CN105552399B - A kind of graphene adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell and preparation method thereof - Google Patents
A kind of graphene adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Conducting polymer modified dual polar plates of proton exchange membrane fuel cell and preparation method thereof is adulterated the present invention relates to a kind of graphene, belongs to field of fuel cell technology.Bipolar plates of the present invention are made of the conducting polymer film layer of metallic plate, polar oxygenated film layer, graphene doping, the polar oxygenated film layer is covered in metal sheet surface, the conducting polymer film layer of the graphene doping is covered in polar oxygenated film surface, the thickness of the conducting polymer film layer of the graphene doping is 0.005~0.3mm, the thickness of the polar oxygenated film layer is 5~30nm, and the thickness of the metallic plate is 0.1~2mm.The present invention is that graphene doping conductive polymer membrane is deposited on pretreated stainless steel surface using electrochemical method for synthesizing, it is smaller by metal double polar plates contact resistance produced by the present invention, corrosion electric current density is low, metal substrate is high with conductive polymer membrane combined with firmness, and the method for the present invention is simple, processing cost is low, can produce in batches.
Description
Technical field
The invention belongs to field of fuel cell technology, are related to a kind of dual polar plates of proton exchange membrane fuel cell and its preparation side
Method, it is more particularly related to which a kind of graphene adulterates conducting polymer modified proton exchange membrane fuel cell metal
Bipolar plates and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is after alkaline fuel cell, phosphoric acid fuel cell, fused carbonate fuel
The 5th Replacing fuel battery to grow up after battery, solid oxide fuel cell is the hydrogen using proton exchange membrane as electrolyte
Or reform gas be fuel, air or oxygen be oxidant novel environment friendly fuel cell, be it is a kind of will be in fuel and oxidant
Chemical energy is converted into the power generator of electric energy.Bipolar plates are that PEMFC cells in series gets up to form the critical component of battery pile,
Its main function is to separate Oxidizing and Reducing Agents, and collected current divides and leads unstrpped gas and generation.Bipolar plates are to the body of battery
Product, weight, cost, the runnability of fuel cell all have a great impact.At present, the research in relation to bipolar plates is concentrated mainly on
In terms of the material selection and flow Field Design of bipolar plates, the modification side of selection and substrate material surface especially for basis material
Many work have been done in face, and final purpose is provided to reduce the corrosion of bipolar plates, extends fuel battery service life, reduce battery into
This, reduces battery volume, further improves battery working efficiency.Bipolar plates, which are used as, to be connected individual fuel cells and battery
The component of interior reaction environment, Proton Exchange Membrane Fuel Cells have the electric conductivity and Corrosion Protection of bipolar plates very high want
It asks.
The fuel cell of current industrialization is mostly using copper (or silver) gilding or graphite block as bipolar
Plate material, they respectively have advantage and disadvantage：First, copper (or silver) gilding electrical and thermal conductivity performance is all very good, can also be made very thin, matter
Amount is light.However, since silver, the price of gold are expensive, it is difficult drop to get up to form battery pile cost by multiple PEMFC cells in series
Get off.If if in addition there is electroplating quality problem during copper electroplating gold, base material copper is to be easily oxidized corrosion
, this can substantially reduce the service life of battery.2nd, Graphite block material, electric conductivity is superior, cheap, but heat conductivility is slightly worse,
Most importantly graphite block bipolar plates can not possibly be made very thin, this makes multiple PEMFC cells in series get up to form cell stack
Product and weight are all very big, it has not been convenient to make portable battery.In addition, graphite block bipolar plate material is very crisp, battery accidentally uses,
If bipolar plates are easy for crushing by impact, entire battery is just broken.
Stainless steel is conductive, and thermal conductivity is preferable, and higher (stainless sheet steel of 0.01mm thickness has well for easy processing and intensity
Intensity), especially its antioxygenic property is superior, more much better than the corrosion resistance of copper in the oxidation environment of fuel cell, adds
Its upper relatively low cost, therefore, stainless steel material has the potentiality as ideal bipolar plates framework material.But compared with noble metal
(such as：Gold) for, the oxidation of burn into cathode side easily occurs for most stainless steels anode side under proton exchange membrane running environment
Also easy progressive additive, corrosion product can gradually be assembled film on MEA, not only led to catalyst poisoning but also reduced membrane conductance.In addition
Stainless steel material ontology electric conductivity is relatively poor, these all influence battery performance.
Conductivity of Conductive Polymers can between conductors and insulators change, have within the scope of common temperature
Very high stability, its application in terms of fuel battery double plates is also by more and more attention.Internal fuel battery side
The well-known scholar Huang Naibao in face is modified bipolar plate of stainless steel, and using electrochemical deposition nano-tube/polyaniline conductive film to modification
Chemical property of the bipolar plates in the case where simulating PEMFC anode-contexts is tested.The result shows that nano polyaniline film layer can make
Corrosion potential of the stainless steel in corrosive liquid is simulated improves；In the case where simulating anode operation current potential, by 10h constant potential polarizations, change
Property bipolar plates are not observed the degradation of film layer and come off.However, conducting polymer composite, in any case it or it is a kind of high
Molecule, electric conductivity, ageing-resistant performance are far short of what is expected more than common metal conductor (such as copper and silver).Therefore, it is as fuel
The surfacing of cell bipolar plate also much wants improved place.In addition, the patent application of Publication No. CN101488574A
Also disclose that a kind of proton exchange membrane fuel cell stainless steel bipolar plate and preparation method thereof, the stainless steel double polar plate surface is covered
One strata pyrroles of lid/polyaniline is anti-corrosion, conductive composite coating, conductive composite coating thickness is 10~25 μm, and bottom polypyrrole applies
The polyaniline coating thickness ratio of layer and top layer is 1:Between 1~4, the coating is synthesized using the method for electrochemistry, but the party
Method synthesizes top layer and the condition of primer coating is harsh, and it is 0~5 DEG C or so to be both needed to using ice-water bath control synthesis temperature, in camera bellows
It inside carries out avoiding illumination, and the contact resistance of metal double polar plates obtained is larger, electric conductivity is not ideal enough.
For graphene as a kind of new inorganic material risen in recent years, it is most hard nanometer that it is most thin, which to be currently world,
Material, it is almost fully transparent；Thermal conductivity factor is up to 5300W/mK, and higher than carbon nanotube and diamond, it is electric under room temperature
Transport factor is more than that carbon nanotubes or silicon crystal are high, and resistivity about 10-6Ω cm, it is lower than copper or silver, it is to current generation
The material of upper known resistivity minimum.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, itself is hard and has
Good heat conductivility is the excellent material that is adapted to make or be modified bipolar plate material.Where the present inventor
Seminar discloses " graphene modified polyaniline/stainless steel composite material bipolar plates " in the achievement in research of early period, and electricity consumption is sunk
Product method deposits one layer of redox graphene (RGO) film in polyaniline/stainless steel surface, and ingredient to film and changes
The performances such as conductive, corrosion-resistant of bipolar plates are studied after property, the results showed that modified RGO/ polyanilines/stainless steel double polar
The corrosion electric current density of plate has dropped an order of magnitude, and the impedance of modified bipolar plates is substantially reduced, but uses the technology system
Bipolar plates polyaniline and RGO film layer hierarchal arrangements, easily cause that combined with firmness between layers are not high to ask
Topic, and may be not wear-resisting using RGO films as outer layer, the final service life for influencing bipolar plates.
Invention content
The present invention is directed to the problem of pointed in background technology and the shortcomings of the prior art, it is an object of the invention to
A kind of graphene is provided and adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell and preparation method thereof.
In order to realize the above-mentioned purpose of the present invention, inventor passes through a large amount of experimental study, has developed a kind of graphene
Adulterate conducting polymer modified dual polar plates of proton exchange membrane fuel cell, the bipolar plates are by metallic plate, polar oxygenated
Film layer, the conducting polymer film layer composition of graphene doping, the polar oxygenated film layer are covered in metal sheet surface, the graphite
The conducting polymer film layer of alkene doping is covered in polar oxygenated film surface, the conducting polymer film layer of the graphene doping
Thickness is 0.005~0.3mm, and the thickness of the polar oxygenated film layer is 5~30nm, the thickness of the metallic plate for 0.1~
2mm。
Further, conducting polymer described in above-mentioned technical proposal can be polyaniline, polypyrrole or other conductive high
Molecular material.
Further, metallic plate described in above-mentioned technical proposal is stainless steel plate or copper coin.
It is further preferred that above-mentioned stainless steel plate is common stainless steel plate material, such as 304,316,316L stainless steels etc.
Material.
Another object of the present invention is to provide a kind of graphene described above to adulterate conducting polymer modified proton friendship
The preparation method of membrane fuel cell metal bipolar plate is changed, described method includes following steps：
(1) electrolyte is prepared：By the dispersion of conducting polymer monomer, carboxylated graphene and inorganic acid in deionized water,
Then ultrasonic disperse is uniform while stirring, is made electrolyte, stand for standby use, and a concentration of the 0.1 of inorganic acid in the electrolyte~
1mol/L, a concentration of 0.05~1mol/L of conducting polymer monomer, the mass fraction of carboxylated graphene is 1~10%；
(2) metallic plate pre-processes：The metallic plate that thickness is 0.1~2mm is chosen, successively using the sand paper of different size to gold
Belong to plate to polish, be put into the oxidation solution containing nitric acid and hydrogen peroxide and carried out at normal temperature oxidation after then being cleaned up with acetone
Reason 3~10 minutes, makes metal sheet surface form polar oxygenated film layer, then rinsed well with deionized water, spare after drying；
(3) metal sheet surface electrochemistry formated graphene doping conducting polymer film layer after the pre-treatment：Using three electricity
The metallic plate using electrochemical method for synthesizing in electrolytic cell, is put into step (1) electrolyte obtained by polar body system
In, using metallic plate as working electrode, platinum electrode is auxiliary electrode, and saturated calomel electrode is reference electrode, described pre- in step (2)
The polar oxygenated film surface chemical synthesis of treated metallic plate deposits the conducting polymer film layer of graphene doping simultaneously, so
The metallic plate that deposition has conducting polymer film layer is put into baking oven afterwards and is heating and curing, the graphene doping conducting polymer is made
The dual polar plates of proton exchange membrane fuel cell of object modification.
Further, electrochemistry formated technology described in above-mentioned technical proposal step (3) can be potentiostatic method, timing electricity
Any one of stream method or cyclic voltammetry electrochemical method.
Further, electrochemical method for synthesizing described in above-mentioned technical proposal step (3) is chronoamperometry, specific heavy
Product condition be：Voltage range is -0.2~1.3V, and the time is 60~600s.
Further, described in above-mentioned technical proposal step (2) in oxidation solution nitric acid a concentration of 5~10%, it is described double
A concentration of the 3~5% of oxygen water.
Carboxylated graphene described in above-mentioned technical proposal step (1) of the present invention is 70~100 by graphene powder
Under the conditions of DEG C through strong acid solution be acidified then dilute, filter after be made.
Further, the temperature of baking oven described in above-mentioned technical proposal step (3) is 120~160 DEG C, hardening time 1
~6h.
Further, each sand paper in above-mentioned technical proposal described in step (2) is 30 to the number that metallic plate is polished
~100 times.
The purpose of step (2) is that stainless steel surface is made to remove fine and close oxide layer in the above-mentioned preparation method of the present invention, together
When be allowed to hydroxylating, tax and polarity, preferably to be combined with conducting polymer film layer.
Compared with prior art, the present invention has following advantageous effect：
(1) the modified metal double polar plates of conducting polymer film layer adulterated through graphene of the present invention can not influence it is bipolar
Its corrosion electric current density under simulated battery anode-context is made to decline 1~3 order of magnitude, contact electricity while other performances of plate
Resistance has dropped 100~400m Ω since the presence of graphene is compared to pure conducting polymer modified bipolar plate of stainless steel
cm2It is compared with non-modified bipolar plate of stainless steel, has dropped 500~1000m Ω cm2；
(2) there is one layer thin polar oxygenated film between metal substrate of the invention and the conducting polymer film layer of graphene doping
Layer so that metal substrate is high with conductive polymer membrane combined with firmness, and metal double polar plates wearability obtained is stronger, extends
The service life of bipolar plates；
(3) present invention is that graphene doping conductive polymer membrane is deposited on pretreated stainless steel surface, pole plate
Main body be still stainless steel, ensure that bipolar plates still have it is corrosion-resistant, structural strength is high, easy processing, it is at low cost the advantages of；
(4) present invention is using electrochemistry formated technology, by implementing electropolymerization conducting polymer and electro-deposition graphite simultaneously
Alkene is modified pretreated bipolar plate of stainless steel, directly synthesizes on stainless steel and deposits conducting polymer/stone
Black alkene film, i.e. graphene adulterate conductive polymer membrane, therefore preparation process of the present invention is simple, and processing cost is low, can batch
Production；
(5) graphene of the invention doping conductive polymer membrane does not have proton exchange membrane any pollution, and can be with shape
Into barrier layer, slow down the poisoning of MEA；
(6) present invention is suitable for the surface modification of low-temperature fuel cell bipolar plates, such as：Proton Exchange Membrane Fuel Cells is stainless
The surface of steel bipolar plates is modified.
Description of the drawings
Fig. 1 is the conducting polymer modified proton exchange membrane combustion of graphene doped polyaniline made from the embodiment of the present invention 1
Expect the structure diagram of battery bipolar plate of stainless steel, wherein, 1- stainless steel plates, the polar oxygenated film layers of 2-, 3- electrically conductive polyanilines/stone
Black alkene film layer.
Specific embodiment
Form is described in further detail, but should not manage this above of present invention again by the following examples
It solves and is only limitted to following embodiment for the range of the above-mentioned theme of the present invention, all technologies realized based on the above of the present invention are equal
Belong to the scope of the present invention.
Carboxylated graphene in following embodiments is made using following methods, is included the following steps：
(11) the 72ml concentrated sulfuric acids and 36ml concentrated nitric acids, magnetic agitation 15 minutes under condition of ice bath are added in into round-bottomed flask
Afterwards, 2g natural flake graphites are slowly added into flask, the stirring that keeps avoids graphite from reuniting, after graphite dispersion is uniform,
44g potassium chlorate is slowly added into flask again, the time for adding for controlling potassium chlorate is 1h, then removes ice bath, at room temperature instead
It answers 96 hours, after the completion of reaction, natural flake graphite has just been oxidized to graphite oxide, then solution is poured into the burning of 1000ml
In cup, deionized water dilution is added in, after being stirred evenly with glass bar, stands 1 hour, is filtered after solution layering, is collected solid
Oxidation graphite solid is made in body；
(12) oxidation graphite solid made from 100g above-mentioned steps (11) is dissolved in the beaker of 1000ml with deionized water
In, the hydrochloric acid 15ml that mass concentration is 5% is added in, after stirring evenly, is filtered after standing 4 hours, collects solid, so repeatedly two
It is secondary；Then one day is stood, after the color of solution becomes kermesinus, is diluted with deionized water, then ultrasound 15 minutes, then
Centrifugation filters, and collects filtrate, obtains homodisperse graphene oxide solution, and it is dense that 20ml is added in graphene oxide solution
The sodium hydroxide solution for 5mol/L is spent, after being stirred evenly with glass bar, stands 30 minutes, graphene oxide solid is flocculated out
Come, then filter, collect solid, then washed with ethyl alcohol to neutrality, to remove the sodium hydroxide in flocculate, finally by institute
Solid is stated to be dried in 40 DEG C of vacuum drying chamber to constant weight to get to graphene oxide solid；
(13) 100mg above-mentioned steps (12) the graphene oxide solid obtained is weighed, the round bottom for being added to 500ml is burnt
In bottle, 300ml deionized waters are then added in, ultrasonic disperse 30 minutes is completely dissolved graphene oxide, then proceedes to add in
75ul hydrazine hydrates and 400ul ammonium hydroxide, magnetic agitation is reacted 4 hours under the conditions of 95 DEG C of oil baths, is then filtered, is washed with deionized water
It washs to neutrality, finally drying to constant weight in vacuum drying chamber, and graphene powder is made；
(14) it is using 50ml mixed strong acids that step (12) graphene powder obtained is sour at a temperature of 70~100 DEG C
Change 30min, then dilute, carboxylated graphene is obtained by filtration, wherein, the mixed strong acids prepared by the concentrated sulfuric acid and concentrated nitric acid and
Into the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3：1.
Using stainless steel plate, the stainless steel plate is pre-processed metallic plate in following embodiments as follows：
First choose thickness be 0.3mm stainless steel plate, it is 13mm × 13mm to cut size with plate shearing machine, successively using 500#, 800#,
The sand paper of four kinds of different sizes of 1500# to 2000# respectively beats stainless steel plate, and the sand paper of each specification polishes 30~
It 100 times, is put into after then being cleaned up with acetone in the oxidation solution containing nitric acid and hydrogen peroxide and carries out normal temperature oxidation processing 3~10
Minute, polar oxygenated layer is formed in stainless steel surface, is then rinsed well again with deionized water, it is spare after drying, wherein, it is described
A concentration of 5~10% of nitric acid described in oxidation solution, a concentration of the 3~5% of the hydrogen peroxide.Metallic plate is pre-processed
Purpose is metal sheet surface to be made to remove fine and close oxide layer, while be allowed to hydroxylating, tax and polarity, so as to preferably with conduction
Macromolecule layer combines.
Current potential described in following embodiment is relative to for calomel electrode.
Embodiment 1
A kind of graphene of the present embodiment adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell,
The bipolar plates are made of 316L stainless steel plates 1, polar oxygenated film layer 2, electrically conductive polyaniline/graphene film layer 3, such as 1 institute of attached drawing
Show, the polar oxygenated film layer 2 is covered in 1 surface of stainless steel plate, and the electrically conductive polyaniline/graphene film layer 3 is covered in polarity
2 surface of oxidation film layer, the thickness of the electrically conductive polyaniline/graphene film layer 3 is about 0.03mm, the thickness of the polar oxygenated film layer
Degree is about 10nm, and the thickness of the stainless steel plate 1 is 0.3mm.
The dual polar plates of proton exchange membrane fuel cell of the present embodiment graphene doped polyaniline modification described above
Preparation method it is as follows：
(1) electrolyte is prepared：By the dispersion of conducting polymer monomer, carboxylated graphene and inorganic acid in deionized water,
Then ultrasonic disperse 25 minutes while stirring, are made electrolyte, stand for standby use, H in the electrolyte2SO4It is a concentration of
0.5mol·L-1, a concentration of 0.3molL of aniline monomer-1, the mass fraction of carboxylated graphene is 4%；
(2) after the pre-treatment stainless steel surface electrochemistry formated simultaneously deposits graphene doping conducting polymer film layer：
Electrochemistry formated experiment carries out in conventional three-electrode system, using chronoamperometry in electrolytic cell, by the metallic plate
It is put into step (1) electrolyte obtained, using pretreated stainless steel plate as working electrode, platinum plate electrode is auxiliary electricity
Pole, saturated calomel electrode are reference electrode, control scanning voltage ranging from -0.2~1.3V, time 300s, by graphene/poly-
Aniline composite material electrochemistry formated deposits to the polar oxygenated film surface on stainless steel electrode simultaneously, and deposition then is had stone
The metallic plate of black alkene/polyaniline composite film layer is put into 125 DEG C of baking oven the 6h that is heating and curing, and it is conductive that the graphene doping is made
Polymer-modified dual polar plates of proton exchange membrane fuel cell.
By the stainless steel substrates of graphene doped conductive polyaniline obtained above modification in simulation pem fuel electricity
Pond (PEMFC) cathode environment (80 DEG C, corrosive liquid 0.01mol/L Na2SO4+ 0.01mol/L HCl solutions, are continuously passed through H2Two is small
When after be put into sample) under corrosion resistance and electric conductivity be tested, test result shows polyaniline/graphene film pair
There is remarkable result in enhancing 316L stainless steel corrosion resistances, blank stainless steel corrosion current density is 1.0581*10-4Amp/
cm2, the corrosion current density of the bipolar plate of stainless steel by the film modified mistake of graphene/polyaniline is 1.2518*10-6Amp/
cm2, the corrosion current density of stainless steel steel disc of graphene doped conductive polyaniline modification has dropped an order of magnitude, anti-corruption
Corrosion can improve, and contact resistance can be reduced to 61m Ω cm2, the raising of current collection efficiency detail；By sinking with independent electrochemistry
Aniline comparison is gathered, inhibition efficiency rises about 30%~40% relative to the stainless steel steel disc of Polyaniline-modified, relative to
The stainless steel that any modification is not done on surface rises 50% or so, and contact resistance is from the 732m Ω cm of former stainless steel substrate2, arrive
Individually use the 356m Ω cm of Polyaniline-modified2, then at present with the 61m Ω cm of graphene doped conductive polyaniline modification2。
Embodiment 2
A kind of graphene of the present embodiment adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell,
The bipolar plates are made of 316L stainless steel plates 1, polar oxygenated film layer 2, electrically conductive polyaniline/graphene film layer 3, the polar oxygen
To change film layer and be covered in metal sheet surface, the conducting polymer film layer of the graphene doping is covered in polar oxygenated film surface,
The thickness of the electrically conductive polyaniline/graphene film layer 3 is about 0.035mm, and the thickness of the polar oxygenated film layer is about 10nm, institute
The thickness for stating stainless steel plate 1 is 0.3mm.
(1) electrolyte is prepared：By the dispersion of conducting polymer monomer, carboxylated graphene and inorganic acid in deionized water,
Then ultrasonic disperse 30 minutes while stirring, are made electrolyte, stand for standby use, H in the electrolyte2SO4It is a concentration of
0.5mol·L-1, a concentration of 0.3molL of aniline monomer-1, the mass fraction of carboxylated graphene is 6%；
(2) stainless steel surface electrochemistry formated graphene doping conducting polymer film layer after the pre-treatment：Electrochemistry
Compound experiment carries out in conventional three-electrode system, and using chronoamperometry in electrolytic cell, the metallic plate is put into step
Suddenly in (1) described electrolyte obtained, using pretreated stainless steel plate as working electrode, platinum plate electrode is auxiliary electrode, is satisfied
It is reference electrode with calomel electrode, scanning voltage ranging from -0.2~1.3V, time 300s is controlled, by graphene/polyaniline
Composite material electrochemistry formated deposits to the polar oxygenated film surface on stainless steel electrode simultaneously, and deposition then is had graphite
The metallic plate of alkene/polyaniline composite film layer is put into 125 DEG C of baking oven the 6h that is heating and curing, and it is conductive poly- that the graphene doping is made
Close the dual polar plates of proton exchange membrane fuel cell of object modification.
By the stainless steel substrates of graphene doped conductive polyaniline obtained above modification in simulation pem fuel electricity
Pond (PEMFC) cathode environment (80 DEG C, corrosive liquid 0.01mol/L Na2SO4+ 0.01mol/L HCl solutions, are continuously passed through H2Two is small
When after be put into sample) under corrosion resistance and electric conductivity be tested, test result show polyaniline/graphene film for
Enhancing 316L stainless steel corrosion resistances have remarkable result, and the corrosion current density of blank stainless steel is 1.0581*10-4Amp/
cm2, the corrosion current density of the bipolar plate of stainless steel by the film modified mistake of graphene/polyaniline is 1.0213*10-6Amp/
cm2, the corrosion current density of stainless steel steel disc of graphene doped conductive polyaniline modification has dropped two orders of magnitude, anti-corruption
Corrosion can improve, and contact resistance can be reduced to 38m Ω cm2, the raising of current collection efficiency detail.By sinking with independent electrochemistry
Aniline comparison is gathered, inhibition efficiency rises about 30%~40% relative to the stainless steel steel disc of Polyaniline-modified, relative to
The stainless steel that any modification is not done on surface rises 55% or so.Contact resistance is from the 732m Ω cm of former stainless steel substrate2, arrive
Individually use the 356m Ω cm of Polyaniline-modified2The 38m Ω cm modified at present with graphene doped conductive polyaniline are arrived again2。
Claims (7)
1. a kind of graphene adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell, it is characterised in that：
The bipolar plates are made of the conducting polymer film layer of metallic plate, polar oxygenated film layer, graphene doping, the polar oxygenated film
Layer is covered in metal sheet surface, and the conducting polymer film layer of the graphene doping is covered in polar oxygenated film surface, described
Conducting polymer is polyaniline or polypyrrole, the thickness of the conducting polymer film layer of graphene doping for 0.005~
0.3mm, the thickness of the polar oxygenated film layer is 5~30nm, and the thickness of the metallic plate is 0.1~2mm；Preparation method packet
Include following steps：
(1) electrolyte is prepared：By the dispersion of conducting polymer monomer, carboxylated graphene and inorganic acid in deionized water, then
Ultrasonic disperse is uniform while stirring, obtained electrolyte, stand for standby use, a concentration of 0.1~1mol/ of inorganic acid in the electrolyte
L, a concentration of 0.05~1mol/L of conducting polymer monomer, the mass fraction of carboxylated graphene is 1~10%；
(2) metallic plate pre-processes：Choose thickness be 0.1~2 metallic plate, successively using the sand paper of different size to metallic plate into
Row polishing, be put into after then being cleaned up with acetone in the oxidation solution containing nitric acid and hydrogen peroxide carries out normal temperature oxidation handle 3~
10 minutes, metal sheet surface is made to form polar oxygenated film layer, then rinsed well with deionized water, it is spare after drying；
(3) metal sheet surface electrochemistry formated graphene doping conducting polymer film layer after the pre-treatment：Using three electrode bodies
Using electrochemical method for synthesizing in electrolytic cell, the metallic plate is put into step (1) electrolyte obtained for system, with
Metallic plate is working electrode, and platinum electrode is auxiliary electrode, and saturated calomel electrode is reference electrode, in step (2) pretreatment
The polar oxygenated film surface chemical synthesis of metallic plate afterwards deposits the conducting polymer film layer of graphene doping simultaneously, then will
The metallic plate that depositing has conducting polymer film layer, which is put into baking oven, to be heating and curing, and the graphene doping conducting polymer is made and repaiies
The dual polar plates of proton exchange membrane fuel cell of decorations.
2. graphene according to claim 1 adulterates conducting polymer modified proton exchange membrane fuel cell metal dual-polarity
Plate, it is characterised in that：The metallic plate is stainless steel plate or copper coin.
3. a kind of adulterate conducting polymer modified proton exchange membrane combustion according to claim 1~2 any one of them graphene
Expect the preparation method of battery metal bi-polar plate, it is characterised in that：Described method includes following steps：
(1) electrolyte is prepared：By the dispersion of conducting polymer monomer, carboxylated graphene and inorganic acid in deionized water, then
Ultrasonic disperse is uniform while stirring, obtained electrolyte, stand for standby use, a concentration of 0.1~1mol/ of inorganic acid in the electrolyte
L, a concentration of 0.05~1mol/L of conducting polymer monomer, the mass fraction of carboxylated graphene is 1~10%；
(2) metallic plate pre-processes：Choose thickness be 0.1~2 metallic plate, successively using the sand paper of different size to metallic plate into
Row polishing, be put into after then being cleaned up with acetone in the oxidation solution containing nitric acid and hydrogen peroxide carries out normal temperature oxidation handle 3~
10 minutes, metal sheet surface is made to form polar oxygenated film layer, then rinsed well with deionized water, it is spare after drying；
(3) metal sheet surface electrochemistry formated graphene doping conducting polymer film layer after the pre-treatment：Using three electrode bodies
Using electrochemical method for synthesizing in electrolytic cell, the metallic plate is put into step (1) electrolyte obtained for system, with
Metallic plate is working electrode, and platinum electrode is auxiliary electrode, and saturated calomel electrode is reference electrode, in step (2) pretreatment
The polar oxygenated film surface chemical synthesis of metallic plate afterwards deposits the conducting polymer film layer of graphene doping simultaneously, then will
The metallic plate that depositing has conducting polymer film layer, which is put into baking oven, to be heating and curing, and the graphene doping conducting polymer is made and repaiies
The dual polar plates of proton exchange membrane fuel cell of decorations.
4. graphene according to claim 3 adulterates conducting polymer modified proton exchange membrane fuel cell metal dual-polarity
The preparation method of plate, it is characterised in that：Electrochemistry formated technology described in step (3) can be potentiostatic method, chronoamperometry
Or any one of cyclic voltammetry electrochemical method.
5. graphene according to claim 4 adulterates conducting polymer modified proton exchange membrane fuel cell metal dual-polarity
The preparation method of plate, it is characterised in that：Electrochemical method for synthesizing described in step (3) be chronoamperometry, specific sedimentary condition
For：Voltage range is -0.2~1.3V, and the time is 60~600s.
6. graphene according to claim 3 adulterates conducting polymer modified proton exchange membrane fuel cell metal dual-polarity
The preparation method of plate, it is characterised in that：Carboxylated graphene described in step (1) is at 70~100 DEG C by graphene powder
Under the conditions of through strong acid solution be acidified then dilute, filter after be made.
7. graphene according to claim 3 adulterates conducting polymer modified proton exchange membrane fuel cell metal dual-polarity
The preparation method of plate, it is characterised in that：The temperature of baking oven described in step (3) is 120~160 DEG C, and hardening time is 1~6h.
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| CN107634238B (en) * | 2017-08-29 | 2024-03-15 | 国网电力科学研究院武汉南瑞有限责任公司 | Bipolar plate with higher strength and manufacturing method thereof |
| CN108199058B (en) * | 2017-12-15 | 2023-05-05 | 中国第一汽车股份有限公司 | Preparation method of conductive polymer-graphene composite bipolar plate |
| CN108832153B (en) * | 2018-06-26 | 2020-11-20 | 山东亚泰新材料科技有限公司 | Flow field plate of proton exchange membrane fuel cell |
| CN108832152B (en) * | 2018-06-26 | 2020-11-24 | 山东亚泰新材料科技有限公司 | Coated metal flow field plate of proton exchange membrane fuel cell |
| CN110875483B (en) * | 2018-09-04 | 2020-12-18 | 大连融科储能装备有限公司 | Integrated electrode-bipolar plate structure and preparation method |
| CN111822024B (en) * | 2019-04-18 | 2023-04-18 | 湖北大学 | Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof |
| CN110364749A (en) * | 2019-07-23 | 2019-10-22 | 南京工业大学 | The preparation method of surface composite coating based on dual polar plates of proton exchange membrane fuel cell |
| CN110690473A (en) * | 2019-11-14 | 2020-01-14 | 上海电气集团股份有限公司 | Preparation method of carbon nanotube array-conductive polymer coating of metal bipolar plate |
| CN114032669A (en) * | 2021-12-15 | 2022-02-11 | 四川大学 | Electrophoretic deposition-electropolymerization synchronous modification method for carbon fiber surface interface and carbon fiber composite material thereof |
| CN114665102A (en) * | 2022-03-21 | 2022-06-24 | 北京氢沄新能源科技有限公司 | Metal bipolar plate of fuel cell and preparation method thereof |
| CN115433914B (en) * | 2022-11-07 | 2023-02-03 | 江苏金亚隆科技有限公司 | Preparation process of high-temperature-resistant and antioxidant graphite product coating |
| CN116154204B (en) * | 2023-02-23 | 2023-07-25 | 浙江菲尔特过滤科技股份有限公司 | Carbon film coating process for fuel cell plate |
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