CN106549165A - A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst - Google Patents
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses a kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst, during the carrier supported catalyst for solve conventional carriers preparation technology complex operation, preparing, easily hinder the service efficiency of catalyst, easily cause the problem of catalyst poisoning, the porous carrier is by toluene sulfochloride, SiO2After reacting with Vulcan XC 72, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, porous carrier is obtained with dimethyl sulfoxide and ethylene glycol dimethacrylate reaction finally；The porous carrier has volatility regulation and control loose structure, after dissolving using the solvent of different ratio, can regulate and control the time and thickness born.A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, has good affinity, with good conducting effect to catalyst, the catalysis activity of catalyst can effectively be improved, its preparation technology is simple to operate, and preparation cost is low, is worthy to be popularized.
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells technical field, more particularly to a kind of used in proton exchange membrane fuel cell
The porous carrier of electrode catalyst.
Background technology
Pem fuel fuel cell（PEMFC）As its operating temperature is relatively low, start fast, electroless liquid loss,
With the specific power higher than other fuel cells, not only stationary electric power plant can be made but also the power supply of destination can have been made, be expected to into
To replace the most competitive dynamic origin of current automobile power.At present, the existing London in the whole world, Canada temperature brother
Many countries and cities such as China, Stuttgart, Germany are proposed the bus line of fuel cell-driven, and many countries show
The fuel-cell vehicle of trial operation.China is also successfully proposed fuel cell-driven during Beijing Olympic Games and Shanghai World's Fair
Bus and car, there is now more than 1000 cars in national more than 10 city trial operation.As fuel cell is matched somebody with somebody
It is arranged the Fast Construction for applying hydrogenation stations, it will there are more fuel-cell vehicles to put into operation.According to Britain FuelCellToday and
U.S.'s Fuel Cells industry statistics, the growth that fuel cell installed capacity in 2012 was achieved at double compared with 2011.So
And which also has a certain distance, mainly high cost from commercial applications, key technology is not well solved.
The key technology of PEMFC mainly has PEM, elctro-catalyst, module loading electrode（MEA）, in the sensitivity and water pipe of CO
And heat management.Wherein, film assembling electrode is the core that guarantee electrochemical reaction efficiently can be carried out, by anode（Fuel electrode）, matter
Proton exchange and negative electrode（Oxygen electrode）Hot pressing is formed, and membrane electrode prepare it is critical only that control elctro-catalyst slurry proportioning with
Coating technique.
Fuel-cell catalyst carrier should possess good electronics (or proton) conducting power, larger specific surface area, close
The pore structure of reason and excellent corrosion resistance.The carrier for using on fuel cell at present is mainly high-graphitized carbon and carries
Body.But carbon carrier is weak with the interaction of noble metal catalyst, carbon carrier holds corrosion-prone problem, has a strong impact on catalyst
Activity and stability.Therefore, cheap stable novel carriers are developed significant.Number of patent application is
200680029098.7 electro-catalyst carriers for disclosing fuel cell, using a kind of cavernous dioxy doped with niobium element
Change titanium (otherwise referred to as " titanium dioxide (titania) ") as platinum or the high surface area of other suitable catalyst
Carrier, which has the characteristic suitable for PEM fuel cell environments, including appropriate surface area, electrical conductivity and chemically stable
Property, but its conducting effect is general, can only be simple play supported catalyst, the catalytic performance and catalytic efficiency to catalyst
Five facilitations, and there is the uppity shortcoming of preparation process；Number of patent application discloses fuel for 200680015088.8
The carrier of cell catalyst, is made up of at least one in titanium carbide and titanium oxide, for load comprising platinum or the conjunction containing platinum
The catalyst of the noble metals such as gold, during fuel cell use, can hinder the service efficiency of noble metal catalyst, and easily make
Into catalyst poisoning.Based on the problems referred to above, the present invention proposes a kind of many of used in proton exchange membrane fuel cell electrode catalyst
Hole carrier.
The content of the invention
For above-mentioned situation, the purpose to overcome the defect of prior art, the present invention is just to provide a kind of PEM
The porous carrier of electrode catalyst for fuel cell, it is therefore intended that solve conventional carriers preparation technology complex operation, the load for preparing
During body supported catalyst, easily hinder the service efficiency of catalyst, easily cause the problem of catalyst poisoning.
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst, the porous carrier is by tosyl
Chlorine, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, it is finally sub- with dimethyl
Sulfone and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control loose structure,
After using the solvent dissolving of different ratio, it is attached on electrode, the time and thickness born can be regulated and controled.
A kind of preparation method of the porous carrier of used in proton exchange membrane fuel cell electrode catalyst, comprises the following steps：
S1, by toluene sulfochloride, SiO2, Vulcan XC-72 and dilute HCl, carry out heated and stirred reaction, heating-up temperature is 110～
130 DEG C, mixing time is 0.8～1.5h, and after being allowed to reaction completely, Jing extracts to obtain organic faciess, and the excessive benzoyl peroxide of Deca
Formyl, obtains gray precipitate, and sucking filtration, vacuum drying obtain final product Lycoperdon polymorphum Vitt product A；
S2, obtained product A in step S1 is added in solvent, is heated to 50～80 DEG C, and with 400～800r/min
Rotating speed high-speed stirred, while stirring add nanoscale SiO2, until SiO2Load capacity reaches 35～45%, is subsequently adding excessive
Sodium dodecyl sulfate solution, continues to react 1～2h with the rotating speed stirring at low speed of 80～180r/min, after the completion of reaction, stands
20～40min, sucking filtration, washing, vacuum drying obtain final product product B；
S3, obtained product B in step S2 is added in tetrahydrofuran, is subsequently adding polydimethylsiloxane and azo
Two isobutyl cyanogen, are heated to 40～70 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing precipitations, filtration, vacuum drying
Obtain final product product C；
S4, obtained product C in step S3 is added in dichloromethane, and adds N,N methylene bis acrylamide,
80～110 DEG C are warming up to, stirring and dissolving adds dimethyl sulfoxide into after uniform solution, continues 0.5～1h of stirring reaction, then
Ethylene glycol dimethacrylate is added, continues 0.5～1h of stirring reaction, after the completion of reaction, Jing precipitations, filtration, washing, vacuum
It is dried, the porous carrier needed for obtaining final product.
Preferably, toluene sulfochloride, SiO in step S12, Vulcan XC-72 mass ratio be 1:1:1, it is described dilute
8.5～11 times for tosyl chlorine dose of the addition of HCl.
Preferably, the solvent in step S2 for deionized water, glycerol and ethylene glycol mixed solution, it is described go from
Sub- water, glycerol, the mass ratio of ethylene glycol are 3～5:0.5～0.8:0.5～0.8.
Preferably, in step S2, the mass ratio of product A and solvent is 1～1.5:7～9.
Preferably, in step S3, the mass ratio of product B and tetrahydrofuran is 1～1.3:3.8～5.2.
Preferably, in step S3, the addition of polydimethylsiloxane is the 0.5～0.8 of product B addition
Times, the addition of the azo-bis-isobutyl cyanide is 0.2～0.5 times of product B addition.
Preferably, in step S4, product C and the mass ratio of dichloromethane are 0.8～1.5:4.7～5.5.
Preferably, in step S4, the addition of N,N methylene bis acrylamide is the 0.9 of product C addition
～1.6 times, the addition of the dimethyl sulfoxide is 3.6～4.8 times of product C addition, the ethylene glycol dimethyl
5.2～6.5 times for product C addition of the addition of acrylate.
Preferably, the filtration in the preparation method refers to and is filtered with the filter that mesh number is 200～400；The system
Washing in Preparation Method refers to that deionized water is washed twice；Vacuum drying in the preparation method refers to and is placed in very product
In empty drying baker, at 70～90 DEG C, 30～50min is dried.
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, which has volatility
Regulation and control loose structure, the porous carrier prepared using the solvent dissolving present invention of different ratio, is attached on electrode, can be regulated and controled
The time born and thickness, have good affinity and conducting effect to catalyst, can effectively improve urging for catalyst
Change activity and utilization ratio, do not result in catalyst poisoning phenomenon, the invention allows for a proton exchanging film fuel battery
With the preparation method of the porous carrier of electrode catalyst, by by toluene sulfochloride, SiO2After Vulcan XC-72 reactions, with
Polydimethylsiloxane and azo-bis-isobutyl cyanide reaction, finally with dimethyl sulfoxide and ethylene glycol dimethacrylate reaction system
Porous carrier is obtained, its preparation technology is simple to operate, and preparation cost is low, be adapted to industrialized production, be worthy to be popularized.
Description of the drawings
Fig. 1 is porous carrier load tin catalyst and existing SnO prepared by the embodiment of the present invention 12Catalyst, Pt/C are urged
The electrode cycle volt-ampere contrast curve of agent；
Fig. 2 is the electrode cycle volt-ampere curve figure that porous carrier prepared by the embodiment of the present invention 2 loads tin catalyst；
Fig. 3 is the electrode cycle volt-ampere curve figure that porous carrier prepared by the embodiment of the present invention 3 loads tin catalyst；
Fig. 4 is the electrode cycle volt-ampere curve figure that porous carrier prepared by the embodiment of the present invention 4 loads tin catalyst；
Fig. 5 is the electrode cycle volt-ampere curve figure that porous carrier prepared by the embodiment of the present invention 5 loads tin catalyst.
Specific embodiment
The present invention is further explained with reference to specific embodiment.
Embodiment one
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, the porous carrier is by first
Benzene sulfonyl chloride, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, finally with two
Methyl sulfoxide and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control porous
Structure, after being dissolved using the solvent of different ratio, is attached on electrode, can regulate and control the time and thickness born.
Its preparation method, specifically includes following steps：
S1, toluene sulfochloride, SiO are weighed respectively215g each with Vulcan XC-72, carries out heated and stirred with dilute HCl of 150ml
Reaction, heating-up temperature are 120 DEG C, and mixing time is 1h, after being allowed to reaction completely, Jing extracts to obtain organic faciess, and Deca is excessive
Benzoyl peroxide, obtains gray precipitate, is placed in vacuum drying oven after sucking filtration, at 80 DEG C, is dried 40min, obtains final product Lycoperdon polymorphum Vitt
Product A；
S2, weigh the mixing that obtained product A in 30g steps S1 is added to 240ml deionized waters, glycerol and ethylene glycol
In solution, 65 DEG C are heated to, and with the rotating speed high-speed stirred of 600r/min, add nanoscale SiO while stirring2, until SiO2It is negative
Carrying capacity reaches 40%, is subsequently adding excessive sodium dodecyl sulfate solution, continues to react with the rotating speed stirring at low speed of 150r/min
1.5h, after the completion of reaction, stands 30min, and sucking filtration, deionized water are washed twice, be subsequently placed in vacuum drying oven,
At 80 DEG C, 40min is dried, obtains final product product B；
S3, weigh obtained product B in 30g steps S2 and be added in the tetrahydrofuran of 140ml, be subsequently adding the poly- of 20g
The azo-bis-isobutyl cyanide of dimethyl siloxane and 10g, is heated to 50 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing
Carry out filtering with the filter that mesh number is 300 after precipitation, be subsequently placed in vacuum drying oven, at 80 DEG C, be dried 40min, i.e.,
Obtain product C；
S4, in S3, obtained product C is added in the dichloromethane of 50ml the step of weigh 10g, and adds the N of 10g, N-
Methylene-bisacrylamide, is warming up to 100 DEG C, and stirring and dissolving into after uniform solution adds the dimethyl sulfoxide of 45ml, continues to stir
Reaction 0.8h is mixed, the ethylene glycol dimethacrylate of 60ml is subsequently adding, continues stirring reaction 1h, after the completion of reaction, Jing sinks
Carried out filtering behind shallow lake with the filter that mesh number is 300, deionized water is washed twice, be subsequently placed in vacuum drying oven,
At 80 DEG C, 40min is dried, the porous carrier needed for obtaining final product.
As shown in figure 1, A represents the electrode cycle volt-ampere curve that porous carrier loads tin catalyst, B represents SnO2Catalyst
Electrode cycle volt-ampere curve, C represents the electrode cycle volt-ampere curve of Pt/C catalyst, contrasts three strip electrode cyclic voltammetry curves
Understand, under identical cell voltage, the electric current density of A is best.
Embodiment two
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, the porous carrier is by first
Benzene sulfonyl chloride, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, finally with two
Methyl sulfoxide and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control porous
Structure, after being dissolved using the solvent of different ratio, is attached on electrode, can regulate and control the time and thickness born.
Its preparation method, specifically includes following steps：
S1, toluene sulfochloride, SiO are weighed respectively215g each with Vulcan XC-72, carries out heated and stirred with dilute HCl of 140ml
Reaction, heating-up temperature are 115 DEG C, and mixing time is 1.2h, and after being allowed to reaction completely, Jing extracts to obtain organic faciess, and Deca excess
Benzoyl peroxide, obtain gray precipitate, be placed in after sucking filtration in vacuum drying oven, at 70 DEG C, be dried 50min, obtain final product ash
Colour response product A；
S2, weigh the mixing that obtained product A in 30g steps S1 is added to 260ml deionized waters, glycerol and ethylene glycol
In solution, 50 DEG C are heated to, and with the rotating speed high-speed stirred of 400r/min, add nanoscale SiO while stirring2, until SiO2It is negative
Carrying capacity reaches 35%, is subsequently adding excessive sodium dodecyl sulfate solution, continues to react with the rotating speed stirring at low speed of 80r/min
1.8h, after the completion of reaction, stands 25min, and sucking filtration, deionized water are washed twice, be subsequently placed in vacuum drying oven,
At 70 DEG C, 50min is dried, obtains final product product B；
S3, weigh obtained product B in 30g steps S2 and be added in the tetrahydrofuran of 120ml, be subsequently adding the poly- of 15g
The azo-bis-isobutyl cyanide of dimethyl siloxane and 8g, is heated to 70 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing
Carry out filtering with the filter that mesh number is 250 after precipitation, be subsequently placed in vacuum drying oven, at 70 DEG C, be dried 50min, i.e.,
Obtain product C；
S4, in S3, obtained product C is added in the dichloromethane of 48ml the step of weigh 10g, and adds the N of 9g, N-
Methylene-bisacrylamide, is warming up to 90 DEG C, and stirring and dissolving adds the dimethyl sulfoxide of 38g into after uniform solution, continues stirring
Reaction 0.5h, is subsequently adding the ethylene glycol dimethacrylate of 55g, continues stirring reaction 0.5h, after the completion of reaction, Jing precipitations
Carried out afterwards filtering with the filter that mesh number is 250, deionized water is washed twice, be subsequently placed in vacuum drying oven,
At 70 DEG C, 50min is dried, the porous carrier needed for obtaining final product.
The porous carrier of above-mentioned preparation loads the electrode cycle volt-ampere curve figure of tin catalyst, as shown in Figure 2.
Embodiment three
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, the porous carrier is by first
Benzene sulfonyl chloride, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, finally with two
Methyl sulfoxide and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control porous
Structure, after being dissolved using the solvent of different ratio, is attached on electrode, can regulate and control the time and thickness born.
Its preparation method, specifically includes following steps：
S1, toluene sulfochloride, SiO are weighed respectively215g each with Vulcan XC-72, carries out heated and stirred with dilute HCl of 160ml
Reaction, heating-up temperature are 130 DEG C, and mixing time is 0.8h, and after being allowed to reaction completely, Jing extracts to obtain organic faciess, and Deca excess
Benzoyl peroxide, obtain gray precipitate, be placed in after sucking filtration in vacuum drying oven, at 85 DEG C, be dried 35min, obtain final product ash
Colour response product A；
S2, weigh the mixing that obtained product A in 30g steps S1 is added to 240ml deionized waters, glycerol and ethylene glycol
In solution, 80 DEG C are heated to, and with the rotating speed high-speed stirred of 500r/min, add nanoscale SiO while stirring2, until SiO2It is negative
Carrying capacity reaches 42%, is subsequently adding excessive sodium dodecyl sulfate solution, continues to react with the rotating speed stirring at low speed of 120r/min
1h, after the completion of reaction, stands 40min, and sucking filtration, deionized water are washed twice, be subsequently placed in vacuum drying oven, 85
At DEG C, 35min is dried, obtains final product product B；
S3, weigh obtained product B in 30g steps S2 and be added in the tetrahydrofuran of 150ml, be subsequently adding the poly- of 18g
The azo-bis-isobutyl cyanide of dimethyl siloxane and 12g, is heated to 40 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing
Carry out filtering with the filter that mesh number is 350 after precipitation, be subsequently placed in vacuum drying oven, at 85 DEG C, be dried 35min, i.e.,
Obtain product C；
S4, in S3, obtained product C is added in the dichloromethane of 52ml the step of weigh 10g, and adds the N of 16g, N-
Methylene-bisacrylamide, is warming up to 110 DEG C, and stirring and dissolving into after uniform solution adds the dimethyl sulfoxide of 40g, continues to stir
Reaction 1h is mixed, the ethylene glycol dimethacrylate of 65g is subsequently adding, continues stirring reaction 0.8h, after the completion of reaction, Jing precipitations
Carried out afterwards filtering with the filter that mesh number is 350, deionized water is washed twice, be subsequently placed in vacuum drying oven,
At 85 DEG C, 35min is dried, the porous carrier needed for obtaining final product.
The porous carrier of above-mentioned preparation loads the electrode cycle volt-ampere curve figure of tin catalyst, as shown in Figure 3.
Example IV
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, the porous carrier is by first
Benzene sulfonyl chloride, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, finally with two
Methyl sulfoxide and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control porous
Structure, after being dissolved using the solvent of different ratio, is attached on electrode, can regulate and control the time and thickness born.
Its preparation method, specifically includes following steps：
S1, toluene sulfochloride, SiO are weighed respectively215g each with Vulcan XC-72, carries out heated and stirred with dilute HCl of 130ml
Reaction, heating-up temperature are 125 DEG C, and mixing time is 1.5h, and after being allowed to reaction completely, Jing extracts to obtain organic faciess, and Deca excess
Benzoyl peroxide, obtain gray precipitate, be placed in after sucking filtration in vacuum drying oven, at 90 DEG C, be dried 30min, obtain final product ash
Colour response product A；
S2, weigh the mixing that obtained product A in 30g steps S1 is added to 270ml deionized waters, glycerol and ethylene glycol
In solution, 60 DEG C are heated to, and with the rotating speed high-speed stirred of 800r/min, add nanoscale SiO while stirring2, until SiO2It is negative
Carrying capacity reaches 38%, is subsequently adding excessive sodium dodecyl sulfate solution, continues to react with the rotating speed stirring at low speed of 100r/min
1.2h, after the completion of reaction, stands 35min, and sucking filtration, deionized water are washed twice, be subsequently placed in vacuum drying oven,
At 90 DEG C, 30min is dried, obtains final product product B；
S3, weigh obtained product B in 30g steps S2 and be added in the tetrahydrofuran of 130ml, be subsequently adding the poly- of 22g
The azo-bis-isobutyl cyanide of dimethyl siloxane and 15g, is heated to 60 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing
Carry out filtering with the filter that mesh number is 200 after precipitation, be subsequently placed in vacuum drying oven, at 90 DEG C, be dried 30min, i.e.,
Obtain product C；
S4, in S3, obtained product C is added in the dichloromethane of 55ml the step of weigh 10g, and adds the N of 12g, N-
Methylene-bisacrylamide, is warming up to 80 DEG C, and stirring and dissolving adds the dimethyl sulfoxide of 36g into after uniform solution, continues stirring
Reaction 0.6h, is subsequently adding the ethylene glycol dimethacrylate of 52g, continues stirring reaction 0.6h, after the completion of reaction, Jing precipitations
Carried out afterwards filtering with the filter that mesh number is 200, deionized water is washed twice, be subsequently placed in vacuum drying oven,
At 90 DEG C, 30min is dried, the porous carrier needed for obtaining final product.
The porous carrier of above-mentioned preparation loads the electrode cycle volt-ampere curve figure of tin catalyst, as shown in Figure 4.
Embodiment five
A kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst proposed by the present invention, the porous carrier is by first
Benzene sulfonyl chloride, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, finally with two
Methyl sulfoxide and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control porous
Structure, after being dissolved using the solvent of different ratio, is attached on electrode, can regulate and control the time and thickness born.
Its preparation method, specifically includes following steps：
S1, toluene sulfochloride, SiO are weighed respectively215g each with Vulcan XC-72, carries out heated and stirred with dilute HCl of 145ml
Reaction, heating-up temperature are 110 DEG C, and mixing time is 1.4h, and after being allowed to reaction completely, Jing extracts to obtain organic faciess, and Deca excess
Benzoyl peroxide, obtain gray precipitate, be placed in after sucking filtration in vacuum drying oven, at 75 DEG C, be dried 45min, obtain final product ash
Colour response product A；
S2, weigh the mixing that obtained product A in 30g steps S1 is added to 230ml deionized waters, glycerol and ethylene glycol
In solution, 70 DEG C are heated to, and with the rotating speed high-speed stirred of 700r/min, add nanoscale SiO while stirring2, until SiO2It is negative
Carrying capacity reaches 45%, is subsequently adding excessive sodium dodecyl sulfate solution, continues to react with the rotating speed stirring at low speed of 180r/min
2h, after the completion of reaction, stands 20min, and sucking filtration, deionized water are washed twice, be subsequently placed in vacuum drying oven, 75
At DEG C, 45min is dried, obtains final product product B；
S3, weigh obtained product B in 30g steps S2 and be added in the tetrahydrofuran of 155ml, be subsequently adding the poly- of 24g
The azo-bis-isobutyl cyanide of dimethyl siloxane and 6g, is heated to 55 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing
Carry out filtering with the filter that mesh number is 400 after precipitation, be subsequently placed in vacuum drying oven, at 75 DEG C, be dried 45min, i.e.,
Obtain product C；
S4, in S3, obtained product C is added in the dichloromethane of 47ml the step of weigh 10g, and adds the N of 14g, N-
Methylene-bisacrylamide, is warming up to 105 DEG C, and stirring and dissolving into after uniform solution adds the dimethyl sulfoxide of 48g, continues to stir
Reaction 0.9h is mixed, the ethylene glycol dimethacrylate of 58g is subsequently adding, continues stirring reaction 0.9h, after the completion of reaction, Jing sinks
Carried out filtering behind shallow lake with the filter that mesh number is 400, deionized water is washed twice, be subsequently placed in vacuum drying oven,
At 75 DEG C, 45min is dried, the porous carrier needed for obtaining final product.
The porous carrier of above-mentioned preparation loads the electrode cycle volt-ampere curve figure of tin catalyst, as shown in Figure 5.
The porous prepared using the mixed solvent dissolving embodiment of the present invention one～five of tetrahydrofuran and dichloromethane is carried
Body, loads same amount of tin catalyst respectively and is attached on electrode, measurement catalysis utilization rate, draws following result：
| Embodiment | One | Two | Three | Four | Five |
| Catalysis utilization rate | 53.1% | 52.6% | 50.8% | 49.9% | 51.3% |
In the case of load identical tin catalyst, the catalysis utilization rate of existing carrier is 30% or so, has the above table can
Know, carrier proposed by the present invention can effectively improve the catalytic efficiency of catalyst, improve its catalysis utilization rate.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, should all be included within the scope of the present invention.
Claims (10)
1. a kind of porous carrier of used in proton exchange membrane fuel cell electrode catalyst, it is characterised in that the porous carrier by
Toluene sulfochloride, SiO2After Vulcan XC-72 reactions, react with polydimethylsiloxane and azo-bis-isobutyl cyanide, finally with
Dimethyl sulfoxide and ethylene glycol dimethacrylate reaction are obtained porous carrier；The porous carrier has volatility regulation and control many
Pore structure, after being dissolved using the solvent of different ratio, is attached on electrode, can regulate and control the time and thickness born.
2. a kind of preparation method of the porous carrier of used in proton exchange membrane fuel cell electrode catalyst, it is characterised in that include
Following steps：
S1, by toluene sulfochloride, SiO2, Vulcan XC-72 and dilute HCl, carry out heated and stirred reaction, heating-up temperature is 110～
130 DEG C, mixing time is 0.8～1.5h, and after being allowed to reaction completely, Jing extracts to obtain organic faciess, and the excessive benzoyl peroxide of Deca
Formyl, obtains gray precipitate, and sucking filtration, vacuum drying obtain final product Lycoperdon polymorphum Vitt product A；
S2, obtained product A in step S1 is added in solvent, is heated to 50～80 DEG C, and with 400～800r/min
Rotating speed high-speed stirred, while stirring add nanoscale SiO2, until SiO2Load capacity reaches 35～45%, is subsequently adding excessive
Sodium dodecyl sulfate solution, continues to react 1～2h with the rotating speed stirring at low speed of 80～180r/min, after the completion of reaction, stands
20～40min, sucking filtration, washing, vacuum drying obtain final product product B；
S3, obtained product B in step S2 is added in tetrahydrofuran, is subsequently adding polydimethylsiloxane and azo
Two isobutyl cyanogen, are heated to 40～70 DEG C, the stirring at low speed in heating, until after the completion of reaction, Jing precipitations, filtration, vacuum drying
Obtain final product product C；
S4, obtained product C in step S3 is added in dichloromethane, and adds N,N methylene bis acrylamide,
80～110 DEG C are warming up to, stirring and dissolving adds dimethyl sulfoxide into after uniform solution, continues 0.5～1h of stirring reaction, then
Ethylene glycol dimethacrylate is added, continues 0.5～1h of stirring reaction, after the completion of reaction, Jing precipitations, filtration, washing, vacuum
It is dried, the porous carrier needed for obtaining final product.
3. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that toluene sulfochloride, SiO in step S12, Vulcan XC-72 mass ratio be 1:1:1, it is described dilute
8.5～11 times for tosyl chlorine dose of the addition of HCl.
4. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that the solvent in step S2 for deionized water, glycerol and ethylene glycol mixed solution, it is described go from
Sub- water, glycerol, the mass ratio of ethylene glycol are 3～5:0.5～0.8:0.5～0.8.
5. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that the mass ratio of product A and solvent is 1～1.5 in step S2:7～9.
6. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that the mass ratio of product B and tetrahydrofuran is 1～1.3 in step S3:3.8～5.2.
7. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that the addition of polydimethylsiloxane for product B addition 0.5～0.8 in step S3
Times, the addition of the azo-bis-isobutyl cyanide is 0.2～0.5 times of product B addition.
8. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that product C and the mass ratio of dichloromethane are 0.8～1.5 in step S4:4.7～5.5.
9. the preparation side of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that the addition of N,N methylene bis acrylamide for product C addition 0.9 in step S4
～1.6 times, the addition of the dimethyl sulfoxide is 3.6～4.8 times of product C addition, the ethylene glycol dimethyl
5.2～6.5 times for product C addition of the addition of acrylate.
10. the preparation of the porous carrier of a kind of used in proton exchange membrane fuel cell electrode catalyst according to claim 2
Method, it is characterised in that the filtration in the preparation method refers to is filtered with the filter that mesh number is 200～400；The system
Washing in Preparation Method refers to that deionized water is washed twice；Vacuum drying in the preparation method refers to and is placed in very product
In empty drying baker, at 70～90 DEG C, 30～50min is dried.
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| CN201810226611.6A CN108321405A (en) | 2016-12-07 | 2016-12-07 | The porous carrier of used in proton exchange membrane fuel cell electrode catalyst |
| CN201810196533.XA CN108321412A (en) | 2016-12-07 | 2016-12-07 | The preparation method of the porous carrier of used in proton exchange membrane fuel cell electrode catalyst |
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| CN101406850A (en) * | 2008-07-24 | 2009-04-15 | 南京航空航天大学 | Method for preparing phosphorus-ordered mesoporous carbon carrier and fuel-cell catalyst containing the carrier |
| CN101491777A (en) * | 2008-11-19 | 2009-07-29 | 南京航空航天大学 | Nickelous chloride assisted synthesis method of fuel cell catalyst carrier ordered mesoporous carbon |
| CN101912791A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Silicon/carbon dioxide composite material as well as preparation and application thereof |
| CN102306810A (en) * | 2011-07-21 | 2012-01-04 | 华南理工大学 | Composite catalyst of self-humidifying fuel cell and manufacturing method and application thereof |
| CN106058276A (en) * | 2016-07-11 | 2016-10-26 | 华南理工大学 | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode |
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| US20070037041A1 (en) * | 2005-08-12 | 2007-02-15 | Gm Global Technology Operations, Inc. | Electrocatalyst Supports for Fuel Cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406850A (en) * | 2008-07-24 | 2009-04-15 | 南京航空航天大学 | Method for preparing phosphorus-ordered mesoporous carbon carrier and fuel-cell catalyst containing the carrier |
| CN101491777A (en) * | 2008-11-19 | 2009-07-29 | 南京航空航天大学 | Nickelous chloride assisted synthesis method of fuel cell catalyst carrier ordered mesoporous carbon |
| CN101912791A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Silicon/carbon dioxide composite material as well as preparation and application thereof |
| CN102306810A (en) * | 2011-07-21 | 2012-01-04 | 华南理工大学 | Composite catalyst of self-humidifying fuel cell and manufacturing method and application thereof |
| CN106058276A (en) * | 2016-07-11 | 2016-10-26 | 华南理工大学 | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode |
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