graphene oxide water solution, for self assembly；
(4) preparation of hydro-thermal precursor solution
It is 2 according to deionized water and absolute ethyl alcohol volume ratio：1, take 20mL deionized waters and 10mL absolute ethyl alcohols mixed respectively
Close, add 0.1g two hydrated stannous chlorides, after being well mixed, pH=9~10 of solution are adjusted with 1M NaOH；
(5), the pretreatment of aluminium alloy
Aluminium alloy is polished through first sequentially passing through 600#, 1000#, 1500#, 2000# silicon carbide paper successively, then uses W3.5
Abrasive paper for metallograph polished.Cleaned again in acetone solution with supersonic wave cleaning machine after 15min or so, then use anhydrous second successively
Alcohol, deionized water rinsing, to remove surface and oil contaminant and grease；
(6), chemical etching
The pretreated aluminium alloy of step (5) is taken out in the etching liquid being immersed in obtained by step (1), in 50 DEG C of water-bath
Under the conditions of carve and clean 5min with deionized water and EtOH Sonicate respectively after 40s, etching；
(7), self assembly is handled
Will step (6) etch after obtained aluminium alloy, be respectively put into step (2), soak in solution made from (3)
8min, samsara circulates 10 self assemblies.
(8), hydro-thermal process
Aluminium alloy after the PDDA/ graphene oxides modification that step (7) is obtained, is put into reactor, and add wherein
Precursor solution made from the step of 10mL (4), carries out 110 DEG C, 8h hydro-thermal reaction, you can obtaining has graphene/dioxy
Change tin Sandwich film surface.
Embodiment 6
A kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film of the present embodiment,
Specifically include following steps：
(1), the preparation of etching liquid
Compound concentration is 1.2M NaOH solution, is used as etching liquid；
(2), the preparation of the PDDA aqueous solution
The PDDA aqueous solution that volume ratio is 1.2% is configured, for self assembly；
(3), the preparation of graphene oxide water solution
Configuration quality fraction is 1.2wt% graphene oxide water solution, for self assembly；
(4) preparation of hydro-thermal precursor solution
It is 4 according to deionized water and absolute ethyl alcohol volume ratio：1, take 40mL deionized waters and 10mL absolute ethyl alcohols mixed respectively
Close, add 0.3g two hydrated stannous chlorides, after being well mixed, pH=9~10 of solution are adjusted with 1M NaOH；
(5), the pretreatment of aluminium alloy
Aluminium alloy is polished through first sequentially passing through 600#, 1000#, 1500#, 2000# silicon carbide paper successively, then uses W3.5
Abrasive paper for metallograph polished.Cleaned again in acetone solution with supersonic wave cleaning machine after 15min or so, then use anhydrous second successively
Alcohol, deionized water rinsing, to remove surface and oil contaminant and grease；
(6), chemical etching
The pretreated aluminium alloy of step (5) is taken out in the etching liquid being immersed in obtained by step (1), in 70 DEG C of water-bath
Under the conditions of carve and clean 5min with deionized water and EtOH Sonicate respectively after 20s, etching；
(7), self assembly is handled
Will step (6) etch after obtained aluminium alloy, be respectively put into step (2), soak in solution made from (3)
15min, samsara circulates 10 self assemblies.
(8), hydro-thermal process
Aluminium alloy after the PDDA/ graphene oxides modification that step (7) is obtained, is put into reactor, and add wherein
Precursor solution made from the step of 10mL (4), carries out 130 DEG C, 4h hydro-thermal reaction, you can obtaining has graphene/dioxy
Change tin Sandwich film surface.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of preparation method of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film, it is characterised in that
Comprise the following steps：
(1) remove ionized water to mix with absolute ethyl alcohol, add two hydrated stannous chlorides, pH is to 9~10 for regulation, obtains body before hydro-thermal
Liquid solution；
(2) take pretreated aluminium alloy bipolar plates to be placed in NaOH solution, carry out chemical etching, clean, dry；
(3) the aluminium alloy bipolar plates samsara after chemical etching is circulated in the PDDA aqueous solution and graphene oxide water solution from group
Fill one or many, taking-up cleaning-drying；
(4) the aluminium alloy bipolar plates after the completion of step (3) self assembly are placed in the hydrothermal precursor solution of step (1) configuration again
In, hydro-thermal reaction is cleaned, and is dried, i.e., obtain graphene/tin ash Sandwich film in aluminium alloy bipolar plate surfaces.
2. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that the ratio between addition of deionized water, absolute ethyl alcohol and two hydrated stannous chlorides is in step (1)
20-40mL：10mL：0.1-0.3g.
3. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that the NaOH solution that the solution in step (1) used in regulation pH is 1M.
4. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that the concentration of NaOH solution is 0.8-1.2M in step (2), the process conditions of chemical etching are：
20-40s is etched under the conditions of 50-70 DEG C.
5. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that in step (2), pretreatment is specially：
By aluminium alloy bipolar plates after grinding process, it is placed in acetone and is cleaned by ultrasonic, then successively with absolute ethyl alcohol, deionized water punching
Wash, to remove aluminum alloy surface greasy dirt and grease.
6. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 5
Preparation method, it is characterised in that grinding process is concretely comprised the following steps：Sequentially pass through 600#, 1000#, 1500#, 2000# water mill
Sand paper is polished, then is polished with W3.5 abrasive paper for metallograph.
7. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that in step (3), the self-assembly process condition in the PDDA aqueous solution is：In volume fraction 0.8-
1.2% PDDA aqueous solution self assemblies 8-15min；
The process conditions of self assembly are in graphene oxide water solution：In the graphene oxide that mass fraction is 0.8-1.2wt%
Self assembly 8-15min in the aqueous solution.
8. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1 or 7
Preparation method, it is characterised in that step (3) samsara circulation assembling number of times be 10 times.
9. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that the condition of hydro-thermal reaction is in step (4)：The hydro-thermal reaction 4-8h in 110-130 DEG C.
10. a kind of aluminium alloy bipolar plate surfaces graphene/tin ash Sandwich film according to claim 1
Preparation method, it is characterised in that in step (4), the condition being cleaned and dried after hydro-thermal reaction is：Drying is whole at 60 DEG C after cleaning
Evening.
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| CN107829084A (en) * | 2017-11-07 | 2018-03-23 | 上海电力学院 | A kind of modification processing method that PEI GO chitosan composite membranes are prepared in aluminum alloy surface |
| CN110034320A (en) * | 2019-04-09 | 2019-07-19 | 东北大学 | The method based on graphene oxide high temperature proton exchange film is prepared using layer-by-layer |
| CN110098417A (en) * | 2019-04-28 | 2019-08-06 | 上海电力学院 | Chitosan/stannic oxide laminated film modified aluminium alloy bipolar plate surfaces method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107829084A (en) * | 2017-11-07 | 2018-03-23 | 上海电力学院 | A kind of modification processing method that PEI GO chitosan composite membranes are prepared in aluminum alloy surface |
| CN107829084B (en) * | 2017-11-07 | 2019-12-27 | 上海电力学院 | Modification treatment method for preparing PEI-GO-chitosan composite membrane on surface of aluminum alloy |
| CN110034320A (en) * | 2019-04-09 | 2019-07-19 | 东北大学 | The method based on graphene oxide high temperature proton exchange film is prepared using layer-by-layer |
| CN110098417A (en) * | 2019-04-28 | 2019-08-06 | 上海电力学院 | Chitosan/stannic oxide laminated film modified aluminium alloy bipolar plate surfaces method |
| CN110098417B (en) * | 2019-04-28 | 2022-05-20 | 上海电力学院 | Method for modifying surface of aluminum alloy bipolar plate by chitosan/tin dioxide composite film |
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