CN105552399A - Graphene-doping conductive polymer modified metal bipolar plate of proton exchange membrane fuel cell and preparation method of metal bipolar plate - Google Patents
Graphene-doping conductive polymer modified metal bipolar plate of proton exchange membrane fuel cell and preparation method of metal bipolar plate 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
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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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Abstract
The invention relates to a graphene-doping conductive polymer modified metal bipolar plate of a proton exchange membrane fuel cell and a preparation method of the metal bipolar plate, belonging to the technical field of a fuel cell. The bipolar plate comprises a metal plate, a polarity oxide film layer and a graphene-doping conductive polymer film layer, wherein the polarity oxide film layer covers the surface of the metal plate, the graphene-doping conductive polymer film layer covers the surface of the polarity oxide film layer, and the thickness of the graphene-doping conductive polymer film layer is 0.005-0.3 millimeter, the thickness of the polarity oxide film layer is 5-30 nanometers, and the thickness of the metal plate is 0.1-2 millimeters. A graphene-doping conductive polymer film is deposited on the surface of a stainless steel plate after preprocessing by an electrochemical synthesis method, the metal bipolar plate prepared according to the invention has the advantages of relatively low contact resistance, low corrosion current density and high bonding firmness of the metal substrate and the conductive polymer film, moreover, the method is simple, the processing cost is low, and mass production can be achieved.
Description
Technical field
The invention belongs to field of fuel cell technology, relate to a kind of dual polar plates of proton exchange membrane fuel cell and preparation method thereof, more particularly, the present invention relates to conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of a kind of Graphene and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is the 5th Replacing fuel battery grown up after alkaline fuel cell, phosphoric acid fuel cell, molten carbonate fuel cell, Solid Oxide Fuel Cell, take proton exchange membrane as electrolyte, hydrogen or reformed gas are fuel, air or oxygen is the novel environment friendly fuel cell of oxidant, be a kind of is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy by the chemical energy in fuel and oxidant.Bipolar plates gets up to form the critical component of battery pile, and its Main Function separates Oxidizing and Reducing Agents, collected current, divides and lead unstrpped gas and produce thing.Bipolar plates is to volume, weight, the cost of battery, and the runnability of fuel cell all has a great impact.At present, research about bipolar plates mainly concentrates on Material selec-tion and the flow Field Design aspect of bipolar plates, particularly do a lot of work for selecting of basis material with the modification aspect of substrate material surface, final purpose is all the corrosion in order to reduce bipolar plates, extend fuel battery service life, reduce battery cost, reduce battery volume, improve battery operated efficiency further.Bipolar plates is as coupling together individual fuel cells and the parts of reaction environment in battery, and Proton Exchange Membrane Fuel Cells has very high requirement to the conductivity of bipolar plates and Corrosion Protection.
The fuel cell of at present industrialization adopts copper (or silver) gilding or graphite block as bipolar plate material mostly, they respectively have pluses and minuses: one, copper (or silver) gilding electrical and thermal conductivity performance is all very good, also can do very thin, quality is light.But, due to silver, price of gold costliness, get up to form battery pile cost by multiple PEMFC cells in series and be difficult to lower.If there is electroplating quality problem in copper electrogilding process in addition, base material copper is easy to oxidized corrosion, and this can reduce the life-span of battery greatly.Two, Graphite block material, electric conductivity is superior, low price, but heat conductivility is slightly poor, the most important thing is that graphite block bipolar plates can not be done very thin, it is all very large that this makes multiple PEMFC cells in series get up to form battery pile volume and weight, is inconvenient to make portable battery.In addition, graphite block bipolar plate material is very crisp, and battery uses because of carelessness, if bipolar plates is subject to impacting just easily broken, whole battery is just bad.
Stainless steel conducts electricity, thermal conductivity is better, easy processing and intensity higher (stainless sheet steel that 0.01mm is thick has good intensity), especially its antioxygenic property is superior, corrosion resistance than copper in the oxidation environment of fuel cell is much better, add its lower cost, therefore, stainless steel material has the potentiality becoming ideal bipolar plates framework material.But compared with noble metal (as: gold), easily there is burn into negative electrode side oxide-film also easy progressive additive in most stainless steel anode side under proton exchange membrane running environment, corrosion product can be assembled gradually on MEA, not only causes catalyst poisoning but also reduce membrane conductance.Stainless steel material body electric conductivity is relatively poor in addition, and these all affect battery performance.
Conductivity of Conductive Polymers can be able to change between conductors and insulators, in conventional temperature range, have very high stability, and its application in fuel battery double plates is also subject to more and more many attention.The well-known scholar Huang Naibao in internal fuel battery aspect uses electrochemical deposition nano-tube/polyaniline conductive film to carry out modification to bipolar plate of stainless steel, and tests the chemical property of modification bipolar plates under simulation PEMFC anode-context.Result shows, nano polyaniline rete can make the corrosion potential of stainless steel in corrosion simulation liquid improve; Under simulation anode operation current potential, through 10h constant potential polarization, modification bipolar plates is not observed the degraded of rete and comes off.But conducting polymer composite, in any case it or a kind of macromolecule, its electric conductivity, ageing-resistant performance are far short of what is expected more than common metal conductor (as copper and silver).Therefore, its place that much will improve in addition as the surfacing of fuel battery double plates.In addition, publication number is that the patent application of CN101488574A also discloses a kind of proton exchange membrane fuel cell stainless steel bipolar plate and preparation method thereof, described bipolar plate of stainless steel surface coverage one deck polypyrrole/polyaniline is anti-corrosion, conduction composite coating, conduction composite coating thickness is 10 ~ 25 μm, the polyaniline coating Thickness Ratio of bottom polypyrrole coating and top layer is between 1:1 ~ 4, described coating adopts electrochemical method to synthesize, but the condition of the method synthesis top layer and primer coating is harsh, all needing to use ice-water bath to control synthesis temperature is about 0 ~ 5 DEG C, carry out avoiding illumination in camera bellows, and the contact resistance of obtained metal double polar plates is larger, electric conductivity is not ideal enough.
Graphene, as a kind of new inorganic material of rising in recent years, be the thinnest is in the world at present but the hardest nano material, is almost completely transparent; Conductive coefficient is up to 5300W/mK, and higher than carbon nano-tube and diamond, under normal temperature, its electron mobility exceedes CNT (carbon nano-tube) or silicon wafer height, and resistivity only about 10
-6Ω cm, than copper or silver lower, be the minimum material of resistivity known in the world up till now.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, and own hard have again good heat conductivility, is the excellent material be applicable to for making or modification bipolar plate material.The present inventor place seminar discloses " Graphene modified polyaniline/stainless steel composite material bipolar plates " in the achievement in research in early stage, Means of Electrodeposition deposits one deck redox graphene (RGO) film at polyaniline/stainless steel surfaces, and to the composition of film and the conduction of modified bipolar plates, the performance such as corrosion-resistant is studied, result shows that the corrosion electric current density of modified RGO/ polyaniline/bipolar plate of stainless steel have dropped an order of magnitude, and the impedance of modified bipolar plates significantly reduces, but the bipolar plates polyaniline adopting this technology obtained and RGO thin layer hierarchal arrangement, easily cause the problem not high in conjunction with firmness between layers, and may not be wear-resisting as skin using RGO film, the final useful life affecting bipolar plates.
Summary of the invention
The present invention is directed to the deficiency of problem pointed in background technology and prior art existence, the object of the present invention is to provide conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of a kind of Graphene and preparation method thereof.
In order to realize above-mentioned purpose of the present invention, inventor is through a large amount of experimental studies, have developed the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of a kind of Graphene, described bipolar plates is by metallic plate, polar oxygenated rete, the conducting polymer rete composition of Graphene doping, described polar oxygenated rete covers metal sheet surface, the conducting polymer rete of described Graphene doping covers polar oxygenated film surface, the thickness of the conducting polymer rete of described Graphene doping is 0.005 ~ 0.3mm, the thickness of described polar oxygenated rete is 5 ~ 30nm, the thickness of described metallic plate is 0.1 ~ 2mm.
Further, conducting polymer described in technique scheme can be polyaniline, polypyrrole or other conducting polymer composite.
Further, metallic plate described in technique scheme is corrosion resistant plate or copper coin.
Further preferably, above-mentioned corrosion resistant plate is common corrosion resistant plate material, as materials such as 304,316,316L stainless steels.
Another object of the present invention is to the preparation method providing the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of a kind of Graphene described above, described method comprises the steps:
(1) electrolyte is prepared: by the dispersion of conducting polymer monomer, carboxylated Graphene and inorganic acid in deionized water, then ultrasonic disperse is even while stirring, obtained electrolyte, stand for standby use, in described electrolyte, the concentration of inorganic acid is 0.1 ~ 1mol/L, the concentration of conducting polymer monomer is 0.05 ~ 1mol/L, and the mass fraction of carboxylated Graphene is 1 ~ 10%;
(2) metallic plate preliminary treatment: choose the metallic plate that thickness is 0.1 ~ 2mm, the sand paper of different size is utilized to polish to metallic plate successively, then the oxidation solution put into after cleaning up with acetone containing nitric acid and hydrogen peroxide carries out normal temperature oxidation process 3 ~ 10 minutes, metal sheet surface is made to form polar oxygenated rete, clean with deionized water rinsing again, dry up rear for subsequent use;
(3) the conductive doped polymer film of metal sheet surface electrochemistry formated Graphene after the pre-treatment: adopt three-electrode system, electrochemical method for synthesizing is utilized in electrolytic cell, described metallic plate is put into the described obtained electrolyte of step (1), take metallic plate as work electrode, platinum electrode is auxiliary electrode, saturated calomel electrode is reference electrode, in the conducting polymer rete of the polar oxygenated film surface chemical synthesis deposited graphite alkene doping simultaneously of the described pretreated metallic plate of step (2), then the metallic plate depositing conducting polymer rete is put into baking oven to be heating and curing, the obtained conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of described Graphene.
Further, electrochemistry formated technology described in technique scheme step (3) can be any one electrochemical method in potentiostatic method, chronoamperometry or cyclic voltammetry.
Further, described in technique scheme step (3), electrochemical method for synthesizing is chronoamperometry, and concrete sedimentary condition is: voltage range is-0.2 ~ 1.3V, and the time is 60 ~ 600s.
Further, in oxidation solution described in technique scheme step (2), the concentration of nitric acid is 5 ~ 10%, and the concentration of described hydrogen peroxide is 3 ~ 5%.
Carboxylated Graphene described in technique scheme step (1) of the present invention be by graphene powder under 70 ~ 100 DEG C of conditions through strong acid solution acidifying, then dilute, filter after obtained.
Further, described in technique scheme step (3), the temperature of baking oven is 120 ~ 160 DEG C, and curing time is 1 ~ 6h.
Further, in technique scheme, often kind of sand paper described in step (2) is 30 ~ 100 times to the number of times that metallic plate is polished.
In the above-mentioned preparation method of the present invention, the object of step (2) makes corrosion resistant plate surface remove fine and close oxide layer, makes it hydroxylating simultaneously, tax and polarity, to be combined with conducting polymer rete better.
Compared with prior art, the present invention has following beneficial effect:
(1) its corrosion electric current density under simulated battery anode-context can be made while not affecting other performances of bipolar plates to decline 1 ~ 3 order of magnitude through the metal double polar plates that the conducting polymer rete of Graphene of the present invention doping is modified, contact resistance have dropped 100 ~ 400m Ω cm because the existence of Graphene is compared to pure conducting polymer modified bipolar plate of stainless steel
2, compare with the bipolar plate of stainless steel of non-modified, have dropped 500 ~ 1000m Ω cm
2;
(2) the thin polar oxygenated rete of one deck is had between the conducting polymer rete that metal substrate of the present invention and Graphene adulterate, make metal substrate high in conjunction with firmness with conductive polymer membrane, and obtained metal double polar plates resistance to wear is stronger, extends the useful life of bipolar plates;
(3) conductive doped for Graphene polymer film is deposited on pretreated corrosion resistant plate surface by the present invention, and the main body of pole plate is still stainless steel, ensure that bipolar plates still have corrosion-resistant, structural strength is high, easily process, the advantage that cost is low;
(4) the present invention utilizes electrochemistry formated technology, by implementing electropolymerization conducting polymer and electro-deposition Graphene carries out modification to pretreated bipolar plate of stainless steel simultaneously, directly synthesize on stainless steel and depositing electrically conductive polymer/graphene film, the i.e. conductive doped polymer film of Graphene, therefore preparation technology of the present invention is simple, processing cost is low, can produce in batches;
(5) the conductive doped polymer film of Graphene of the present invention is to proton exchange membrane without any pollution, and can form barrier layer, slows down the poisoning of MEA;
(6) the present invention is applicable to the surface modification of low-temperature fuel cell bipolar plates, as: the surface modification of proton exchange membrane fuel cell stainless steel bipolar plate.
Accompanying drawing explanation
Fig. 1 is the structural representation of the conducting polymer modified proton exchange membrane fuel cell stainless steel bipolar plate of the obtained Graphene doped polyaniline of the embodiment of the present invention 1, wherein, and 1-corrosion resistant plate, the polar oxygenated rete of 2-, 3-electrically conductive polyaniline/Graphene rete.
Embodiment
Form is described in further detail foregoing of the present invention again by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Carboxylated Graphene in following embodiment is all adopt following method to obtain, and comprises the steps:
(11) in round-bottomed flask, the 72ml concentrated sulfuric acid and 36ml red fuming nitric acid (RFNA) is added, after condition of ice bath lower magnetic force stirs 15 minutes, 2g natural flake graphite is slowly added in flask, the stirring that keeps avoids graphite to reunite, after graphite dispersion is even, 44g potassium chlorate is slowly added again in flask, the time for adding controlling potassium chlorate is 1h, then ice bath is removed, at room temperature react 96 hours, after having reacted, natural flake graphite has just been oxidized to graphite oxide, then solution is poured in the beaker of 1000ml, add deionized water dilution, after stirring with glass bar, leave standstill 1 hour, suction filtration after solution layering, collect solid, obtained oxidation graphite solid,
(12) with deionized water, the oxidation graphite solid that 100g above-mentioned steps (11) is obtained is dissolved in the beaker of 1000ml, add the hydrochloric acid 15ml that mass concentration is 5%, after stirring, leave standstill suction filtration after 4 hours, collect solid, so repeat twice, then one day is left standstill, after the color of solution becomes kermesinus, dilute with deionized water, then ultrasonic 15 minutes, then centrifugal, suction filtration, collect filtrate, obtain homodisperse graphene oxide solution, the sodium hydroxide solution that 20ml concentration is 5mol/L is added in graphene oxide solution, after stirring with glass bar, leave standstill 30 minutes, graphene oxide solid is flocculated out, then suction filtration, collect solid, then extremely neutral with ethanol washing, to remove the NaOH in the middle of flocculate, finally described solid is dried to constant weight in the vacuum drying chamber of 40 DEG C, namely graphene oxide solid is obtained,
(13) the described obtained graphene oxide solid of 100mg above-mentioned steps (12) is taken, join in the round-bottomed flask of 500ml, then add 300ml deionized water, ultrasonic disperse 30 minutes, makes graphene oxide dissolve completely, then continue to add 75ul hydrazine hydrate and 400ul ammoniacal liquor, at 95 DEG C of oil bath condition lower magnetic force stirring reactions 4 hours, then suction filtration, spend deionized water to neutral, finally dry in vacuum drying chamber to constant weight, obtained graphene powder;
(14) utilize 50ml mixed strong acids by described for step (12) obtained graphene powder acidifying 30min at 70 ~ 100 DEG C of temperature, then dilute, filter and obtain carboxylated Graphene, wherein, described mixed strong acids by the concentrated sulfuric acid and red fuming nitric acid (RFNA) formulated, the volume ratio of the described concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1.
Metallic plate in following embodiment all adopts corrosion resistant plate, described corrosion resistant plate carries out preliminary treatment as follows: first choose the corrosion resistant plate that thickness is 0.3mm, cutting size with plate shearing machine is 13mm × 13mm, utilize 500# successively, 800#, the sand paper of 1500# to 2000# four kinds of different sizes carries out beating to corrosion resistant plate respectively, the sand paper of often kind of specification is all polished 30 ~ 100 times, then the oxidation solution put into after cleaning up with acetone containing nitric acid and hydrogen peroxide carries out normal temperature oxidation process 3 ~ 10 minutes, polar oxygenated layer is formed at stainless steel surfaces, and then it is clean with deionized water rinsing, dry up rear for subsequent use, wherein, the concentration of nitric acid described in described oxidation solution is 5 ~ 10%, the concentration of described hydrogen peroxide is 3 ~ 5%.Carrying out pretreated object to metallic plate is make metal sheet surface remove fine and close oxide layer, makes it hydroxylating simultaneously, tax and polarity, to be combined with electroconductive polymer layer better.
Current potential described in following examples is all for calomel electrode.
Embodiment 1
The conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of a kind of Graphene of the present embodiment, described bipolar plates is made up of 316L corrosion resistant plate 1, polar oxygenated rete 2, electrically conductive polyaniline/Graphene rete 3, as shown in Figure 1, described polar oxygenated rete 2 covers corrosion resistant plate 1 surface, described electrically conductive polyaniline/Graphene rete 3 covers polar oxygenated rete 2 surface, the thickness of described electrically conductive polyaniline/Graphene rete 3 is about 0.03mm, the thickness of described polar oxygenated rete is about 10nm, and the thickness of described corrosion resistant plate 1 is 0.3mm.
The preparation method of the dual polar plates of proton exchange membrane fuel cell of the Graphene doped polyaniline modification that the present embodiment is described above 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, obtained electrolyte, stand for standby use, H in described electrolyte
2sO
4concentration be 0.5molL
-1, the concentration of aniline monomer is 0.3molL
-1, the mass fraction of carboxylated Graphene is 4%;
(2) after the pre-treatment corrosion resistant plate surface electrochemistry synthesis and the conductive doped polymer film of deposited graphite alkene: electrochemistry formated experiment carry out in the three-electrode system of routine, chronoamperometry is adopted in electrolytic cell, described metallic plate is put into the described obtained electrolyte of step (1), with pretreated corrosion resistant plate for work electrode, platinum plate electrode is auxiliary electrode, saturated calomel electrode is reference electrode, gated sweep voltage range is-0.2 ~ 1.3V, time is 300s, grapheme/polyaniline composite material electrochemistry formated is deposited to simultaneously the polar oxygenated film surface on stainless steel electrode, then the baking oven metallic plate depositing graphene/polyaniline composite film being put into 125 DEG C is heating and curing 6h, the obtained conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of described Graphene.
The stainless steel substrates that above-mentioned obtained Graphene doped conductive polyaniline is modified simulation Proton Exchange Membrane Fuel Cells (PEMFC) cathode environment (80 DEG C, corrosive liquid 0.01mol/LNa
2sO
4+ 0.01mol/LHCl solution, passes into H continuously
2put into sample after two hours) under corrosion resistance and electric conductivity test, test result shows, polyaniline/graphene film has remarkable result for enhancing 316L stainless steel corrosion resistance, and blank stainless steel corrosion current density is 1.0581*10
-4amp/cm
2, be 1.2518*10 through the corrosion current density of the bipolar plate of stainless steel of the film modified mistake of graphene/polyaniline
-6amp/cm
2, the corrosion current density of the stainless steel steel disc that Graphene doped conductive polyaniline is modified have dropped an order of magnitude, and corrosion resistance improves, and contact resistance can be reduced to 61m Ω cm
2, current collection efficiency detail improves; By contrasting with independent electrochemical deposition polyaniline, its inhibition efficiency rises about 30% ~ 40% relative to the stainless steel steel disc of Polyaniline-modified, the stainless steel not doing any modification relative to surface rises about 50%, and contact resistance is from the 732m Ω cm of former stainless steel substrate
2, to the 356m Ω cm of independent Polyaniline-modified
2, more up till now with the 61m Ω cm that Graphene doped conductive polyaniline is modified
2.
Embodiment 2
The conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of a kind of Graphene of the present embodiment, described bipolar plates is made up of 316L corrosion resistant plate 1, polar oxygenated rete 2, electrically conductive polyaniline/Graphene rete 3, described polar oxygenated rete covers metal sheet surface, the conducting polymer rete of described Graphene doping covers polar oxygenated film surface, the thickness of described electrically conductive polyaniline/Graphene rete 3 is about 0.035mm, the thickness of described polar oxygenated rete is about 10nm, and the thickness of described corrosion resistant 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, obtained electrolyte, stand for standby use, H in described electrolyte
2sO
4concentration be 0.5molL
-1, the concentration of aniline monomer is 0.3molL
-1, the mass fraction of carboxylated Graphene is 6%;
(2) the conductive doped polymer film of corrosion resistant plate surface electrochemistry synthesizing graphite alkene after the pre-treatment: electrochemistry formated experiment is carried out in the three-electrode system of routine, chronoamperometry is adopted in electrolytic cell, described metallic plate is put into the described obtained electrolyte of step (1), with pretreated corrosion resistant plate for work electrode, platinum plate electrode is auxiliary electrode, saturated calomel electrode is reference electrode, gated sweep voltage range is-0.2 ~ 1.3V, time is 300s, grapheme/polyaniline composite material electrochemistry formated is deposited to simultaneously the polar oxygenated film surface on stainless steel electrode, then the baking oven metallic plate depositing graphene/polyaniline composite film being put into 125 DEG C is heating and curing 6h, the obtained conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of described Graphene.
The stainless steel substrates that above-mentioned obtained Graphene doped conductive polyaniline is modified simulation Proton Exchange Membrane Fuel Cells (PEMFC) cathode environment (80 DEG C, corrosive liquid 0.01mol/LNa
2sO
4+ 0.01mol/LHCl solution, passes into H continuously
2put into sample after two hours) under corrosion resistance and electric conductivity test, test result shows, polyaniline/graphene film has remarkable result for enhancing 316L stainless steel corrosion resistance, and blank stainless corrosion current density is 1.0581*10
-4amp/cm
2, be 1.0213*10 through the corrosion current density of the bipolar plate of stainless steel of the film modified mistake of graphene/polyaniline
-6amp/cm
2, the corrosion current density of the stainless steel steel disc that Graphene doped conductive polyaniline is modified have dropped two orders of magnitude, and corrosion resistance improves, and contact resistance can be reduced to 38m Ω cm
2, current collection efficiency detail improves.By contrasting with independent electrochemical deposition polyaniline, its inhibition efficiency rises about 30% ~ 40% relative to the stainless steel steel disc of Polyaniline-modified, and the stainless steel not doing any modification relative to surface rises about 55%.Contact resistance is from the 732m Ω cm of former stainless steel substrate
2, to the 356m Ω cm of independent Polyaniline-modified
2again up till now with the 38m Ω cm that Graphene doped conductive polyaniline is modified
2.
Claims (9)
1. the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene, it is characterized in that: the conducting polymer rete that described bipolar plates is adulterated by metallic plate, polar oxygenated rete, Graphene forms, described polar oxygenated rete covers metal sheet surface, the conducting polymer rete of described Graphene doping covers polar oxygenated film surface, the thickness of the conducting polymer rete of described Graphene doping is 0.005 ~ 0.3mm, the thickness of described polar oxygenated rete is 5 ~ 30nm, and the thickness of described metallic plate is 0.1 ~ 2mm.
2. the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 1, is characterized in that: described conducting polymer is polyaniline or polypyrrole.
3. the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 1, is characterized in that: described metallic plate is corrosion resistant plate or copper coin.
4. a preparation method for the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of the Graphene according to any one of claims 1 to 3, is characterized in that: described method comprises the steps:
(1) electrolyte is prepared: by the dispersion of conducting polymer monomer, carboxylated Graphene and inorganic acid in deionized water, then ultrasonic disperse is even while stirring, obtained electrolyte, stand for standby use, in described electrolyte, the concentration of inorganic acid is 0.1 ~ 1mol/L, the concentration of conducting polymer monomer is 0.05 ~ 1mol/L, and the mass fraction of carboxylated Graphene is 1 ~ 10%;
(2) metallic plate preliminary treatment: choose the metallic plate that thickness is 0.1 ~ 2, the sand paper of different size is utilized to polish to metallic plate successively, then the oxidation solution put into after cleaning up with acetone containing nitric acid and hydrogen peroxide carries out normal temperature oxidation process 3 ~ 10 minutes, metal sheet surface is made to form polar oxygenated rete, clean with deionized water rinsing again, dry up rear for subsequent use;
(3) the conductive doped polymer film of metal sheet surface electrochemistry formated Graphene after the pre-treatment: adopt three-electrode system, electrochemical method for synthesizing is utilized in electrolytic cell, described metallic plate is put into the described obtained electrolyte of step (1), take metallic plate as work electrode, platinum electrode is auxiliary electrode, saturated calomel electrode is reference electrode, in the conducting polymer rete of the polar oxygenated film surface chemical synthesis deposited graphite alkene doping simultaneously of the described pretreated metallic plate of step (2), then the metallic plate depositing conducting polymer rete is put into baking oven to be heating and curing, the obtained conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of described Graphene.
5. the preparation method of the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 4, is characterized in that: electrochemistry formated technology described in step (3) can for any one electrochemical method in potentiostatic method, chronoamperometry or cyclic voltammetry.
6. the preparation method of the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 5, it is characterized in that: described in step (3), electrochemical method for synthesizing is chronoamperometry, concrete sedimentary condition is: voltage range is-0.2 ~ 1.3V, and the time is 60 ~ 600s.
7. the preparation method of the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 4, it is characterized in that: in oxidation solution described in step (2), the concentration of nitric acid is 5 ~ 10%, the concentration of described hydrogen peroxide is 3 ~ 5%.
8. the preparation method of the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 4, is characterized in that: the carboxylated Graphene described in step (1) be by graphene powder under 70 ~ 100 DEG C of conditions through strong acid solution acidifying, then dilute, filter after obtained.
9. the preparation method of the conductive doped polymer-modified dual polar plates of proton exchange membrane fuel cell of Graphene according to claim 4, it is characterized in that: described in step (3), the temperature of baking oven is 120 ~ 160 DEG C, curing time is 1 ~ 6h.
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| CN201510937054.5A CN105552399B (en) | 2015-12-15 | 2015-12-15 | A kind of graphene adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell and preparation method thereof |
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| CN107634238A (en) * | 2017-08-29 | 2018-01-26 | 国网电力科学研究院武汉南瑞有限责任公司 | A kind of bipolar plates and its manufacture method with higher-strength |
| CN108199058A (en) * | 2017-12-15 | 2018-06-22 | 中国第汽车股份有限公司 | A kind of preparation method of conducting polymer-graphene composite dual-electrode plates |
| CN108832152A (en) * | 2018-06-26 | 2018-11-16 | 李荣旭 | A kind of band coating proton exchange membrane fuel cell metal flow-field plate |
| CN108832153A (en) * | 2018-06-26 | 2018-11-16 | 李荣旭 | The flow-field plate of one proton exchanging film fuel battery |
| 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 |
| CN110875483A (en) * | 2018-09-04 | 2020-03-10 | 大连融科储能装备有限公司 | Integrated electrode-bipolar plate structure and preparation method |
| CN111822024A (en) * | 2019-04-18 | 2020-10-27 | 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 |
| 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 |
| CN115433914A (en) * | 2022-11-07 | 2022-12-06 | 江苏金亚隆科技有限公司 | Preparation process of high-temperature-resistant and antioxidant graphite product coating |
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| CN111822024A (en) * | 2019-04-18 | 2020-10-27 | 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 |
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