CN101257116A - Catalyst layer for fuel cells and fuel cell using the same - Google Patents
Catalyst layer for fuel cells and fuel cell using the same Download PDFInfo
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- CN101257116A CN101257116A CNA2008100813603A CN200810081360A CN101257116A CN 101257116 A CN101257116 A CN 101257116A CN A2008100813603 A CNA2008100813603 A CN A2008100813603A CN 200810081360 A CN200810081360 A CN 200810081360A CN 101257116 A CN101257116 A CN 101257116A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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Abstract
A general purpose of the present invention is to improve the ion conductivity of a catalyst layer used in a fuel cell. The catalyst layer includes a catalytic metal, a carbon particle, and an ion exchanger. The catalytic metal is carried on the carbon particle. The ion exchanger includes a first functional group capable of being adsorbed or bound to the catalytic metal, and a second functional group providing the ion conductivity. The ion exchanger is adsorbed or bound to the catalytic metal via the first functional group. The bond between the catalytic metal and the ion exchanger includes a covalent bond, a coordinate bond or an ion bond, etc.
Description
Technical field
The present invention relates to a kind of fuel cell, more specifically, the present invention relates to a kind of catalyst layer that in the membrane-electrode assembly of fuel cell of packing into, uses.
Background technology
In recent years, effciency of energy transfer height and get most of the attention by the fuel cell that electric power generation reaction does not produce harmful substance.As one of such fuel cell, known polymer electrolyte fuel cell at the low-temperature working below 100 ℃.
Polymer electrolyte fuel cell, has the basic structure that will be configured in as the solid polymer membrane of dielectric film between fuel electrode and the air electrode, and supply with the fuel gas contain hydrogen to fuel electrode, supplying with the oxidant gas that contains oxygen to air electrode, is the device that generates electricity by following electrochemical reaction.
Fuel electrode: H
2→ 2H
++ 2e
-(1)
Air electrode: 1/2O
2+ 2H
++ 2e
-→ H
2O (2)
Anode and negative electrode, the structure that is obtained by stacked catalyst layer and gas diffusion layers constitutes respectively.The catalyst layer clamping solid polymer membrane subtend configuration of each electrode constitutes fuel cell.Catalyst layer, the layer that forms by ion exchange resin bonding for catalyst-loaded carbon particle.Gas diffusion layers becomes the approach that passes through of oxidant gas or fuel gas.
In anode, the hydrogen that contains in the fuel of supply is decomposed into hydrogen ion and electronics shown in above-mentioned formula (1).Wherein hydrogen ion moves to air electrode in the inside of solid polyelectrolyte membrane, and electronics moves to air electrode by the external circuit.On the other hand, in negative electrode, supply to the oxygen that contains in the oxidant gas of negative electrode, react, shown in above-mentioned formula (2), generate water with hydrogen ion that moves from fuel electrode and electronics.Like this, externally the loop electronics moves to air electrode from fuel electrode, thereby sends electric power.
Summary of the invention
In the past, general catalyst layer is the type of mixing Nafion plasma permutoid in carbon supported catalyst.The catalyst layer that uses in the fuel cell in the past (Nafion mixed type), the utilance of its catalyst metals is low.This is because the three phase boundary of fuel gas and catalyst metals and ion exchanger does not have the effectively cause of formation.Can more specifically enumerate as reason:, have the part (ion exchanger becomes block part) of thickening, so the diffusion of gas is bad, has the cut part of proton conduction path because of evenly not mixing Nafion plasma permutoid in the catalyst metals.
The present invention makes in view of such problem, the technology that its purpose is to provide the fuel gas diffusivity that makes the catalyst layer that uses in the fuel cell and ionic conductivity to improve.
One embodiment of the present invention are the catalyst layer that fuel cell is used.The catalyst layer that this fuel cell is used, it is characterized in that, possess catalyst metals and have adsorbable or be combined in the 1st functional group on the catalyst metals and give the ion exchanger of the 2nd functional group of ionic conductivity, wherein, the 1st functional group absorption or be incorporated into catalyst metals.
According to the catalyst for fuel cell layer of above-mentioned execution mode, owing to the raising of the adaptation between catalyst metals and the ion exchanger and evenly attached on the catalyst metals, so gas diffusibility and ionic conductivity raising.
In the catalyst for fuel cell layer of above-mentioned execution mode, combining of the 1st functional group and catalyst metals can be for chemical bond or based on the combination of electrostatic interaction.As chemical bond, can enumerate covalent bond, coordinate bond, ionic bond etc.
In the catalyst for fuel cell layer of above-mentioned execution mode, the 1st functional group is selected from the group who is made up of at least a kind functional group containing sulphur, oxygen, nitrogen, phosphorus, carbon, boron, halogen atom.
In the catalyst for fuel cell layer of above-mentioned execution mode, ion exchanger can be straight chain polymer.According to this execution mode, extend to fartherly as the proton conduction path of basic point with catalyst metals, therefore, the ionic conductivity of catalyst for fuel cell layer is improved.
In addition, in the catalyst for fuel cell layer of above-mentioned execution mode, ion exchanger can be dendroid branched chain type polymer.Thus, ion exchanger forms dendritic structure, so the three-dimensional expansion of proton conduction path.Its contact between ion exchanger of adjacency as a result increases, and therefore, proton-conducting is improved.In addition, also possess the material with carbon element of catalyst-loaded metal this moment, and the 2nd functional group can join with catalyst metals or material with carbon element.In addition, the 2nd functional group can be sulfonic group, phosphate or their combination.
Another embodiment of the invention is a fuel cell.This fuel cell is characterized in that, possesses dielectric film, is engaged in the negative electrode of a face of dielectric film and the anode that is engaged in another face of dielectric film, and negative electrode and/or anode contain the catalyst of above-mentioned any kind of execution mode.
In the fuel cell of above-mentioned execution mode, can be laminated with diverse catalyst layer.
Description of drawings
Fig. 1 is the perspective view of the structure of the fuel cell of representing that schematically execution mode 1 relates to.
Fig. 2 is the profile of Fig. 1 on the A-A line.
Fig. 3 is the concept map of the structure of the expression catalyst layer that constitutes the anode that execution mode 1 relates to.
Fig. 4 is the concept map of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 2.
Fig. 5 is the significant points expanded view of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 2.
Fig. 6 is the concept map of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 3.
Fig. 7 is the concept map of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 4.
Fig. 8 is the concept map of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 5.
Fig. 9 is the schematic diagram of expression catalyst structure A.
Figure 10 is the concept map of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 6.
Figure 11 is the concept map of the structure of the catalyst layer that has of the fuel cell that relates to of expression execution mode 7.
Figure 12 is the curve chart of the power generation characteristics measurement result of expression embodiment battery 1 and comparative example battery 1.
Embodiment
The below explanation of the execution mode by reference the present invention, but this not delimit the scope of the invention, and just illustration the present invention.
(execution mode 1)
Fig. 1 is the perspective view of structure of schematically representing the electrode catalyst that execution mode 1 relates to and using its fuel cell 10.Fig. 2 is the profile of Fig. 1 on the A-A line.Fuel cell 10 possesses flat battery 50, and is provided with dividing plate 34 and dividing plate 36 in the both sides of this battery 50.A battery 50 only is shown in this example, but can constitutes fuel cell 10 by dividing plate 34 or dividing plate 36 stacked a plurality of batteries 50.Battery 50 has solid polyelectrolyte membrane 20, anode 22 and negative electrode 24.Anode 22 has the duplexer that is made of catalyst layer 26 and gas diffusion layers 28, and same negative electrode 24 has the duplexer that is made of catalyst layer 30 and gas diffusion layers 32.The catalyst layer 26 of anode 22 and the catalyst layer 30 of negative electrode 24, clamping solid polyelectrolyte membrane 20 and subtend setting.
The dividing plate 34 of anode 22 1 side settings is provided with gas flow path 38, and the manifold (not shown) of being used by fuel supply distributes fuel gas to gas flow path 38, by gas flow path 38 to battery 50 fueling gases.Similarly, on the dividing plate 36 of negative electrode 24 1 side settings gas flow path 40 is set, the manifold (not shown) of being supplied with usefulness by oxidant distributes oxidant gas to gas flow path 40, supplies with oxidant gas by gas flow path 40 to battery 50.Particularly, during fuel cell 10 work, by fuel gas for example hydrogen gas flow path 38 in, circulate anode 22 fueling gases from top to bottom along the surface of gas diffusion layers 28.On the other hand, during fuel cell 10 work, by oxidant gas for example air along the surface circulation gas flow path 40 in from top to bottom of gas diffusion layers 32, to negative electrode 24 supply oxidant gas.Thus, in battery 50, react.When catalyst layer 26 hydrogen supplies, the hydrogen in the gas becomes proton by gas diffusion layers 28, this proton in solid polyelectrolyte membrane 20 to negative electrode 24 1 side shiftings.The electronics that emit this moment moves to the external circuit, flows into negative electrode 24 from the external circuit.On the other hand, when catalyst layer 30 air supplies, oxygen combines with proton and forms water by gas diffusion layers 32.Its result externally in the loop electronics flow and can send electric power to negative electrode 24 from anode 22.
Fig. 3 is the concept map of the structure of the expression catalyst layer 26 that constitutes anode 22.Catalyst layer 26 as shown in Figure 3, comprises catalyst metals 60, carbon particle 62, ion exchanger 64.Catalyst metals 60 is supported on the carbon particle 62.Ion exchanger 64 is by the functional group that can adsorb or combine with catalyst metals described later, adsorbs or is incorporated into catalyst metals 60.Catalyst metals 60 combines with ion exchanger 64, can enumerate chemical bond or based on the combination of electrostatic interaction.As chemical bond, can enumerate covalent bond, coordinate bond, ionic bond etc.
As the catalyst metals 60 that on carbon particle 62, supports, can enumerate the alloy or the monomer that for example are selected from Sc, Y, Ti, Zr, V, Nb, Fe, Co, Ni, Ru, Rh, Pd, Pt, Os, Ir, lanthanide series or the actinides.On the carbon particle 62 of catalyst-loaded metal 60, have acetylene black, section's qin carbon black (ケ ッ チ ェ Application Block ラ ッ Network), carbon nano-tube etc. in addition.
The ion exchanger 64 of present embodiment is a straight chain polymer.As straight chain polymer, can enumerate aromatic hydrocarbon or fluorine class ion exchanger etc.
As the straight chain polymer that ion exchanger 64 works, has the functional group that to adsorb or to combine with catalyst metals.As the functional group that can adsorb or combine with catalyst metals, can enumerate-SH ,-NHR ,-NH
2,-N
2H
4,-OH ,-OR ,-SO
3H ,-CN ,-PR
3,-P (OR)
3,-SR
2,-PO
3 2-, disulphide etc. contains a kind of functional group that is selected from sulphur, oxygen, nitrogen, phosphorus, carbon, boron, halogen atom at least.Above-mentioned R can enumerate hydro carbons functional group, functional group of the fragrant same clan, alkoxyl, amide groups or their combination.
In addition, as the straight chain polymer that ion exchanger 64 works, has the functional group that is used to guarantee ionic conductivity.Be used to guarantee the functional group of ionic conductivity, can enumerate sulfonic group, phosphate or their combination more than 1.
According to the catalyst layer 26 of present embodiment, because ion exchanger 64 be the straight chain shape, extend to fartherly from the conduction path of catalyst metals, so can improve ionic conductivity.In addition,, guaranteed the circulating pathway of gas, therefore can improve gas diffusibility because the contact gear ratio between the ion exchanger of adjacency is less.
Get back to the explanation of anode 22, constitute the gas diffusion layers 28 of anode 22, the minute aperture layer that has the anodic gas diffusion substrates and on the anodic gas diffusion substrates, be coated with.The anodic gas diffusion substrates preferably is made of the porous body with electronic conductivity, for example, can use carbon paper, carbon to weave cotton cloth or nonwoven fabrics etc.
The minute aperture layer that is coated with on the anodic gas diffusion substrates is the pasty state homomixture that electroconductive powder and waterproofing agent mixing are obtained.As electroconductive powder, can use for example carbon black.In addition, as waterproofing agent, can use tetrafluoroethylene resin fluorine-type resins such as (PTFE).Waterproofing agent preferably has adhesiveness, and at this, adhesiveness is meant and connects the few or defeated and dispersed easily material of viscosity and can make it have the character of viscosity (state).Because waterproofing agent has adhesiveness,, can obtain sticking with paste by with electroconductive powder and waterproofing agent mixing.
Constituting the catalyst layer 30 and the gas diffusion layers 32 of negative electrode 24, is identical formation with the catalyst layer 26 and the gas diffusion layers 28 that constitute anode 22 respectively.Therefore, omit the explanation of catalyst layer 30 and gas diffusion layers 32.
(catalyst layer manufacture method)
At this, the manufacture method of the catalyst layer that uses in the fuel cell that relates to about present embodiment describes.
At first, the solution of the ion exchanger of the straight chain polymer by will having sulfydryl in carbon supported catalyst mixes, and makes the catalyst layer ink.As carbon supported catalyst, can enumerate the alloy or the monomer that are selected from Sc, Y, Ti, Zr, V, Nb, Fe, Co, Ni, Ru, Rh, Pd, Pt, Os, Ir, lanthanide series or the actinides.
The solution of ion exchanger is meant straight chain polymer dissolving or the solution that disperses.As solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols and ion exchange water etc.As straight chain polymer, can enumerate aromatic hydrocarbon or fluorine class ion exchanger etc.
The mixing ratio of ion exchanger, catalyst and solvent is set at ion exchanger: catalyst: solvent=0.5g: 5g: 9.5g.The ratio of the ion exchanger in the present embodiment in the organic solvent, for above-mentioned 5%, but also can be between 1～20%.The ratio of the ion exchanger in the present embodiment in the catalyst ink is 3%, but also can be between 0.5%～15%.
Then, negative electrode one side, anode one side at dielectric film sprays the catalyst layer ink respectively.Solvent in the catalyst ink carries out drying by hot blast, vacuum, low temperature wind etc.As baking temperature, preferred 80～350 ℃, more preferably 100～250 ℃.Afterwards, by hot pressing (5MPa, 150 ℃, 90 seconds) catalyst layer and dielectric film integral body are carried out thermo-compressed.By above operation, can make the catalyst layer that execution mode relates to.
(execution mode 2)
Fig. 4 is the concept map of the structure of the catalyst layer 26 that has of the fuel cell that relates to of expression execution mode 2.In the present embodiment, as ion exchanger 64, can use dendroid branched chain type polymer.Dendroid branched chain type polymer is the polymer with dendritic branched structure of arbitrary shape.As dendroid branched chain type polymer, can enumerate dendritic (デ Application De リ マ one), dendron (デ Application De ロ Application), dissaving polymer (Ha ィ パ one Block ラ Application チ Port リ マ one) etc.
Dendroid branched chain type polymer and above-mentioned straight chain polymer are same, have can adsorb with catalyst metals 60 or functional group that combines and the functional group that is used to guarantee ionic conductivity.As shown in Figure 5, dendroid branched chain type polymer 80 by the functional group 82 that can adsorb or combine with catalyst metals 60, adsorbs or is combined on the catalyst metals 60.In the present embodiment, at least 1 functional group 84 that is used to guarantee ionic conductivity is connected on the catalyst metals 60 that supports on the carbon particle 62 in addition.As shown in Figure 5, can support a plurality of catalyst metals 60 on the carbon particle 62, at this moment, the functional group 84 of dendroid branched chain type polymer 80 can adsorb with functional group 82 or near catalyst metals 60 catalyst metals 60 of combination are connected.In addition, the functional group 84 of dendroid branched chain type polymer 80 can be connected on the carbon particle 62.
In the present embodiment, because ion exchanger 64 forms dendritic structure, so the three-dimensional expansion of ion (proton) conduction path.Therefore its result can make ion (proton) conductibility improve because the contact between the ion exchanger 64 of adjacency increases.In addition, be used to guarantee that by sulfonic group etc. the conductive functional group of ion (proton) is connected catalyst metals 60, can increase the situation that generates proton.In addition, ion exchanger evenly adheres to homogeneous thickness on catalyst metals 60, so gas diffusibility is good.Carbon particle 62 is very approaching in catalyst layer 26, has therefore fully guaranteed electrical conductivity path (Fig. 3～Fig. 9 is a schematic diagram of emphasizing the ionic conduction path, and the electrical conductivity path is three-dimensionally formed).
(synthetic method) with dendroid branched chain type polymer of sulfydryl
At this, describe about the synthetic method of dendroid branched chain type polymer with sulfydryl.At first, with 3,5-two [3, two (benzyloxy) benzyloxies of 5-] benzyl bromide a-bromotoluene 1.62g (2.0mmol) compd A mixes in solvent (dimethyl sulfoxide (DMSO) (DMSO) 10mL) with thiocarbamide 0.18g (2.4mmol), stirred under the room temperature 12 hours.In the reactant mixture that obtains, add 10wt% NaOH 5mL, stirred 1 hour under the room temperature.Then, regulate pH to 3, extract with ethyl acetate with watery hydrochloric acid.With the ethyl acetate layer dried over mgso that obtains, remove and desolvate.Thus, can obtain the dendroid branched chain type compound with sulfydryl of following chemical formulation.
Change 1
Then, with 10% aqueous sulfuric acid with have the dendroid branched chain type compound of sulfydryl, at room temperature stirred 10 hours.Its result can obtain following chemical formulation, phenyl ring is through dendroid branched chain type ion exchanger sulfonation, that have sulfydryl.
Change 2
(execution mode 3)
Fig. 6 is the concept map of the structure of the catalyst layer 26 that has of the fuel cell that relates to of expression execution mode 3.The catalyst layer 26 that execution mode 3 relates on the formation of the catalyst layer of execution mode 1, also possesses Nafion electrolyte 90 such as (registered trade marks).Thus, the ion exchanger absorption by the straight chain shape or be combined in not on the catalyst metals 60 that is covered by electrolyte 90, active catalyst metals 60 increases, and three bed boundarys increase.
(catalyst layer manufacture method)
At first, use carbon to carry platinum, mix the 5wt%Nafion solution that ァ Le De リ ッ チ company makes as carbon supported catalyst.The combined amount of Nafion is preferably than the catalyst layer amount still less of only making ion exchanger usually of Nafion.Then, add the ion-exchange liquid solution that comprises straight chain polymer by operations such as sprayings.Afterwards, by adopting the manufacture method same, make the catalyst layer that execution mode 3 relates to execution mode 1.
(execution mode 4)
Fig. 7 is the concept map of the structure of the catalyst layer 26 that has of the fuel cell that relates to of expression execution mode 4.The catalyst layer 26 that execution mode 4 relates on the formation of the catalyst layer of execution mode 2, also possesses electrolyte 90 such as Nafion.Thus, by dendroid branched chain type polymer absorption or be combined in not on the catalyst metals 60 that is covered by electrolyte 90, active catalyst metals 60 increases, and three bed boundarys increase.In addition, contact between the dendroid branched chain type polymer by adjacency, the proton conduction path further connects, so ionic conductivity improves.
(catalyst layer manufacture method)
At first, use carbon to carry platinum, mix the 5wt%Nafion solution that ァ Le De リ ッ チ company makes as carbon supported catalyst.The combined amount of Nafion is preferably than the catalyst layer amount still less of only making ion exchanger usually of Nafion.Then, add the ion-exchange liquid solution that comprises dendroid branched chain type polymer by operations such as sprayings.Afterwards, by adopting the manufacture method same, make the catalyst layer that execution mode 4 relates to execution mode 1.
(execution mode 5)
In execution mode 1 and 2, illustration with the example of carbon supported catalyst, but also can use the platinum black that is not supported on the carbon etc. as shown in Figure 8 as catalyst metals 60.In the catalyst layer 26 that execution mode 5 relates to, comprise ion exchanger 64 absorption of dendroid branched chain type polymer or be combined on the catalyst metals 60.Usually platinum black is compared with carbon supported catalyst, and the catalyst metals amount is increased.In addition, also can adsorb on the catalyst metals 60 or in conjunction with straight chain polymer.
(catalyst layer manufacture method)
The catalyst layer of present embodiment, except using platinum black as the catalyst particle, can be by making with the same method of execution mode 1.
Embodiment
(embodiment 1)
As embodiment 1, become the battery of the object lesson of execution mode 5 according to following sequentially built.
(adjusting of catalyst slurry)
In platinum black 5g, add entry 10g, stir as catalyst.In execution mode 2, add DMSO (dimethyl sulfoxide (DMSO)) 9.5g among the dendroid branched chain type ion exchanger 0.5g (referenceization 2) of explanation, stir, make dendroid branched chain type ion exchanger DMSO solution.Add dendroid branched chain type ion exchanger DMSO solution in the catalyst after stirring, obtain mixture.This mixture fully stirred obtain the catalyst slurry.
(catalyst layer making)
The above-mentioned catalyst slurry of spraying makes catalyst reach 4～6mg/cm on above-mentioned gas diffusion layer 32
2, make negative electrode thus.Use the catalyst slurry that in carbon supported platinum catalyst, mixes Nafion about anode,, make catalyst be reached for 0.5mg/cm by silk screen printing
2, on above-mentioned gas diffusion layer 28, form catalyst layer thus.
(making of battery)
Under 150 ℃, 90 seconds, 2.1kN, clamping Nafion film carries out hot pressing between negative electrode and anode, and the making electrode area is 4cm
2Battery.This battery as the battery that embodiment 1 relates to, is used this battery as described later, estimate the characteristic of monocell with Blast Furnace Top Gas Recovery Turbine Unit (TRT).
(execution mode 6)
In above-mentioned execution mode 1 to 5, catalyst layer is an individual layer, is sandwich construction but also can make catalyst layer.In the execution mode 6, as shown in figure 10, catalyst layer 26 has 2 layers of structure that constitute by the 1st layer 100 and the 2nd layers 110.In addition, catalyst layer 30 has and comprises 2 layers of structure of the 1st layer 120 and the 2nd layers 130.Each layer can be set at the combination in any of following catalyst structure.
Carry the catalyst structure A that mixes Nafion in the platinum at present known carbon: particularly, catalyst structure A, as shown in Figure 9, on carbon particle 62, support the catalyst metals 60 that constitutes by platinum, around catalyst metals 60 and carbon particle 62, have the structure of lining Nafion 63.
Shown in the execution mode 1, carry at carbon and to make the ion exchanger absorption that constitutes by straight chain polymer or the catalyst structure B of combination on the platinum
Shown in the execution mode 2, carry at carbon and to make the ion exchanger absorption that constitutes by dendroid branched chain type polymer on the platinum or to be attached to catalyst structure C on the catalyst metals
Shown in the execution mode 3, after mixing Nafion, make the ion exchanger absorption that constitutes by straight chain polymer or the catalyst structure D of combination
Shown in the execution mode 4, after mixing Nafion, make the ion exchanger absorption that constitutes by dendroid branched chain type polymer or the catalyst structure E of combination
The combination of the concrete catalyst structure when the expression catalyst layer is 2 layers of structure in the table 1.
Table 1
| The 1st layer catalyst structure | The 2nd layer catalyst structure | |
| Catalyst configuration example 1 | A | B |
| Catalyst configuration example 2 | A | C |
| Catalyst configuration example 3 | A | D |
| Catalyst configuration example 4 | A | E |
| Catalyst configuration example 5 | C | D |
| Catalyst configuration example 6 | C | E |
| Catalyst configuration example 7 | B | D |
| Catalyst configuration example 8 | B | E |
According to above catalyst layer, gas diffusibility and proton-conducting improve, and three phase boundary is increased.
(execution mode 7)
In execution mode 7, as shown in figure 11, catalyst layer 26 has by the 1st layer of 100, the 2nd layers of 110 and the 3rd layers of 112 3-tier architecture that constitutes.In addition, catalyst layer 30 has by the 1st layer of 120, the 2nd layers of 130 and the 3rd layers of 132 3-tier architecture that constitutes.Each catalyst layer can be set at the combination in any of following catalyst structure.
The combination of the concrete catalyst structure when the expression catalyst layer is 3-tier architecture in the table 2.
Table 2
| The 1st layer catalyst structure | The 2nd layer catalyst structure | The 3rd layer catalyst structure | |
| Catalyst configuration example 9 | A | D | C |
| Catalyst configuration example 10 | A | D | B |
| Catalyst configuration example 11 | A | E | C |
| Catalyst configuration example 12 | A | E | B |
| Catalyst configuration example 13 | A | E | D |
According to above catalyst layer, when keeping three bed boundarys, gas diffusibility and proton-conducting are improved.
(comparative example)
When regulating the catalyst for cathode slurry among the embodiment 1, use dendroid branched chain type ion exchanger (referenceization 2).For with the contrast of embodiment 1,1 use dendroid branched chain type compound (referenceization 1) as a comparative example, use catalyst for cathode slurry is according to following sequentially built battery.
(adjusting of catalyst slurry)
In platinum black 5g, add entry 10g, stir as catalyst.In execution mode 2, add DMSO 9.5g among the dendroid branched chain type compound 0.5g (referenceization 1) of explanation and dissolve, make dendroid branched chain type Compound D MSO solution.Add dendroid branched chain type Compound D MSO solution in the catalyst after stirring, obtain mixture.This mixture fully stirred obtain the catalyst slurry.Use this catalyst slurry, make battery with method similarly to Example 1.
(power generation characteristics test)
Use the battery of embodiment 1 and comparative example 1, carry out the comparison of power generation characteristics separately.Particularly, generate electricity under dividing at 60 ℃ of temperature of generating, hydrogen flow 200ml/ branch, air mass flow 620ml/.Its result as shown in figure 12.Its result becomes sulfonic group by the hydrogen replacement with dendroid branched chain type compound, observes the difference of performance.Become in the sulfonic compound not replacing, do not have ionic conductivity, so proton can not move to dielectric film from catalyst.Therefore think that the reaction pair generating that only takes place makes contributions near dielectric film, thereby on the current density that obtains, difference occurs.
Claims (14)
1. catalyst for fuel cell layer is characterized in that possessing:
Catalyst metals and
Ion exchanger, it has the 2nd functional group adsorbable or that be incorporated into the 1st functional group of described catalyst metals and give ionic conductivity,
Wherein, described the 1st functional group absorption or be incorporated into described catalyst metals.
2. catalyst for fuel cell layer according to claim 1, wherein, described the 1st functional group combines with described catalyst metals, for chemical bond or based on the combination of electrostatic interaction.
3. catalyst for fuel cell layer according to claim 1, wherein, described the 1st functional group is selected from the group who is made up of the functional group of containing in sulphur, oxygen, nitrogen, phosphorus, carbon, boron, the halogen atom at least a kind.
4. catalyst for fuel cell layer according to claim 2, wherein, described the 1st functional group is selected from the group who is made up of at least a kind functional group containing sulphur, oxygen, nitrogen, phosphorus, carbon, boron, halogen atom.
5. catalyst for fuel cell layer according to claim 1, wherein, described ion exchanger is a straight chain polymer.
6. catalyst for fuel cell layer according to claim 2, wherein, described ion exchanger is a straight chain polymer.
7. catalyst for fuel cell layer according to claim 1, wherein, described ion exchanger is a dendroid branched chain type polymer.
8. catalyst for fuel cell layer according to claim 2, wherein, described ion exchanger is a dendroid branched chain type polymer.
9. catalyst for fuel cell layer according to claim 7 wherein, also possesses the material with carbon element that supports described catalyst metals, and described the 2nd functional group is connected with described catalyst metals or described material with carbon element.
10. catalyst for fuel cell layer according to claim 8 wherein, also possesses the material with carbon element that supports described catalyst metals, and described the 2nd functional group is connected with described catalyst metals or described material with carbon element.
11. catalyst for fuel cell layer according to claim 1, wherein, described the 2nd functional group is sulfonic group, phosphate or their combination.
12. catalyst for fuel cell layer according to claim 2, wherein, described the 2nd functional group is sulfonic group, phosphate or their combination.
13. a fuel cell is characterized in that possessing: dielectric film,
Be engaged in described dielectric film a face negative electrode and
Be engaged in the anode of another face of described dielectric film,
Wherein, described negative electrode and/or anode contain each described catalyst for fuel cell layer in the claim 1 to 12.
14. fuel cell according to claim 13 wherein, is laminated with diverse described catalyst layer.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007047983 | 2007-02-27 | ||
| JP2007047983 | 2007-02-27 | ||
| JP2007-047983 | 2007-02-27 | ||
| JP2008009409A JP5393984B2 (en) | 2007-02-27 | 2008-01-18 | Fuel cell |
| JP2008009409 | 2008-01-18 | ||
| JP2008-009409 | 2008-01-18 |
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| Publication Number | Publication Date |
|---|---|
| CN101257116A true CN101257116A (en) | 2008-09-03 |
| CN101257116B CN101257116B (en) | 2013-05-29 |
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|---|---|---|---|
| CN2008100813603A Expired - Fee Related CN101257116B (en) | 2007-02-27 | 2008-02-25 | Catalyst layer for fuel cells and fuel cell using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466205A (en) * | 2009-04-23 | 2015-03-25 | 3M创新有限公司 | Catalyst property control with intermixed inorganics |
| CN109565058A (en) * | 2017-06-23 | 2019-04-02 | 可隆工业株式会社 | Electrode and its manufacturing method including organo-functional's metal oxide, membrane electrode assembly, and the fuel cell including the component |
| CN110603675A (en) * | 2017-05-08 | 2019-12-20 | 宝马股份公司 | Use of electrically conductive carbon materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5388104B2 (en) * | 2009-03-06 | 2014-01-15 | シャープ株式会社 | Power generator and electronic equipment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100347889C (en) * | 2002-10-31 | 2007-11-07 | 松下电器产业株式会社 | Porous electrode, and electrochemical element made using the same |
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2008
- 2008-01-18 JP JP2008009409A patent/JP5393984B2/en not_active Expired - Fee Related
- 2008-02-25 CN CN2008100813603A patent/CN101257116B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466205A (en) * | 2009-04-23 | 2015-03-25 | 3M创新有限公司 | Catalyst property control with intermixed inorganics |
| CN110603675A (en) * | 2017-05-08 | 2019-12-20 | 宝马股份公司 | Use of electrically conductive carbon materials |
| CN110603675B (en) * | 2017-05-08 | 2022-09-02 | 宝马股份公司 | Use of electrically conductive carbon materials |
| CN109565058A (en) * | 2017-06-23 | 2019-04-02 | 可隆工业株式会社 | Electrode and its manufacturing method including organo-functional's metal oxide, membrane electrode assembly, and the fuel cell including the component |
| US11444288B2 (en) | 2017-06-23 | 2022-09-13 | Kolon Industries, Inc. | Electrode comprising organic functional metal oxide, manufacturing method therefor, membrane-electrode assembly comprising same, and fuel cell comprising membrane-electrode assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5393984B2 (en) | 2014-01-22 |
| JP2008243801A (en) | 2008-10-09 |
| CN101257116B (en) | 2013-05-29 |
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