CN1770521A - Method for modifying proton exchange membrane fuel cell metal dual-polarity board - Google Patents
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Abstract
This invention relates to one photon exchange film fuel battery process technique and in detail to one improvement method on the double electrode board, which Adopts three electrode system and integrates into modified electrode board by the electrochemical technique on the metal surface polymer to make the polymer single is ofaniline or thiofuran or pyrrole. The modification process comprises the following steps: putting the metal board into the liquid of oxalic acid, dipping acid or Fraude's reagent and polymer single liquid; using metal board as work electrode and carbon board as couple electrode and saturated calomel electrode as reference electrode. The invention modifies the metal board to realize the metal double board functions of anti-erosion.
Description
Technical Field
The invention relates to a preparation technology of a proton exchange membrane fuel cell bipolar plate, in particular to a method for modifying a proton exchange membrane fuel cell metal bipolar plate.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are fuel cells in which a perfluorosulfonic acid-type solid polymer is used as an electrolyte, hydrogen or purified reformed gas is used as a fuel, and air or oxygen is used as an oxidant, and the electrode reaction is similar to that of other acid electrolyte fuel cells. The reaction of hydrogen at the anode under the action of the catalyst is as follows: the electrons generated by the electrode reaction reach the cathode through an external circuit, the hydrogen ions reach the cathode through the electrolyte membrane, and the oxygen, the hydrogen ions and the electrons react at the cathode to generate water: 1/2O2+2H++2e-→H2The water produced by O is mostly present in liquid form and is usually discharged via the tail gas.
The PEMFC has the general characteristics of a fuel cell, such as high energy conversion efficiency, environmental friendliness, rapid start at room temperature, no electrolyte loss, long service life, high specific power and specific energy, and the like. Therefore, it can be used not only for building decentralized power stations, but also as a mobilepower source, and it is the best domestic power source in the future hydrogen energy era with hydrogen as the main energy carrier.
Bipolar plates are one of the key components of a fuel cell and typically include a plate and a flow field. The main functions of the polar plate in the fuel cell are: a) collects current and must therefore be a good conductor of electricity; b) the implementation of the scheme of ensuring the uniform temperature distribution of the battery and heat removal needs to be a good heat conductor; c) the surface resistance is low, and the internal resistance of the battery is reduced; d) the material has certain mechanical strength and rigidity, and does not creep under the battery operation environment; e) the fuel and the oxidant are non-permeable and can separate the oxidant from the reductant; f) corrosion resistance in the electrochemical environment of the cell; g) low density to improve the power density of the battery, etc. The flow field is used for uniformly distributing fuel and oxidant, so that the current density is uniformly distributed, local overheating is avoided, and reaction tail gas can be discharged out of the battery to generate water.
In PEMFCs, bipolar plates occupy not only a major portion of volume and weight, but also a significant proportion of production cost, and are one of the key components that hinder the commercialization of proton exchange membrane fuel cells. The bipolar plates can be classified into carbon plates and metal plates, and the carbon plates can be further classified into pure graphite bipolar plates, die-cast bipolar plates and expanded graphite bipolar plates. The pure graphite bipolar plate is prepared by mixing graphite powder, crushed coke and graphitizable resin or asphalt, heating to 2700-2500 ℃ in a graphitization furnace according to a certain temperature rise program strictly, preparing graphite blocks with no holes or low porosity (less than 1percent and only containing nano-scale holes), cutting and grinding to prepare graphite plates with the thickness of 2-5 mm, machining a common pore channel and engraving a required flow field on the surface of the graphite plates by using a computer engraving machine.
The bipolar plate is prepared by mixing graphite powder with thermoplastic resin (such as Vinylester), optionally adding catalyst, retarder, release agent and reinforcing agent (such as carbon fiber), and press molding at a certain temperature under a pressure of tens to hundreds of atmospheres. Because the resin does not realize graphitization, the phase resistance of the die-cast bipolar plate and the contact resistance with the electrode diffusion layer are higher than those of the graphite bipolar plate.
The expanded graphite bipolar plate is prepared by using expanded graphite through a stamping or rolling embossing method. Gibb, R, Peter (european patent No.: WO 00/41260) also made bipolar plates from specially treated flexible graphite.
The thin-layer metal plate not only has enough mechanical strength, but also is easy to machine and form and mass production, and is the most potential carbon plate replacement material. However, untreated metal plates are susceptible to corrosion in the cell environment, and metal ions formed by corrosion are deposited in the proton exchange membrane, which reduces the proton permeability and seriously affects the cell performance, so the metal plates must be modified. Fronk Matthey Howard et al (U.S. Pat. No. US 6372376) have proposed a method of coating a composite conductive layer (carbon or conductive polymer + water-insoluble polymer) on an aluminum or titanium substrate, which, although convenient to operate, does not solve the problem of stress concentration of the composite conductive layer after increasing the conductivity. Another patent reports a modification method of covering both sides of aluminumwith a conductive polymer, and mechanical treatment must be performed on the surface of aluminum in order to enhance the bonding force between the substrate and the conductive polymer. Wangyuxin et al (GB01144972) disclose a method of sandwiching a metal sheet or a polypyrrole or polyaniline network layer between graphite worm layers, which is characterized by electropolymerizing polyaniline or polypyrrole in the middle gap after placing a metal sheet in two layers of graphite worms and then pressure forming or pressure forming the graphite worms. Since the overall structure of the plate is a graphite worm, there is a problem in mechanical strength. Lishucheng et al (Chinese patent No. GB02155187) invented a modification method for coating a conductive oxide on a metal surface. Zeng XianXilin et al (Chinese patent No. GB01118343.8) proposed a method for making an injection molded resin surface coated with nickel, titanium, gold, etc.
In conclusion, the carbon plate has great brittleness, poor mechanical strength and expensive processing cost, so that the large-scale commercial application of the carbon plate has great difficulty. The aluminum plate is particularly active and extremely easy to corrode in the PEMFC environment, no suitable modification method exists so far, the internal resistance of the titanium plate is remarkably increased by the oxidation film of the titanium plate, the titanium plate is usually a precious metal such as electroplated gold, and the processing cost is not easy to accept during batch production. Thin stainless steel plates, which are easy to machine and mass produce, are the most promising replacement materials for plates, but thin metal plates also present corrosion problems in the PEMFC environment. From published literature at home and abroad, research on bipolar plates has focused on modifying metal plates which are easy to mass produce and low in price. Therefore, the development of a novel modification method which canimprove the corrosion resistance of the metal plate in the battery environment and does not influence the electrical property of the metal plate is very necessary for reducing the cost of the bipolar plate and prolonging the service life of the bipolar plate, and has important practical significance for the commercialization process of the proton exchange membrane fuel cell.
Disclosure of Invention
The invention aims to provide a simple and feasible method for modifying a metal bipolar plate of a proton exchange membrane fuel cell by combining with special requirements of the fuel cell on the bipolar plate.
The technical scheme of the invention is as follows: adopting a three-electrode system, electropolymerizing a conductive polymer film on the surface of a metal plate by using an electrochemical synthesis technology (such as constant potential, constant current, cyclic voltammetry, pulse or step) in an electrolytic cell to synthesize a modified polar plate, wherein the used conductive polymer monomer can be aniline, pyrrole or thiophene; the modification process comprises the following steps: putting a metal plate into a solution of oxalic acid, sulfuric acid or perchloric acid and a conductive polymer monomer which are pre-filled with nitrogen, and depositing a conductive polymer by taking the metal plate as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode;
the concentration of the oxalic acid solution is 0.01-0.8 mol/L, the concentration of the sulfuric acid solution is 0.01-3 mol/L, the concentration of the perchloric acid solution is 0.01-1 mol/L, and the concentration of the conductive polymer monomer solution is 0.1-2.0 mol/L;
the conditions for polymerizing the conductive polymer by pulse polymerization were: the potential of the cathodic pulse is-600 mV to-200 mV, the pulse time is 1s to 300s, the potential of the anodic pulse is 700mV to 1200mV, the pulse time is 1s to 300s, and the continuous pulse frequency can be changed between 1 to 15 times; the conditions for polymerizing the conductive polymer using cyclic voltammetry scanning were: the scanning interval is-600 mV- + 200mV- +800 mV- +1200mV, the scanning speed is 10 mV/s-100 mV/s, and the number of scanning cycles is 5-50 circles;
surfactant can be added in the electropolymerization process to synthesize doped conductive polymer; the surfactant is dodecyl benzene sulfonic acid or sodium dodecyl sulfonate;
the metal plate is made of a common stainless steel plate such as 304, 316L, 2Cr13, 4Cr13 or 1Cr18Ni9Ti stainless steel.
The invention has the following beneficial effects:
1. the thin-layer metal bipolar plate modified by the conductive polymer can improve the corrosion potential of the thin-layer metal bipolar plate by 600mV under the environment of a simulated battery anode without influencing the performance of the battery, and the corrosion resistance is obviously improved.
2. The invention only deposits the conductive polymer protective film on the surface of the metal plate, and the main body of the polar plate is still a stainless steel plate, so the polar plate still has enough mechanical strength.
3. The invention utilizes electrochemical synthesis technology, electropolymerization conductive polymer modifies stainless steel bipolar plate, and directly synthesizes conductive polymer on metal plate, the preparation process is simple, the processing cost is low, and the invention has important practical significance for reducing the production cost of proton exchange membrane fuel cell bipolar plate and acceleratingthe commercialization process thereof.
4. The conductive polymer film of the invention has no pollution to proton exchange membranes.
5. Has wide application prospect. The conductive polymer film is directly synthesized on the surface of the thin-layer metal plate by an electrochemical method, so that the corrosion resistance of the thin-layer metal plate can be obviously improved, the performance of the battery is not influenced, the mass production can be realized, and the conductive polymer film has wide application prospect for fuel batteries which are about to enter a commercial market. The invention is suitable for surface modification of thin-layer metal bipolar plates for low-temperature fuel cells, in particular to surface modification of thin-layer stainless steel bipolar plates for proton exchange membrane fuel cells.
Drawings
FIG. 1 is a schematic diagram of a modified thin-layer metal plate structure.
Fig. 2 is an anodic polarization curve of untreated and polyaniline-modified 1Cr18Ni9Ti in a simulated anodic environment.
Fig. 3 is a polarization curve of untreated and polyaniline-modified 1Cr18Ni9Ti cells.
FIG. 4 illustrates the continuous H-flow of a stainless steel material made of 304 stainless steel according to the conventional and inventive techniques20.01mol/L Na at 80 DEG C2SO4Polarization curve in +0.01mol/L HCl solution.
Detailed Description
Example 1
Taking 1Cr18Ni9Ti stainless steel, polishing, washing with water, washing with alcohol, degreasing and dryingPutting the polyaniline into 0.01mol/L oxalic acid +0.1mol/L aniline solution which is pre-filled with 30 minutes of nitrogen, adopting a pulse mode, taking stainless steel as a working electrode, a carbon plate as a counter electrode, a saturated calomel electrode as a reference electrode, and pulse polymerizing the polyaniline (the potential of a cathode pulse is-200 mV, the pulse time is 10s, the pulse potential of an anode is 1200mV, the pulse time is 10s, and the continuous pulse frequency can be 15 times). The cross section structure of the modified pole plate is shown in figure 1, the inner layer is a thin metal plate, the outer layer is conductive polymer, and the thickness is controlled by using polymerization time and is between several micrometers and hundreds of micrometers. The modified polar plate is in the environment of the anode of the simulated battery (the temperature is 80 ℃, and the corrosive liquid is 0.01mol/L Na)2SO4+0.01mol/L HCl solution, continuously feeding H2Put into the pattern after two hours) is shown in fig. 2. After polyaniline modification, the corrosion potential of the 1Cr18Ni9Ti in the corrosive liquid is increased from-350 mV in blank to 250mV, and the corrosion resistance is obviously improved.
In fig. 1: 1 is a thin metal plate and 2 is a conductive polymer layer.
For polyaniline modified 1Cr18Ni9Ti 5cm2Battery plate, measured with H2-O2Is burnedThe Pt content of the MEA was 0.7mg/cm2Polarization curves for 50% oxygen utilization, and compared to polarization curves for untreated plates, as shown in figure 3. The polymer film has no influence on the battery performance.
Example 2
The difference from the embodiment 1 is that:
taking a 304 stainless steel plate, polishing, washing with water, washing withalcohol, degreasing, drying, putting into a 3mol/L sulfuric acid and 2.0mol/L aniline solution which is pre-filled with 30 minutes of nitrogen, taking stainless steel as a working electrode, a carbon plate as a counter electrode, and a saturated calomel electrode as a reference electrode, and carrying out cyclic voltammetry scanning polymerization of polyaniline (the scanning interval is-600 mV- +800mV, the scanning speed is 10mV/s, and the number of scanning cycles is 50 circles).
As a result: the corrosion potential of the polyaniline modified 304 stainless steel in simulated corrosive liquid is improved by nearly 600mV, the passivation current density is reduced, and the corrosion resistance is also improved obviously (see figure 4).
Example 3
The difference from the embodiment 2 is that:
putting into 0.01mol/L perchloric acid and 0.15mol/L aniline solution which are pre-filled with nitrogen, taking stainless steel as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode, and carrying out cyclic voltammetry scanning on polyaniline (the scanning interval is-300 mV- +1200mV, the scanning speed is 100mV/s, and the number of scanning turns is 5 circles).
Example 4
The difference from the embodiment 2 is that:
putting into 0.01mol/L sulfuric acid and 0.1mol/L aniline solution which are pre-filled with nitrogen, taking 4Cr13 stainless steel as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode, and carrying out cyclic voltammetry scanning on polymeric polyaniline (the scanning interval is-200 mV- +1200mV, the scanning speed is 100mV/s, and the number of scanning cycles is 5 circles).
Example 5
The difference from the embodiment 2 is that:
putting the polyaniline into a 1mol/L sulfuric acid and 0.15mol/L aniline solution which is pre-filled with nitrogen, taking 4Cr13 stainless steel as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode, and carrying out cyclic voltammetry scanning on the polyaniline (the scanning interval is-400 mV- +1000mV, the scanning speed is 50mV/s, and the number of scanning cycles is 30 cycles).
Example 6
The difference from the embodiment 1 is that:
taking 316 or 316L stainless steel, polishing, washing with water, washing with alcohol, degreasing, drying, putting into 1mol/L perchloric acid and 2mol/L aniline solution which are pre-filled with 30 minutes of nitrogen, taking the stainless steel as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode, and sequentially pulse-polymerizing polyaniline (the potential of a cathode pulse is-600 mV, the pulse time is 150s, the potential of an anode pulse is 800mV, the pulse time is 150s, and the continuous pulse frequency can be 7 times) to obtain the modified polar plate.
Example 7
The difference from the embodiment 1 is that:
taking 4Cr13 stainless steel, polishing, washing with water, washing with alcohol, degreasing and drying, putting into 0.8mol/L oxalic acid and 0.1mol/L aniline solution which are pre-filled with 30 minutes of nitrogen, taking the stainless steel as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode, and sequentially pulse-polymerizing polyaniline (the potential of a cathode pulse is-400 mV, the pulse time is 300s, the potential of an anode pulse is 700mV, the pulse time is 300s, and the continuous pulse frequency can be 2 times) to obtain the modified polar plate.
The invention can also adopt a constant potential, constant current or step mode; surfactant can be added in the electropolymerization process to synthesize doped conductive polymer (dodecyl benzene sulfonic acid or dodecyl sodium sulfonate); in addition, the conductive polymer film synthesized on the surface of the metallic stainless steel may be a single layer, a double layer or a multi-layer. The conductive polymer monomer used may also be pyrrole or thiophene.
Comparative example 1
GB Patent 01144972 is a processing method for attaching a metal sheet or polypyrrole or polyaniline network layer between graphite worm layers, and the method is characterized in that polyaniline or polypyrrole is electropolymerized in a middle gap after a metal sheet is placed in two layers of graphite worms and then pressure forming is carried out or after the pressure forming of the graphite worms is carried out. Since the overall structure of the plate is a graphite worm, there is a problem in mechanical strength.
Comparative example 2
US 5527363 is a pure graphite bipolar plate with a flow field, which has good electrical and thermal conductivity, but the electrical and thermal conductivity of graphite is reduced due to multiple pore filling, and the processing cost is too high.
Comparative example 3
The flexible graphite bipolar plate of WO 00/41260 also suffers from excessive tooling costs.
Comparative example 4
GB01118343.8 proposes a method for producing an injection molded resin coated with nickel, titanium, gold, or the like. The metal of the outer layer is easy to corrode and pollute the proton exchange membrane.
Claims (8)
1. A method for modifying a metal bipolar plate of a proton exchange membrane fuel cell is characterized by comprising the following steps: adopting a three-electrode system, electropolymerizing a conductive polymer film on the surface of a metal plate in an electrolytic cell by utilizing an electrochemical synthesis technology to synthesize a modified polar plate; the modification process comprises the following steps: putting the metal plate into a monomer solution of oxalic acid, sulfuric acid or perchloric acid and a conductive polymer, which is pre-filled with nitrogen, and polymerizing the conductive polymer by taking the metal plate as a working electrode, a carbon plate as a counter electrode and a saturated calomel electrode as a reference electrode.
2. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 1, wherein: the conductive polymer monomer used may be aniline, pyrrole or thiophene.
3. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 1, wherein: the concentration of the oxalic acid solution is 0.01-0.8 mol/L, the concentration of the sulfuric acid solution is 0.01-3 mol/L, the concentration of the perchloric acid solution is 0.01-1 mol/L: the concentration of the conductive polymer monomer is 0.1-2.0 mol/L.
4. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 1, wherein: the conditions for polymerizing the conductive polymer by pulse polymerization were: the potential of the cathodic pulse is-600 mV to-200 mV, the pulse time is 1s to 300s, the potential of the anodic pulse is 700mV to 1200mV, the pulse time is 1s to 300s, and the continuous pulse frequency can be changed between 1 to 15 times.
5. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 1, wherein: the conditions for polymerizing the conductive polymer using cyclic voltammetry scanning were: the scanning interval is-600 mV- + 200mV- +800 mV- +1200mV, the scanning speed is 10 mV/s-100 mV/s, and the number of scanning turns is 5-50 turns.
6. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 1, wherein: a surfactant may be added during the electropolymerization to synthesize a doped conductive polymer.
7. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 6, wherein: the surfactant is dodecyl benzene sulfonic acid or sodium dodecyl sulfonate.
8. The method for modifying the metal bipolar plate of the proton exchange membrane fuel cell as recited in claim 1, wherein: the metal plate was a common stainless steel plate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020845A (en) * | 2010-11-25 | 2011-04-20 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| CN103695979A (en) * | 2013-12-02 | 2014-04-02 | 常州大学 | Novel magnesium alloy surface treatment method |
| 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 |
| CN114318455A (en) * | 2022-03-10 | 2022-04-12 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372376B1 (en) * | 1999-12-07 | 2002-04-16 | General Motors Corporation | Corrosion resistant PEM fuel cell |
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2004
- 2004-11-03 CN CNB2004100827260A patent/CN100353598C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020845A (en) * | 2010-11-25 | 2011-04-20 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| CN102020845B (en) * | 2010-11-25 | 2012-05-23 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| CN103695979A (en) * | 2013-12-02 | 2014-04-02 | 常州大学 | Novel magnesium alloy surface treatment method |
| CN103695979B (en) * | 2013-12-02 | 2016-08-17 | 常州大学 | A kind of method that Mg alloy surface processes |
| 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 |
| CN114318455A (en) * | 2022-03-10 | 2022-04-12 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
| CN114318455B (en) * | 2022-03-10 | 2022-06-17 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
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