CN101170175A - Electrode for fuel cell, membrane-electrode assembly for fuel cell including same, and fuel cell system including the same - Google Patents
Electrode for fuel cell, membrane-electrode assembly for fuel cell including same, and fuel cell system including the same Download PDFInfo
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- CN101170175A CN101170175A CNA2007101655301A CN200710165530A CN101170175A CN 101170175 A CN101170175 A CN 101170175A CN A2007101655301 A CNA2007101655301 A CN A2007101655301A CN 200710165530 A CN200710165530 A CN 200710165530A CN 101170175 A CN101170175 A CN 101170175A
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- heteropoly acid
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
An electrode for a fuel cell includes an electrode substrate and a catalyst layer on the electrode substrate. The catalyst layer includes an active catalyst and a heteropoly acid additive including a heteropoly acid supported on an inorganic carrier.
Description
Technical field
The membrane-membrane electrode for fuel cell assembly and the fuel cell system that the present invention relates to electrode for fuel cell and comprise this electrode.
Background technology
Fuel cell is a kind of electricity generation system, and its electrochemical redox reaction by oxidant and fuel produces electric energy, and described fuel for example is hydrogen or such as hydrocarbon materials such as methyl alcohol, ethanol, natural gases.
Fuel cell is a kind of clean energy resource alternative that can substitute fossil fuel.In addition, fuel cell has higher relatively power output density and energy conversion efficiency, but working and room temperature, and can have the less relatively size that can closely seal.Therefore, fuel cell can be applicable to wide spectrum, for example pollution-free automobile, electricity generation system, be used for the compact power of mobile device and military equipment etc.
Typical example fuel cell comprises polymer dielectric film fuel cell (PEMFC) and direct oxidation fuel cell (DOFC).Direct oxidation fuel cell comprises the direct methanol fuel cell of using methyl alcohol to act as a fuel.
Polymer electrolyte fuel cells has relative high energy density and high power, but need be used to handle the extra ability of controlling and relevant auxiliary device of hydrogen (or hydrogen-rich gas), the processor of for example reforming, be used for reforming methane or methyl alcohol, natural gas etc., thereby produce the hydrogen that acts as a fuel.
Comparatively speaking, direct oxidation fuel cell has lower energy density than polymer electrolyte fuel cells, but it does not need the fuel reforming processor, and because its relatively low working temperature and can be at working and room temperature.
In fuel cell system, the heap of generating comprises the element cell of adjacent stacks, and each element cell is made of membrane electrode assembly (MEA) and one or more dividing plate (being also referred to as bipolar plates).This membrane electrode assembly comprises: anode (being also referred to as " fuel electrode " or " oxidizing electrode "), negative electrode (being also referred to as " air electrode " or " reducing electrode ") and be in polymer dielectric film between anode and the negative electrode.
Generating is carried out in the following manner.Fuel is fed into anode, is adsorbed by anode catalyst, and is oxidized then and produce proton and electronics.Electronics is transferred to negative electrode by external circuit, and proton is transferred to negative electrode by polymer dielectric film.In addition, oxidant is fed into negative electrode.Then, oxidant, proton and electronics react to each other under the effect of cathod catalyst and produce heat and water.
Summary of the invention
According to the embodiment of each side, the present invention relates to a kind of electrode for fuel cell that reduces the fuel cell manufacturing cost and increase the power output of fuel cell, and membrane electrode assembly and fuel cell system with this electrode.
According to the embodiment of an aspect, the invention provides a kind of electrode that can reduce the fuel cell manufacturing cost and improve its power characteristic.
According to embodiment on the other hand, the invention provides a kind of membrane electrode assembly with described electrode.
According to the embodiment of another aspect, the invention provides a kind of fuel cell system with described membrane electrode assembly.
Embodiment of the present invention provide a kind of electrode for fuel cell.Described electrode comprises electrode base material and the catalyst layer on described electrode base material.Described catalyst layer comprises active catalyst and heteropoly acid additive, and this heteropoly acid additive comprises the heteropoly acid that is supported by inorganic carrier.
In one embodiment, the average grain diameter of described additive at about 1nm to about 100 mu m ranges.
In one embodiment, described inorganic carrier comprises the material of selecting from the group of being made up of silicon dioxide, zeolite, aluminium oxide and combination thereof.
In one embodiment, described heteropoly acid comprises having following anionic compound, and described anion is from by [PMo
12O
40]
3-, [PW
12O
40]
3-, [GeMo
12O
40]
4-, [GeW
12O
40]
4-, [P
2W
18O
62]
6-, [SiW
12O
40]
4-, [PMo
11O
39]
7-, [P
2Mo
5O
23]
6-, [H
2W
12O
40]
6-, [PW
11O
39]
7-And make up in the group of being formed and select.
In one embodiment, described heteropoly acid comprises having H
+Cationic compound.
In one embodiment, with respect to the weight of described carrier, the amount of described heteropoly acid is in the scope of about 0.01wt% to about 10wt%.
In one embodiment, with respect to the total weight of described catalyst layer, the amount of described additive is in the scope of about 0.1wt% to about 5wt%.
Another embodiment of the present invention provides a kind of membrane-membrane electrode for fuel cell assembly.Described membrane-membrane electrode for fuel cell assembly comprises: anode; Negative electrode in the face of described anode; And be placed in polymer dielectric film between described anode and the described negative electrode.At this, at least one in described anode or the described negative electrode comprises electrode base material and the catalyst layer on described electrode base material, and described catalyst layer comprises active catalyst and heteropoly acid additive, and this heteropoly acid additive comprises the heteropoly acid that is supported by inorganic carrier.
Another embodiment of the present invention provides a kind of fuel cell system.Described fuel cell system comprises: generating element; Fuel feeder is used to described generating element fueling; The oxidant feeder is used to described generating element to supply with oxidant.Described generating element comprises: anode, and face the negative electrode of described anode, and be placed in the polymer dielectric film between described anode and the described negative electrode.In described anode or the described negative electrode at least one comprises electrode base material and the catalyst layer on described electrode base material, and described catalyst layer comprises active catalyst and heteropoly acid additive, and this heteropoly acid additive comprises the heteropoly acid that is supported by inorganic carrier.
Description of drawings
Fig. 1 represents the cross sectional representation of membrane electrode assembly according to embodiments of the present invention.
Embodiment
In the following detailed description, only show and describe particular exemplary embodiment of the present invention by illustration.What those skilled in the art will recognize that is that the present invention can specialize according to multi-form, and should not be considered to only limit to embodiment shown here.In the text, identical Reference numeral refers to components identical.
Embodiment of the present invention relate to electrode for fuel cell.Recently, study for electrode catalyst with relative greater activity.
For such as H
3PW
12O
40Study Deng heteropoly acid.Heteropoly acid is the solid catalyst with higher relatively electronics and proton-conducting, and is considered to the substitute of high activity platinum class catalyst.It has some shortcomings, is soluble in such as water, methyl alcohol and the ethanol isopolarity aqueous solution, thereby makes it not have high reaction activity, and its shortcoming is that also it is easy to separate from carrier.
According to embodiment of the present invention, heteropoly acid is supported by inorganic carrier, thereby is used as the additive (or heteropoly acid additive) of electrode, in order to improve power characteristic.
The electrode of embodiment of the present invention comprises electrode base material and the catalyst layer that is placed on the electrode base material.Catalyst layer comprises catalyst and additive.Additive can comprise the heteropoly acid that is supported by inorganic carrier.Can't help inorganic carrier when supporting when heteropoly acid, dissolve in such as in the reactants such as fuel, described fuel for example is the mixture of hydrocarbon fuel or fuel and water, makes that like this heteropoly acid is diluted and thereby can not keep desirable power.
In one embodiment, the average grain diameter of additive is from about 50nm to about 100nm (or 50～100nm) scopes.When the average grain diameter of additive was in above-mentioned scope, additive had the size of catalyst of being very similar to.Correspondingly, catalyst and additive can evenly mix, and realize desirable catalyst and additive result of use.
Above-mentioned inorganic carrier is selected from the group of being made up of silicon dioxide, zeolite, aluminium oxide and combination thereof.Such carrier can stably support heteropoly acid, and thereby the additive effect of heteropoly acid is maximized.
Heteropoly acid can be for having following anionic compound, and described anion is from by [PMo
12O
40]
3-, [PW
12O
40]
3-, [GeMo
12O
40]
4-, [GeW
12O
40]
4-, [P
2W
18O
62]
6-, [SiW
12O
40]
4-, [PMo
11O
39]
7-, [P
2Mo
5O
23]
6-, [H
2W
12O
40]
6-, [PW
11O
39]
7-And make up in the group of being formed and select.Heteropoly acid can comprise H
+, as the cation that combines with anion.Such heteropoly acid has the conductibility of high electronics and proton.
With respect to the weight of carrier, the amount of heteropoly acid is in the scope (or 0.01～10wt%) of about 0.01wt% to about 10wt%.For example, the weight ratio of heteropoly acid and carrier was 0.01: 100 to 10: 100 scope.When the amount of heteropoly acid during less than 0.01wt%, the effect deficiency of interpolation; And when its amount surpassed 10wt%, it may be dissolved in the solvent in the process that forms catalyst layer.
By heteropoly acid is dissolved in the solvent, then this solution is mixed with the inorganic carrier with nano-sized particles, can obtain above-mentioned additive.At this, described solvent can comprise any suitable material with polarity, for example water, ethanol, methyl alcohol, isopropyl alcohol etc.
According to embodiment of the present invention, with respect to the total weight of catalyst layer, the amount of above-mentioned additive (comprising the heteropoly acid by supported carrier) is in the scope of 0.1～5wt%.When the amount of additive during less than 0.1wt%, it may almost not have result of use.On the other hand, when it measures greater than 5wt%, catalyst layer meeting thickening, thus make power output variation.
Active catalyst can be any suitable catalyst of carrying out fuel cell reaction.Typical catalyst can comprise platinum class catalyst.This platinum class catalyst comprises platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palldium alloy, platinum-M alloy or its combination, wherein, the transition metal of M for from the group of forming by Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Mo, W, Rh, Ru and combination thereof, selecting.The representative example of catalyst comprises the material of selecting from the group of being made of Pt, Pt/Ru, Pt/W, Pt/Ni, Pt/Sn, Pt/Mo, Pt/Pd, Pt/Fe, Pt/Cr, Pt/Co, Pt/Ru/W, Pt/Ru/Mo, Pt/Ru/V, Pt/Fe/Co, Pt/Ru/Rh/Ni, Pt/Ru/Sn/W and combination thereof.
Such catalyst can use with the form (black catalyst) of metal self, perhaps can be used by supported carrier.This carrier can comprise carbon, for example graphite, Deng Kahei (denka black), Kai Qinhei (ketjen black), acetylene black, carbon nano-tube, carbon nano-fiber, carbon nano wire, activated carbon etc., perhaps comprise inorganic particle, for example aluminium oxide, silicon dioxide, zirconia, titanium oxide etc.In one embodiment, use carbon.
Catalyst layer can comprise binder resin, to improve its caking property and proton transport performance.
Binder resin can be for having the proton-conducting polymer resin of cation exchange group on side chain, this cation exchange group is selected from the group of being made up of sulfonic group, carboxylic acid group, phosphate, phosphonate group and derivative thereof.In one embodiment, this fluoropolymer resin comprises the proton-conducting polymer of selecting from the group of being made up of perfluor base polymer, benzimidazole base polymer, polyimides base polymer, Polyetherimide base polymer, polyphenylene sulfide base polymer, polysulfones-like polymer, polyether sulfone polymer, polyether-ketone base polymer, polyethers-ether ketone polymer, polyphenylene quinoxaline polymer and combination thereof.In one embodiment, this proton-conducting polymer is: poly-perfluorinated sulfonic acid, poly-perfluorocarboxylic acid, the copolymer with sulfonic tetrafluoroethene and fluorovinyl ether, defluorinate polyether-ketone sulfide, aryl ketones, poly-(2,2 '-metaphenylene-5,5 '-bisbenzimidazole) and/or poly-(2, the 5-benzimidazole).
Hydrogen in the cation exchange group of proton-conducting polymer (H) can be replaced by Na, K, Li, Cs or TBuA.When the H in the cation exchange group of proton-conducting polymer side chain terminal is replaced with Na or TBuA, when the preparation carbon monoxide-olefin polymeric, can use NaOH or TBAH respectively.When H is replaced with K, Li or Cs, can use suitable alternative compounds (for example can use suitable hydroxide compound).
Binder resin can only comprise one type resin or use with other resin-bonded.And then this resin can use with one or more non-conducting polymer, with the caking property of improvement with polymer dielectric film.The amount of binder resin can change to realize specific expected characteristics.
The limiting examples of non-conducting polymer comprises polytetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene/tetrafluoroethylene (ETFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), Kynoar, Kynoar-hexafluoropropylene copolymer (PVdF-HFP), DBSA, sorbierite and combination thereof.
The electrode base material support electrode also is provided for fuel and oxidant are transferred to the path of catalyst layer.
In one embodiment, electrode base material is by forming such as materials such as carbon paper, carbon cloth, carbon felt or hardware cloths (perforated membrane that is formed by metallic fiber or the lip-deep metal film that is arranged on polymer fiber cloth).Electrode base material is not limited in this.
Electrode base material can use fluorine-type resin to handle and have a hydrophobicity, worsens with the diffuser efficiency that prevents (or protection and avoid) fuel cell.This deterioration may take place owing to the water that produces in operation of fuel cells.This fluorine-type resin can comprise: polytetrafluoroethylene, Kynoar, polyhexafluoropropylene, poly-perfluoroalkyl vinyl ether, poly-perfluor sulfonyl Fluoroalkyloxy vinyl ethers, fluorinated ethylene propylene, polytrifluorochloroethylene or its copolymer, but be not limited in this.
Microporous layers (MPL) be introduced between former electrodes base material and the catalyst layer to increase the diffusion effect of reactant.Microporous layers generally includes the conductive powder with specified particle diameter.This electric conducting material can include but not limited to: carbon dust, carbon black, acetylene black, Kai Qinhei (ketjen black), activated carbon, carbon fiber, fullerene (fullerene), nano-sized carbon or its combination.Nano-sized carbon can comprise such as materials such as carbon nano-tube, carbon nano-fiber, carbon nano wire, carbon nanohorn, carbon nano ring or its combinations.
Microporous layers is coated on the conductive base by the composition that will comprise conductive powder, binder resin and solvent and forms.Binder resin can include but are not limited to: polytetrafluoroethylene, Kynoar, polyhexafluoropropylene, poly-perfluoroalkyl vinyl ether, poly-perfluor sulfonyl fluorine, alkoxy vinyl ethers, polyvinyl alcohol, cellulose acetate or its copolymer.Solvent can include but are not limited to: such as alcohol such as ethanol, isopropyl alcohol, normal propyl alcohol, butanols, water, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone or oxolane.Coating process can include but are not limited to: silk screen printing, spraying, scraper plate coating, intaglio printing coating, dip coated, silk screen cover, brushing etc., and this depends on the viscosity of composition.
According to one embodiment of the invention, electrode comprises carbon monoxide-olefin polymeric, and described carbon monoxide-olefin polymeric prepares in the following manner: additive is mixed with active catalyst, then this mixture is mixed with adhesive; Perhaps, will at first additive be mixed with adhesive, then the mixture that obtains be mixed with active catalyst.Mixed process can be carried out in specific solvent, or can not comprise solvent, and this is because adhesive is usually included in the solvent as ready-made product.When using solvent, this solvent can include but are not limited to: such as alcohol such as ethanol, isopropyl alcohol, normal propyl alcohol, butanols, water, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone or oxolane.Coating process can include but are not limited to: silk screen printing, spraying, scraper plate coating etc., this depends on the viscosity of composition.
According to one embodiment of the invention, have the applicable male or female of doing of electrode of said structure, or suitable simultaneously anode and the negative electrode done.When electrode of the present invention was used as anode, it can improve oxidized.When electrode was used as negative electrode, it can improve proton-conducting.Consequently, electrode can have the redox reaction of improvement, and thereby provides the membrane electrode assembly with relative higher-wattage.In addition, because the cost of heteropoly acid is lower than traditional platinum class catalyst and also useful as catalysts, therefore, the electrode cost can reduce pro rata with the amount of used heteropoly acid.
According to one embodiment of the invention, membrane electrode assembly comprises anode and negative electrode, and is placed in the polymer dielectric film between anode and the negative electrode.At this, at least one in the male or female can have aforesaid electrode structure.
Polymer dielectric film is as ion-exchange unit, and the proton transport that is used for anode catalyst layer is produced is to cathode catalyst layer.The polymer dielectric film of membrane electrode assembly can comprise the proton-conducting polymer resin.The proton-conducting polymer resin can be for having the fluoropolymer resin of cation exchange group on its side chain, described cation exchange group is selected from the group of being made up of sulfonic group, carboxylic acid group, phosphate, phosphonate group and derivative thereof.
In one embodiment, fluoropolymer resin can comprise the proton-conducting polymer of selecting from the group of being made up of fluorine-based polymer, benzimidazole base polymer, polyimides base polymer, Polyetherimide base polymer, polyphenylene sulfide base polymer, polysulfones-like polymer, polyether sulfone polymer, polyether-ketone base polymer, polyethers-ether ketone polymer, polyphenylene quinoxaline polymer and combination thereof.In one embodiment, this proton-conducting polymer is: poly-perfluorinated sulfonic acid (Nafion
TM), poly-perfluorocarboxylic acid, copolymer, defluorinate polyether-ketone sulfide, aryl ketones, poly-(2,2 '-metaphenylene-5,5 '-bisbenzimidazole) and/or gather (2, the 5-benzimidazole) with sulfonic tetrafluoroethene and fluorovinyl ether.
Hydrogen (H) in the proton-conducting group of proton-conducting polymer can be replaced by Na, K, Li, Cs or TBuA.When the H in the ion-exchange group of proton-conducting polymer side chain terminal is replaced with Na or TBuA, can use NaOH or TBAH respectively.When H is replaced with K, Li or Cs, can use suitable alternative compounds.
In one embodiment of the invention, fuel cell system comprises aforesaid membrane electrode assembly.At this, fuel cell system comprises: at least one generating element, fuel feeder and oxidant feeder.
Generating element comprises membrane electrode assembly and dividing plate.Membrane electrode assembly comprises polymer dielectric film and places anode and negative electrode on this polymer dielectric film opposite side respectively.Generating element generates electricity by the reduction of fuel oxidation and oxidant.
Fuel feeder is used to the generating element fueling.The oxidant feeder is used to generating element to supply with such as oxidants such as oxygen or air.
Fuel comprises the hydrogen of liquid state or gaseous state, or such as hydrocarbon fuel such as methyl alcohol, ethanol, propyl alcohol, butanols, natural gases.
Fig. 1 represents the schematic construction of fuel cell system according to embodiments of the present invention.At this, fuel cell system is shown as, and fuel and oxidant are provided for generating element by pump, but the present invention is not limited in such structure.Fuel cell system of the present invention alternately comprises the structure that fuel and oxidant are provided with diffusion way.
In addition, fuel feeder 5 is equipped with the jar 9 and the coupled petrolift 11 of fuel-in-storage.Petrolift 11 is supplied with the fuel that the pump power that can be scheduled to will be stored in the jar 9.
The oxidant feeder 7 of supplying with oxidant for generating element 3 is equipped with at least one pump 13, is used for supplying with oxidant with pump power (can be scheduled to).
Generating element 3 comprises the membrane electrode assembly 17 that is used for oxidizes hydrogen gas or fuel and reduction-oxidation agent, lays respectively at the dividing plate 19 and 19 ' that is used for hydrogen supply or fuel and oxidant on the opposite side of this membrane electrode assembly.Heap 15 can comprise one or more generating elements 3.
Embodiment hereinafter in more detail illustration the present invention.But the present invention is not limited in these embodiment.
With H
3PW
12O
40Water-soluble, then by average grain diameter with 100nm and 150m
2The SiO of the specific area of/g
2Supported carrier has by SiO thereby prepare
2The H of supported carrier
3PW
12O
40H
3PW
12O
40Additive.At this, with respect to SiO
2Weight, H
3PW
12O
40(or by supported carrier) amount that supports for 0.01wt%.For example, H
3PW
12O
40With SiO
2Weight ratio be 0.01: 100.
The H of 5wt%
3PW
12O
40(Johnson Matthey, HiSpec6000) anode catalyst mixes platinum-ruthenium black of additive and 95wt%.The mixture that obtains mixes with the weight ratio of 88wt%: 12wt% with the adhesive that consists of 5wt%-Nafion/ water/2-propyl alcohol (solution technique company), thereby prepares the carbon monoxide-olefin polymeric that is used for anode.
On the other hand, platinum black (Johnson Matthey, HiSpec 100) cathod catalyst mixes with the weight ratio of 88wt%: 12wt% with the adhesive that consists of 5wt%-Nafion/ water/2-propyl alcohol (solution technique company), thereby prepares the carbon monoxide-olefin polymeric that is used for negative electrode.
Being used for anode is coated on respectively on the carbon paper to prepare anode and negative electrode with the carbon monoxide-olefin polymeric that is used for negative electrode.
The anode that use prepares, the negative electrode for preparing and commercially available Nafion 115 (perfluorinated sulfonic acid) polymer dielectric film form membrane electrode assembly.
The membrane-membrane electrode for fuel cell assembly is inserted between two spacer blocks, is inserted into two then and has between specific (or the predetermined) gas passage of shape and the dividing plate of cooling duct, and compress between the copper end plate and make element cell.
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, with respect to SiO
2Weight, H
3PW
12O
40Loading be 1wt%.For example, H
3PW
12O
40With SiO
2Weight ratio be 1: 100.
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, with respect to SiO
2Weight, H
3PW
12O
40Loading be 2wt%.
Embodiment 4
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, with respect to SiO
2Weight, H
3PW
12O
40Loading be 6wt%.
Embodiment 5
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, with respect to SiO
2Weight, H
3PW
12O
40Loading be 10wt%.
Reference example 1
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, with respect to SiO
2Weight, H
3PW
12O
40Loading be 0.001wt%.
Reference example 2
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, with respect to SiO
2Weight, H
3PW
12O
40Loading be 11wt%.
Reference examples 1
Platinum-ruthenium black (Johnson Matthey, HiSpec 6000) anode catalyst mixes with the weight ratio of 88wt%: 12wt% with the adhesive that consists of 5wt%-Nafion/ water/2-propyl alcohol (solution technique company), thereby prepares the carbon monoxide-olefin polymeric that is used for anode.
And then, platinum black (Johnson Matthey, HiSpec 100) cathod catalyst mixes with the weight ratio of 88wt%: 12wt% with the adhesive that consists of 5wt%-Nafion/ water/2-propyl alcohol (solution technique company), thereby prepares the carbon monoxide-olefin polymeric that is used for negative electrode.
The carbon monoxide-olefin polymeric that is used for anode and negative electrode is coated on respectively on the carbon paper to prepare anode and negative electrode.
Then, use the anode, the negative electrode for preparing and commercially available Nafion 115 (perfluorinated sulfonic acid) polymer dielectric film that prepare to form membrane electrode assembly.
The membrane-membrane electrode for fuel cell assembly is inserted between two spacer blocks, is inserted into two then and has between specific (or the predetermined) gas passage of shape and the dividing plate of cooling duct, and compress between the copper end plate and make element cell.
According to embodiment 1-5, reference example 1 and 2 and the power density of the element cell made of reference examples 1 when 0.35V, 0.4V and the 0.45V under 70 ℃, measure, its result is as shown in table 1.
Table 1
| Addition (H 3PW 12O 40/SiO 2)，wt％ | 70℃，mW/cm 2 | |||
| 0.45V | 0.4V | 0.35V | ||
| Reference example 1 |
0.001 0.01 1 2 6 10 11 0 | 85 85 90 95 98 86 82 85 | 112 113 125 128 135 115 110 112 | 128 132 145 154 165 145 131 131 |
As shown in table 1, according to SiO in the electrode of embodiment 1-5
2Infiltrate the H that (or supporting) has 0.01～10wt% in the carrier
3PW
12O
40, comprise the battery of such electrode and compare the power density that demonstrates improvement according to the situation of non-additive reference examples 1.And then, (wherein add 0.001wt%H relatively more slightly according to the battery of reference example 1
3PW
12O
40) with (wherein relative more amount ground adds 11wt%H according to the battery of reference example 2
3PW
12O
40), and compare according to the battery of reference examples 1, demonstrate lower power density.
Embodiment 6
By with the method manufacturing cell battery of embodiment 1 identical (or basic identical), its difference is, shown in embodiment 3, with respect to SiO
2Weight, H
3PW
12O
40Loading be 2wt%, then, with the H that obtains of 0.1 wt%
3PW
12O
40Platinum-ruthenium black of additive and 99.9wt% (JohnsonMatthey, HiSpec 6000) anode catalyst mixes.
By with the method manufacturing cell battery of embodiment 6 identical (or basic identical), its difference is, with the H of 1wt%
3PW
12O
40Platinum-ruthenium black of additive and 99wt% (Johnson Matthey, HiSpec 6000) anode catalyst mixes.
Embodiment 8
By with the method manufacturing cell battery of embodiment 6 identical (or basic identical), its difference is, with the H of 2wt%
3PW
12O
40Platinum-ruthenium black of additive and 98wt% (Johnson Matthey, HiSpec 6000) anode catalyst mixes.
Embodiment 9
By with the method manufacturing cell battery of embodiment 6 identical (or basic identical), its difference is, with the H of 3wt%
3PW
12O
40Platinum-ruthenium black of additive and 97wt% (Johnson Matthey, HiSpec 6000) anode catalyst mixes.
Reference example 3
By with the method manufacturing cell battery of embodiment 6 identical (or basic identical), its difference is, with the H of 0.01wt%
3PW
12O
40Platinum-ruthenium black of additive and 99.99wt% (JohnsonMatthey, HiSpec 6000) anode catalyst mixes.
Reference example 4
By with the method manufacturing cell battery of embodiment 6 identical (or basic identical), its difference is, with the H of 6wt%
3PW
12O
40Platinum-ruthenium black of additive and 94wt% (Johnson Matthey, HiSpec 6000) anode catalyst mixes.
The power density of the element cell of making according to embodiment 6-9, reference example 3 and 4 when 0.35V, 0.4V and 0.45V measured under 70 ℃, and its result is as shown in table 2.As a comparison, also provided the measurement result of embodiment 3 and reference examples 1.
Table 2
| With respect to the additive capacity of catalytic amount, wt% | 70℃，mW/cm 2 | |||
| 0.45V | 0.4V | 0.35V | ||
| Reference example 3 embodiment 6 |
0.01 0.1 1 2 3 5 6 0 | 85 86 88 90 93 95 81 85 | 112 114 121 123 123 126 128 112 | 131 132 148 150 152 154 120 131 |
As shown in table 2, according in the electrode of embodiment 3 and 6-9 with the H of 0.1～5wt%
3PW
12O
40Additive mixes with anode catalyst, comprises the battery of such electrode and compares the power density that demonstrates improvement according to the situation of non-additive reference examples 1.And then, according to the battery (wherein adding the 0.01wt% additive relatively more slightly) of reference example 3 and battery (wherein relative more amount ground adds the 6wt% additive), and compare according to the battery of reference examples 1 according to reference example 4, demonstrate lower power density.
Embodiment 10
Shown in embodiment 3, with respect to SiO
2Weight, H
3PW
12O
40Loading be 2wt%, then, with the H that obtains of 0.1wt%
3PW
12O
40Platinum-ruthenium black of additive and 99.9wt% (JohnsonMatthey, HiSpec 6000) cathod catalyst mixes.The mixture that obtains mixes with the weight ratio of 88wt%: 12wt% with the adhesive that consists of 5wt%-Nafion/ water/2-propyl alcohol (solution technique company), thereby prepares the carbon monoxide-olefin polymeric that is used for negative electrode.Use this carbon monoxide-olefin polymeric to make negative electrode.
On the other hand, platinum-ruthenium black (Johnson Matthey, HiSpec 100) cathod catalyst mixes with the weight ratio of 88wt%: 12wt% with the adhesive that consists of 5wt%-Nafion/ water/2-propyl alcohol (solution technique company), thereby prepares the carbon monoxide-olefin polymeric that is used for anode.
The carbon monoxide-olefin polymeric that is used for anode is coated on the carbon paper to form anode.
The anode that use prepares, the negative electrode for preparing and commercially available Nafion 115 (perfluorinated sulfonic acid) polymer dielectric film form membrane electrode assembly.
The membrane-membrane electrode for fuel cell assembly is inserted between two spacer blocks, is inserted into two then and has between specific (or the predetermined) gas passage of shape and the dividing plate of cooling duct, and compress between the copper end plate and make element cell.
By with the method manufacturing cell battery of embodiment 10 identical (or basic identical), its difference is, with the H of 2wt%
3PW
12O
40The platinum black of additive and 98wt% (Johnson Matthey, HiSpec 6000) cathod catalyst mixes.
Embodiment 12
By with the method manufacturing cell battery of embodiment 10 identical (or basic identical), its difference is, with the H of 5wt%
3PW
12O
40The platinum black of additive and 95wt% (Johnson Matthey, HiSpec 6000) cathod catalyst mixes.
Reference example 5
By with the method manufacturing cell battery of embodiment 10 identical (or basic identical), its difference is, with the H of 0.01wt%
3PW
12O
40The platinum black of additive and 99.99wt% (JohnsonMatthey, HiSpec 6000) cathod catalyst mixes.
Reference example 6
By with the method manufacturing cell battery of embodiment 10 identical (or basic identical), its difference is, with the H of 6wt%
3PW
12O
40The platinum black of additive and 94wt% (Johnson Matthey, HiSpec 6000) cathod catalyst mixes.
The power density of the element cell of making according to embodiment 10-12 and reference example 5 and 6 when 0.35V, 0.4V and 0.45V measured under 70 ℃, and its result is as shown in table 3.As a comparison, also provided the measurement result of reference examples 1.
Table 3
| With respect to the additive capacity of catalytic amount, wt% | 70℃，mW/cm 2 | |||
| 0.45V | 0.4V | 0.35V | ||
| Reference example 5 embodiment 10 |
0.01 0.1 2 5 6 0 | 85 87 96 89 86 85 | 112 114 130 118 118 112 | 131 133 150 134 134 131 |
As shown in table 3, according in the electrode of embodiment 10-12 with the H of 0.1～5wt%
3PW
12O
40Additive mixes with cathod catalyst, comprises the battery of such electrode and compares the power density that demonstrates improvement according to the situation of non-additive reference examples 1.And then, according to the battery (wherein adding the 0.01wt% additive relatively more slightly) of reference example 5 and battery (wherein relative more amount ground adds the 6wt% additive), and compare according to the battery of reference examples 1 according to reference example 6, demonstrate lower power density.
This shows that the electrode of embodiment of the present invention can provide the fuel cell of relative higher-wattage, and saves cost simultaneously, this be because, comprising having the higher relatively electronics and an additive of proton-conducting.
Though invention has been described with reference to the particular exemplary embodiment, but be understood that, the present invention is not limited in disclosed embodiment, on the contrary, the invention is intended to be encompassed in the interior various modifications and the equivalent structure of spirit and scope of claims and equivalent thereof.
Claims (21)
1. electrode for fuel cell comprises:
Electrode base material; With
Catalyst layer on described electrode base material,
Wherein, described catalyst layer comprises active catalyst and heteropoly acid additive, and this heteropoly acid additive comprises the heteropoly acid that is supported by inorganic carrier.
2. electrode according to claim 1, wherein, the average grain diameter of described additive at about 1nm to about 100 mu m ranges.
3. electrode according to claim 1, wherein, described inorganic carrier comprises the material of selecting from the group of being made up of silicon dioxide, zeolite, aluminium oxide and combination thereof.
4. electrode according to claim 1, wherein, described heteropoly acid comprises having following anionic compound, described anion is from by [PMo
12O
40] 3-, [PW
12O
40]
3-, [GeMo
12O
40]
4-, [GeW
12O
40]
4-, [P
2W
18O
62]
6-, [SiW
12O
40]
4-, [PMo
11O
39]
7-, [P
2Mo
5O
23]
6-, [H
2W
12O
40]
6-, [PW
11O
39]
7-And make up in the group of being formed and select.
5. electrode according to claim 1, wherein, described heteropoly acid comprises having H
+Cationic compound.
6. electrode according to claim 1, wherein, with respect to the weight of described carrier, the amount of described heteropoly acid is in the scope of about 0.01wt% to about 10wt%.
7. electrode according to claim 1, wherein, with respect to the total weight of described catalyst layer, the amount of described additive is in the scope of about 0.1wt% to about 5wt%.
8. membrane-membrane electrode for fuel cell assembly comprises:
Anode;
Negative electrode in the face of described anode; With
Be placed in the polymer dielectric film between described anode and the described negative electrode,
Wherein, at least one in described anode or the described negative electrode comprise electrode base material and the catalyst layer on described electrode base material and
Described catalyst layer comprises active catalyst and heteropoly acid additive, and this heteropoly acid additive comprises the heteropoly acid that is supported by inorganic carrier.
9. membrane electrode assembly according to claim 8, wherein, the average grain diameter of described additive at about 1nm to about 100 mu m ranges.
10. membrane electrode assembly according to claim 8, wherein, described inorganic carrier comprises the material of selecting from the group of being made up of silicon dioxide, zeolite, aluminium oxide and combination thereof.
11. membrane electrode assembly according to claim 8, wherein, described heteropoly acid comprises having following anionic compound, and described anion is from by [PMo
12O
40]
3-, [PW
12O
40]
3-, [GeMo
12O
40]
4-, [GeW
12O
40]
4-, [P
2W
18O
62]
6-, [SiW
12O
40]
4-, [PMo
11O
39]
7-, [P
2Mo
5O
23]
6-, [H
2W
12O
40]
6-, [PW
11O
39]
7-And make up in the group of being formed and select.
12. membrane electrode assembly according to claim 8, wherein, described heteropoly acid comprises having H
+Cationic compound.
13. membrane electrode assembly according to claim 8, wherein, with respect to the weight of described carrier, the amount of described heteropoly acid is in the scope of about 0.01wt% to about 10wt%.
14. membrane electrode assembly according to claim 8, wherein, with respect to the total weight of described catalyst layer, the amount of described additive is in the scope of about 0.1wt% to about 5wt%.
15. a fuel cell system comprises:
Generating element;
Fuel feeder is used to described generating element fueling; With
The oxidant feeder is used to described generating element to supply with oxidant,
Wherein, described generating element comprises: anode, and face the negative electrode of described anode, and be placed in the polymer dielectric film between described anode and the described negative electrode;
Wherein, at least one in described anode or the described negative electrode comprise electrode base material and the catalyst layer on described electrode base material and
Described catalyst layer comprises active catalyst and heteropoly acid additive, and this heteropoly acid additive comprises the heteropoly acid that is supported by inorganic carrier.
16. fuel cell system according to claim 15, wherein, the average grain diameter of described additive at about 1nm to about 100 mu m ranges.
17. fuel cell system according to claim 15, wherein, described inorganic carrier comprises the material of selecting from the group of being made up of silicon dioxide, zeolite, aluminium oxide and combination thereof.
18. fuel cell system according to claim 15, wherein, described heteropoly acid comprises having following anionic compound, and described anion is from by [PMo
12O
40]
3-, [PW
12O
40]
3-, [GeMo
12O
40]
4-, [GeW
12O
40]
4-, [P
2W
18O
62]
6-, [SiW
12O
40]
4-, [PMo
11O
39]
7-, [P
2Mo
5O
23]
6-, [H
2W
12O
40]
6-, [PW
11O
39]
7-And make up in the group of being formed and select.
19. fuel cell system according to claim 15, wherein, described heteropoly acid comprises having H
+Cationic compound.
20. fuel cell system according to claim 15, wherein, with respect to the weight of described carrier, the amount of described heteropoly acid is in the scope of about 0.01wt% to about 10wt%.
21. fuel cell system according to claim 15, wherein, with respect to the total weight of described catalyst layer, the amount of described additive is in the scope of about 0.1wt% to about 5wt%.
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| KR20060104465 | 2006-10-26 | ||
| KR1020060104465 | 2006-10-26 | ||
| KR1020070106771 | 2007-10-23 |
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| CN101170175A true CN101170175A (en) | 2008-04-30 |
| CN100547834C CN100547834C (en) | 2009-10-07 |
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ID=39390690
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101655301A Expired - Fee Related CN100547834C (en) | 2006-10-26 | 2007-10-26 | Electrode for fuel cell, membrane-membrane electrode for fuel cell assembly and fuel cell system |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100953617B1 (en) |
| CN (1) | CN100547834C (en) |
| DE (1) | DE602007009462D1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468510A (en) * | 2010-11-18 | 2012-05-23 | 北京科技大学 | Indirect methanol fuel cell device based on heteropoly compound energy storage |
| CN102522571A (en) * | 2011-12-31 | 2012-06-27 | 中国科学院长春应用化学研究所 | Preparation method of proton-exchanging membrane fuel-cell catalyst composite carrier |
| CN103738917A (en) * | 2012-12-31 | 2014-04-23 | 刘军 | Low-temperature liquid phase fuel reforming hydrogen generator and preparation method of high-purity hydrogen |
| CN105655603A (en) * | 2015-12-31 | 2016-06-08 | 北京化工大学 | Fuel-cell catalyst and preparation method thereof |
| CN105870462A (en) * | 2016-04-19 | 2016-08-17 | 西南大学 | Preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material and product and application of carbon felt/carbon nanotube/phosphomolybdic acid composite material |
| CN109075362A (en) * | 2016-04-28 | 2018-12-21 | 可隆工业株式会社 | Membrane-membrane electrode for fuel cell component |
| CN114182294A (en) * | 2021-11-11 | 2022-03-15 | 深圳市欧格尼绿氢科技有限公司 | Double-catalyst system and method for producing hydrogen by electrochemically degrading biomass refined organic waste |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101368387B1 (en) * | 2012-03-27 | 2014-03-03 | 한국에너지기술연구원 | Catalysts for anode of direct methanol fuel cell, preparation method thereof, membrane electrode assembly for direct methanol fuel cell and direct methanol fuel cell system using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100773635B1 (en) * | 2001-09-11 | 2007-11-05 | 세키스이가가쿠 고교가부시키가이샤 | Membrane-Electrode Assembly, Its Manufacturing Method, and Solid Polymer Fuel Cell Using the Same |
| JP3714930B2 (en) * | 2002-11-29 | 2005-11-09 | 三洋電機株式会社 | Fuel cell electrode and fuel cell using the same |
| JP2004241307A (en) * | 2003-02-07 | 2004-08-26 | Matsushita Electric Ind Co Ltd | Electrode carrying heteropolyacid, and electrochemical element using the same |
| JP2005129285A (en) * | 2003-10-22 | 2005-05-19 | Matsushita Electric Ind Co Ltd | Electrochemical element and its manufacturing method |
-
2007
- 2007-10-23 KR KR1020070106771A patent/KR100953617B1/en not_active IP Right Cessation
- 2007-10-25 DE DE602007009462T patent/DE602007009462D1/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102468510A (en) * | 2010-11-18 | 2012-05-23 | 北京科技大学 | Indirect methanol fuel cell device based on heteropoly compound energy storage |
| CN102522571A (en) * | 2011-12-31 | 2012-06-27 | 中国科学院长春应用化学研究所 | Preparation method of proton-exchanging membrane fuel-cell catalyst composite carrier |
| CN103738917A (en) * | 2012-12-31 | 2014-04-23 | 刘军 | Low-temperature liquid phase fuel reforming hydrogen generator and preparation method of high-purity hydrogen |
| WO2014101858A1 (en) * | 2012-12-31 | 2014-07-03 | 益阳金能新材料有限责任公司 | Low-temperature liquid phase fuel reformer for flow battery |
| CN105655603B (en) * | 2015-12-31 | 2018-06-12 | 北京化工大学 | A kind of fuel-cell catalyst and preparation method thereof |
| CN105655603A (en) * | 2015-12-31 | 2016-06-08 | 北京化工大学 | Fuel-cell catalyst and preparation method thereof |
| CN105870462A (en) * | 2016-04-19 | 2016-08-17 | 西南大学 | Preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material and product and application of carbon felt/carbon nanotube/phosphomolybdic acid composite material |
| CN105870462B (en) * | 2016-04-19 | 2018-06-15 | 西南大学 | Preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material and products thereof and application |
| CN109075362A (en) * | 2016-04-28 | 2018-12-21 | 可隆工业株式会社 | Membrane-membrane electrode for fuel cell component |
| CN109075362B (en) * | 2016-04-28 | 2021-07-23 | 可隆工业株式会社 | Membrane electrode assembly for fuel cell |
| US11114684B2 (en) | 2016-04-28 | 2021-09-07 | Kolon Industries, Inc. | Fuel cell membrane-electrode assembly |
| CN114182294A (en) * | 2021-11-11 | 2022-03-15 | 深圳市欧格尼绿氢科技有限公司 | Double-catalyst system and method for producing hydrogen by electrochemically degrading biomass refined organic waste |
| CN114182294B (en) * | 2021-11-11 | 2023-11-14 | 深圳市欧格尼绿氢科技有限公司 | Dual-catalyst system and method for producing hydrogen by electrochemical degradation of biomass refining organic wastes |
Also Published As
| Publication number | Publication date |
|---|---|
| DE602007009462D1 (en) | 2010-11-11 |
| KR100953617B1 (en) | 2010-04-20 |
| KR20080037531A (en) | 2008-04-30 |
| CN100547834C (en) | 2009-10-07 |
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