CN102569842A - Preparation method of hybrid ordered mesoporous carbon coat for protecting stainless steel bipolar plate of proton exchange membrane fuel cell - Google Patents

Preparation method of hybrid ordered mesoporous carbon coat for protecting stainless steel bipolar plate of proton exchange membrane fuel cell Download PDF

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CN102569842A
CN102569842A CN2012100109397A CN201210010939A CN102569842A CN 102569842 A CN102569842 A CN 102569842A CN 2012100109397 A CN2012100109397 A CN 2012100109397A CN 201210010939 A CN201210010939 A CN 201210010939A CN 102569842 A CN102569842 A CN 102569842A
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stainless steel
coating
solution
mesoporous carbon
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CN102569842B (en
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何建平
王涛
张晓雪
孙新
刘明珠
薛海荣
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Nanjing University of Aeronautics and Astronautics
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Abstract

The invention relates to a preparation method of hybrid ordered mesoporous carbon coat for protecting a stainless steel bipolar plate of a proton exchange membrane fuel cell, which comprises the following steps that: a surface active agent is dissolved in absolute ethyl alcohol to be blended, then ethanol solution of phenolic resin is dropped to be uniformly blended, ethanol solution of boric acid or phosphoric acid is added to be blended to obtain light yellow transparent sol-gel, the sol-gel is gradually dropped onto a stainless steel sheet to perform dropping and homogenizing treatment; then the stainless steel sheet solvent which is coated with the solution is evaporated for at least 8 hours and is thermally polymerized for at least 24 hours under the temperature of 70 to 120 DEG C, so a light yellow coat is formed on the surface of the stainless steel; and finally a black ordered mesoporous carbon coat or carbon-boron coat or a carbon-phosphorus coat is obtained after being carbonized at the nitrogen atmosphere. Due to the adoption of the preparation method, heteroatom is directly doped into a precursor of the carbon to obtain heteroatom which is uniformly distributed so as to maintain the ordered mesoporous structure, at the same time the electric conductivity and the hydrophobic property of the mesoporous carbon coat on the 304-type stainless steel matrix can be improved, and the corrosion resistance of the mesoporous carbon coat in the sulfuric acid solution can be improved.

Description

A kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection
Technical field
The present invention relates to a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection, belong to bipolar plate of stainless steel protective coating preparing technical field.
Background technology
Bipolar plates is the important component part of Proton Exchange Membrane Fuel Cells, account for total weight nearly 80% and total cost 50%.Can must have high conductivity, high corrosion-resistant, excellent mechanical intensity, low-permeable and lower-price characteristic as the material of bipolar plates.In recent years, current research shows because stainless steel in the advantage of aspects such as mechanical strength, corrosion resistance, hardness, surface finish and cleaning, has become the optimal selection of metal double polar plates.But; Some problems that stainless steel still exists as bipolar plates, a main difficult problem are that metal double polar plates can form one deck passivating film on the surface after the medium-term and long-term work of corrosive medium; Prevent that metal from further corroding; But this layer passivating film makes surface contacted resistance increase, and along with the growth of operating time, passivation layer can be more and more thicker.Another problem is under weakly acidic condition, to have SO 4 2, Cl , F Plasma makes stainless steel in use can be corroded and dissolve, to such an extent as to the polluted membrane electrode.The passivation of metal and solubility behavior can make the part electric energy be converted into thermal dissipation undoubtedly and influence the gross efficiency of fuel cell.Various coatings are used as the protection metal double polar plates, for example carbon coating and metal coating.The stainless steel that carbon film applies because cheap, volume is little, is considered to the good material as the bipolar plates of proton membrane fuel battery.Many researchs show, when on the metal double polar plates of having removed fully at passivating film during the coated carbon coating, interface contact resistance obviously reduces [Tomokazu Fukutsuka; Takayuki Yamaguchi; Shin-Ichi Miyano, Yoshiaki Matsuo, Yosohiro Sugie; Zempachi Ogumi, Journal of Power Sources 174 (2007) 199 – 205].
Therefore, various material with carbon elements, like graphite, conducting polymer, diamond-like-carbon and organic self-assembled material, be used as bipolar plates carbon coating and by broad research.Fukutsuka representes through plasma auxiliary CVD method [T. Fukutsuka, T. Yamaguchi, S.I. Miyano; Y. Matsuo; Y. Sugie, Z. Ogumi, J. Power Sources 1 (2007) 199-205.] generate carbon film on stainless steel (304SS) surface; With compare and have high conductivity before the deposition; And between carbon-coating and 304SS, do not form passivating film, but under the Proton Exchange Membrane Fuel Cells condition of work, the 304SS of depositing carbon film presents stronger polarization phenomena.Chung [C.Y. Chung, S.K. Chen, P.J. Chiu; M.H. Chang; T.T. Hung, T.H. Ko, J. Power Sources 1 (2008) 276-281.] etc. system research the corrosion behavior of carbon coating 304SS as the proton membrane fuel battery bipolar plates; Find that carbon film shows the chemical stability similar with graphite electrode, 304SS is protected in the corrosive environment of proton membrane fuel battery.[Kai Feng, Xun Cai, Hailin Sun such as Feng; Zhuguo Li, Paul K. Chu, Diamond & Related Materials 19 (2010) 1354-1361. Kai Feng; Yao Shen, Hailin Sun, Dongan Liu; Quanzhang An, Xun Cai; Paul K. Chu, i n t e r n a t i o n a l j o u rna l o f hydrogen energy 34 (2 00 9) 6771 – 6777] apply fine and close, continuous, unbodied carbon film through non-balance magnetically controlled sputter at 316L stainless steel sample surfaces, its performance is superior to traditional graphite bi-polar plate.The hydrophobicity of this carbon film and interface contact resistance all are superior to graphite, and because it has chemical inertness well, have significantly strengthened the stainless corrosion resistance of coating 316L.
A kind of new method is on stainless steel substrate, to form the mesoporous carbon film through spin-coating method, and the carbon back composite membrane shows best barrier propterty, and its corresponding potential polarization process is highly stable under the fuel cell environment of simulation.[T. Wang, J.P. He, D. Sun, J.H. Zhou; Y.X. Guo, X.C. Ding, S.C. Wu; J.Q. Zhao, J. Tang, Corrosion Science 53 (2011) 1498-1504.] though the mesoporous carbon film have many good qualities; Like the favorable protection performance, but because the existence of a large amount of silicon dioxide needs further to improve electrical conductance.Many researchs show, in material with carbon element, mix power supply or electrophilic element, and N for example, P, B can change the electric property of carbon film, and forms the additional function group on the carbon film surface.Most ordered mesoporous carbon materials are that the method is very simple through other atoms of reprocessing doping, but all bad control aspect content and dopant profiles makes order mesoporous structure division or thorough destruction, and this is very serious deficiency in application.
Summary of the invention
Technical problem:In order to address the above problem, it is simple and have a preparation method of the hybrid ordered mesoporous carbon coating of excellent anticorrosive performance to the objective of the invention is to propose a kind of technology.
Technical scheme:1, a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection is characterized in that comprising following steps:
(1), surfactant is dissolved in the absolute ethyl alcohol solution that stirring formation is transparent; Drip the ethanolic solution of phenolic resins then, stir, subsequent use;
(2), 0.6 mol/L HCl solution is joined in the absolute ethyl alcohol, regulate pH3 ~ 5, add boric acid or phosphoric acid again, stir and obtain solution; Subsequent use;
(3), solution that step (2) is obtained dropwise joins in the solution that step (1) obtains, the boric acid that every 1g surfactant is corresponding or the addition scope of phosphoric acid are 0.02 ~ 0.16 g, stir it is mixed, and obtain yellowish transparent sol-gel;
(4), with the sol-gel that step (1) or (3) prepare, dropwise drip on stainless steel substrates, drip glue and even glue and handle;
(5), the stainless steel substrates that is coated with solution that step (4) is obtained is at 25 ℃ of following solvent evaporation at least 8 h, at 70～120 ℃ of thermal polymerization at least 24 h, forms faint yellow coating at stainless steel surfaces then; Obtain ordered mesopore carbon-boron coating or the carbon-phosphor coating or the carbon coating of black at last in the nitrogen atmosphere carbonization.
Surfactant is polyoxyethylene/polyoxypropylene/polyoxyethylene amphiphilic block copolymer F127 in the said step (1), and molecular formula is PEO 106-PPO 70-PEO 106
Per 1 g surfactant is dissolved in the 15mL absolute ethyl alcohol in the described step (1), and the mass fraction of the ethanolic solution of phenolic resins is 20%.
In the described step (4), dripping glue speed is 400 ~ 800 rpm, drips glue times 10 ~ 20 s, and even glue speed selection is 1500 ~ 3000 rpm, and even glue times 45 ~ 60 s repeats to drip glue and even glue process 5 times.
Carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas in the described step (5), and 350 ℃ are incubated 3 ~ 5 h down, and 400 ~ 700 ℃ are incubated 2 h down under the target temperature, and heating rate is strict controlled in 1 ℃/min
The ethanolic solution (phenolic resins mass fraction 20%) of phenolic resins in the step (1), concrete preparation method is: at first, in beaker, take by weighing 6.1 g phenol, slowly be warming up to 40 ~ 42 ℃ and make its fusing; In beaker, slowly drip NaOH (mass fraction 20%) aqueous solution of 1.3 g then, magnetic agitation 10 min make solution even simultaneously; Then, dropwise add 10.5 g formalins (mass fraction 37%), and be warming up to 70 ~ 75 ℃, vigorous stirring 60 min make phenol and formaldehyde polymerization reaction take place; After reaction finishes solution is naturally cooled to room temperature, with the HCl solution of 0.6 mol/L the pH value of solution in the beaker is adjusted to neutrality (7.0) then; The solution that mixes up the pH value is placed vacuum drying chamber, at 45 ℃ of following volatilization moisture, during can see that the NaCl crystal of adularescent separates out; At last, the phenolic resins in the beaker is partially dissolved in the absolute ethyl alcohol, and to be made into mass fraction be 20% phenolic resins ethanolic solution, subsequent use.
Beneficial effect:The present invention directly is doped to hetero-atom in the precursor of carbon; Obtain equally distributed hetero-atom; Keeping orderly meso-hole structure, simultaneously improve the conductivity and the hydrophobicity of the mesoporous carbon coating on the stainless steel base, with and corrosion resistance in sulfuric acid solution.
Description of drawings
Fig. 1 is order mesoporous CB-x-500 coating XRD figure spectrum,
Wherein Fig. 1 a is the little angle XRD figure spectrum of order mesoporous CB-x-500 coating, can know along with the boric acid consumption increases, 0.8 from collection of illustrative plates oLittle angle, position XRD diffraction maximum reduces gradually, means the reduction of the CB-x-500 coating degree of order, explains that the addition of boric acid more helps the maintenance of order mesoporous structure at 0.2-0.8;
Fig. 1 b is a CB-x-500 coating big angle XRD figure spectrum;
Fig. 2 is the XRD figure spectrum of order mesoporous CB-0.08-y coating,
Wherein: Fig. 2 a is the little angle XRD figure spectrum of order mesoporous CB-0.08-y coating, and Fig. 2 b is the big angle XRD figure spectrum of order mesoporous CB-0.08-y coating; It is intact to find out that from Fig. 2 a the degree of order of coating all keeps;
Fig. 3 is the XRD figure spectrum of order mesoporous CP-0.06-500 coating,
Wherein: Fig. 3 a is the little angle XRD figure spectrum of order mesoporous CP-0.06-500 coating, and Fig. 3 b is the big angle XRD figure spectrum of order mesoporous CP-0.06-500 coating;
Fig. 4 is the TEM figure of order mesoporous CB-x-500 coating: (a, b) CB-0-500; (c, d) CB-0.02-500; (e, f) CB-0.04-500; (g, h) CB-0.08-500; (i, j) CB-0.16-500; Wherein the illustration among Fig. 4 h is the CB-0.08-500 electron diffraction diagram, explains that this coating mainly is that amorphous carbon is main;
Fig. 5 is the TEM figure of order mesoporous CB-0.08-y coating: (a, b) CB-0.08-400; (c, d) CB-0.08-500; (e, f) CB-0.08-600; (g, h) CB-0.08-700;
Fig. 6 is the N of orderly CB-x-500 coating 2Adsorption desorption isothermal curve and pore size distribution curve,
Wherein: Fig. 6 a is the N of CB-x-500 coating 2Adsorption desorption isothermal curve, Fig. 6 b are the pore size distribution curves of CB-x-500 coating;
Fig. 7 is the N of orderly CB-0.08-y coating 2Adsorption desorption isothermal curve and pore size distribution curve,
Wherein: Fig. 7 a is the N of CB-0.08-y coating 2Adsorption desorption isothermal curve, Fig. 7 b are the pore size distribution curves of CB-0.08-y coating;
Fig. 8 is that orderly CB-x-500 coating is at 0.5 M H 2SO 4Tafel curve under the system; The electrochemical data calculated is listed in the table 2 from figure, can find out that from table the corrosion protection of addition coating between 0.02 ~ 0.08 g of boric acid is relatively good;
Fig. 9 is that orderly CB-0.08-y coating is at 0.5 M H 2SO 4Tafel curve under the system.The electrochemical data of from figure, calculating is listed in the table 2, from table, can find out that the corrosion protection of heat treatment temperature coating between 400 ~ 600 ℃ is relatively good.
Embodiment
The naming method of the coating that following examples obtain is: with the carbon coating product of the formal notation boron-doping of CB-x-y, wherein xExpression adds the quality (g) of boric acid, yRepresent final heat treatment temperature, mix the carbon coating product of phosphorus with the formal notation of CP-x-y, wherein xExpression adds the quality (g) of phosphoric acid, yRepresent final heat treatment temperature, then sample is named like following table among each embodiment:
Embodiment 1:
(1) 1 g polyoxyethylene/polyoxypropylene/polyoxyethylene amphiphilic block copolymer F127 (available from Sigma-Aldrich company) is dissolved in the 15.0 ml absolute ethyl alcohols, stirs 1 h and form transparent solution A; Simultaneously with 1.8 ml HCl solution (0.6 mol/L) join in the 5 ml absolute ethyl alcohols, regulate pH in 3 ~ 5 scopes, slowly add 0.02 g boric acid again, magnetic agitation obtains solution B; Slowly the ethanolic solution (phenolic resins mass fraction 20%) of Dropwise 5 g phenolic resins stirs 10 min in solution A; Dropwise solution B is added in the solution A then, stirs 1 h it is mixed, thereby obtain yellowish transparent carbon-B solution;
Carbon-boron the sol-gel that (2) will on desk-top sol evenning machine, will prepare before dropwise drips on stainless steel substrates, and dripping a glue speed selection is 500 rpm; Drip glue times 10 s; Even glue speed selection is 1500 rpm/s, and even glue times 60 s repeats to drip glue and even glue process 5 times;
The stainless steel substrates that (3) will be coated with solution is transferred in the baking oven, at 25 ℃ of following solvent evaporation 8 h, at 70～120 ℃ of thermal polymerization 24 h, forms faint yellow coating at stainless steel surfaces then;
(4) will apply cated stainless steel substrates and put into porcelain boat, prepare carbonization.Carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas, and 350 ℃ are incubated 3 h down, and target temperature is incubated 2 h down for following 500 ℃, and heating rate is strict controlled in 1 ℃/min;
Obtain the CB-0.02-500 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 4 (c, d)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare the corrosion potential that is coated with the CB-0.02-500 coating about 500 mV that shuffle, the corrosion electric current density one magnitude that descended with 304 type stainless steels of uncoated coating.
Embodiment 2:
Present embodiment is 0.04 g except the boric acid addition, and all the other contents are all with embodiment 1.
Obtain the CB-0.04-500 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 4 (e, f)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare the corrosion potential that is coated with the CB-0.04-500 coating about 500 mV that shuffle, the corrosion electric current density one magnitude that descended with 304 type stainless steels of uncoated coating.
Embodiment 3:
Present embodiment is 0.08 g except the boric acid addition, and all the other contents are all with embodiment 1.
Obtain the CB-0.08-500 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 4 (g, h)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare the corrosion potential that is coated with the CB-0.08-500 coating about 500 mV that shuffle, the corrosion electric current density one magnitude that descended with 304 type stainless steels of uncoated coating.
Embodiment 4:
Present embodiment is 0.16 g except the boric acid addition, and all the other contents are all with embodiment 1.
Obtain the CB-0.16-500 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 4 (i, j)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare with 304 type stainless steels of uncoated coating, the corrosion potential that is coated with the CB-0.16-500 coating about 500 mV that shuffle, corrosion electric current density has descended one times.
Embodiment 5:
Present embodiment is 400 ℃ of insulation 2 h down except target temperature, and all the other contents are all with embodiment 3.
Obtain the CB-0.08-400 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 5 (a, b)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare the corrosion potential that is coated with the CB-0.08-400 coating about 500 mV corrosion electric current densities one magnitude that descended of shuffling with 304 type stainless steels of uncoated coating.
Embodiment 6:
Present embodiment is 600 ℃ of insulation 2 h down except target temperature, and all the other contents are all with embodiment 3.
Obtain the CB-0.08-600 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 5 (e, f)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare the corrosion potential that is coated with the CB-0.08-600 coating about 500 mV that shuffle, the corrosion electric current density one magnitude that descended with 304 type stainless steels of uncoated coating.
Embodiment 7:
Present embodiment is 700 ℃ of insulation 2 h down except target temperature, and all the other contents are all with embodiment 3.
Obtain the CB-0.08-700 coating, high degree of dispersion is in the carbon matrix in carbonisation for the B element, and this has just guaranteed not to be destroyed the order mesoporous structure of coating, and (see Fig. 1 and Fig. 5 (g, h)), the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare with 304 type stainless steels of uncoated coating, the corrosion potential that is coated with the CB-0.08-700 coating about 300 mV that shuffle, corrosion electric current density has descended one times.
Embodiment 8:
(1) 1 g surfactant F127 is dissolved in the 20.0 ml absolute ethyl alcohols, stirs 1 h and form transparent solution A; Slowly the ethanolic solution (phenolic resins mass fraction 20%) of Dropwise 5 g phenolic resins stirs and obtains yellowish transparent carbon solution in solution A;
Carbon sol-the gel that (2) will on desk-top sol evenning machine, will prepare before dropwise drips on stainless steel substrates, and dripping a glue speed selection is 800 rpm/s; Drip glue times 20 s; Even glue speed selection is 3000 rpm/s, and even glue time 45s repeats to drip glue and even glue process 5 times;
The stainless steel substrates that (3) will be coated with solution is transferred in the baking oven, at 25 ℃ of following solvent evaporation 8 h, at 70～120 ℃ of thermal polymerization 24 h, forms faint yellow coating at stainless steel surfaces then;
(4) will apply cated stainless steel substrates and put into porcelain boat, prepare carbonization.Carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas, and 350 ℃ are incubated 5 h down, and target temperature is incubated 2 h down for following 500 ℃, and heating rate is strict controlled in 1 ℃/min;
Obtaining the CB-0-500 coating has the meso-hole structure of high-sequential (see Fig. 1 and Fig. 4 (a, b)), the concrete structure data is seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare the corrosion potential that is coated with the CB-0-500 coating about 300 mV that shuffle, the corrosion electric current density one magnitude that descended with 304 type stainless steels of uncoated coating.
Embodiment 9:
Present embodiment replaces boric acid except additive in the step (1) by phosphoric acid, and addition is outside the 0.06g, and all the other contents are all with embodiment 1.
The CP-0.06-500 coating that obtains has the meso-hole structure (see figure 3) of high-sequential, and the concrete structure data are seen table 1.At 0.5 M H 2SO 4In carry out Tafel test data see table 2, from table 2, can find out, compare with 304 type stainless steels of uncoated coating, the corrosion potential that is coated with the CP-0.06-500 coating about 550 mV that shuffle, corrosion electric current density has descended one times.
Table 1 is by N 2The order mesoporous CB that the adsorption desorption isothermal curve calculates and the pore structure parameter of CP coating
Figure 2012100109397100002DEST_PATH_IMAGE002
From table 1, can see that the order mesoporous carbon coating behind interpolation B or the P has bigger specific area, at 400 ~ 700 m 2Between/the g, and mesoporous ratio is all higher, all more than 78%, and combines Fig. 6 b and Fig. 7 b can know that the pore-size distribution of CB coating is very concentrated.
Table 2 is conductivity of sample, contact angle, and at 0.5 M H 2SO 4In carry out the corrosion potential of Tafel test and from corrosion electric current density
Figure 2012100109397100002DEST_PATH_IMAGE003
From table 2, can see all corresponding increase of conductivity of adding the order mesoporous carbon coating behind B or the P, and addition is big more, conductivity and contact angle increase many more with contact angle.But characterizing the addition that can release boric acid through corrosion protection should be between 0.02 ~ 0.08 g, and heat treatment temperature is preferably between 400 ~ 600 ℃.

Claims (6)

1. preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection is characterized in that comprising following steps:
(1), surfactant is dissolved in the absolute ethyl alcohol solution that stirring formation is transparent; Drip the ethanolic solution of phenolic resins then, the mass ratio of surfactant and phenolic resins is 1:5, stirs, and is subsequent use;
(2), regulate absolute ethyl alcohol pH3 ~ 5, add boric acid or phosphoric acid again, stir and obtain solution with HCl solution; Subsequent use;
(3), solution that step (2) is obtained dropwise joins in the solution that step (1) obtains, the boric acid that every 1g surfactant is corresponding or the addition scope of phosphoric acid are 0.02 ~ 0.16 g, stir it is mixed, and obtain yellowish transparent sol-gel;
(4), with the sol-gel that step (1) or (3) prepare, dropwise drip on stainless steel substrates, drip glue and even glue and handle;
(5), the stainless steel substrates that is coated with solution that step (4) is obtained is at 25 ℃ of following solvent evaporation at least 8 h, at 70～120 ℃ of thermal polymerization at least 24 h, forms faint yellow coating at stainless steel surfaces then; Obtain the order mesoporous carbon coating or the carbon-boron coating or the carbon-phosphor coating of black at last in the nitrogen atmosphere carbonization.
2. a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection according to claim 1; It is characterized in that: surfactant is polyoxyethylene/polyoxypropylene/polyoxyethylene amphiphilic block copolymer F127 in the said step (1), and molecular formula is PEO 106-PPO 70-PEO 106
3. a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection according to claim 1; It is characterized in that: per 1 g surfactant is dissolved in the 15mL absolute ethyl alcohol in the described step (1), and the mass fraction of the ethanolic solution of phenolic resins is 20%.
4. a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection according to claim 1, it is characterized in that: the HCl solution concentration is 0.6 mol/L in the described step (2).
5. a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection according to claim 1; It is characterized in that: in the described step (4); Dripping glue speed is 400 ~ 800 rpm, drips glue times 10 ~ 20 s, and even glue speed selection is 1500 ~ 3000 rpm; Even glue times 45 ~ 60 s repeats to drip glue and even glue process 5 times.
6. a kind of preparation method who is used for the hybrid ordered mesoporous carbon coating of proton exchange membrane fuel cell stainless steel bipolar plate protection according to claim 1; It is characterized in that: carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas in the described step (5); 350 ℃ are incubated 3 ~ 5 h down; 400 ~ 700 ℃ are incubated 2 h down under the target temperature, and heating rate is strict controlled in 1 ℃/min.
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CN103933869A (en) * 2013-01-23 2014-07-23 同济大学 Preparing method of ordered mesoporous carbon-stainless steel wire mesh composite separating membrane
CN105776177A (en) * 2016-03-11 2016-07-20 北京化工大学 Laminar boron-doped ordered mesoporous carbon and preparation method thereof
CN106784869A (en) * 2017-02-14 2017-05-31 上海源紊新能源科技有限公司 A kind of fuel cell
CN111446463A (en) * 2020-03-06 2020-07-24 浙江中合天空科技股份有限公司 Industrial production process of flexible carbon-based bipolar plate of fuel cell

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