CN102598377A - Apparatus for production of catalyst layer for fuel cell, method for production of catalyst layer for fuel cell, polyelectrolyte solution, and process for production of polyelectrolyte solution - Google Patents
Apparatus for production of catalyst layer for fuel cell, method for production of catalyst layer for fuel cell, polyelectrolyte solution, and process for production of polyelectrolyte solution 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
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Abstract
Disclosed are: a catalyst layer for a fuel cell, which enables the smooth procession of an electrochemical reaction; a polyelectrolyte solution; and a process for producing the polyelectrolyte solution. Each of a cathode catalyst layer (93a) and an anode catalyst layer (92a) as illustrated in the working examples is composed of a catalyst paste (42). In the production of the catalyst paste (42), in a water-removing step, 10 g of DE2020, which serves as a pre-solution, is warmed in simmering water until the concentration of water in DE2020 becomes 5%. Subsequently, 32 g of IPA is mixed with the resulting product, and the mixture is agitated using a planetary centrifugal mixer (35) to produce a polyelectrolyte solution (41). In an agitation step, the polyelectrolyte solution (41) is mixed with a pre-paste (40) to produce a catalyst paste (42). The catalyst paste (42) is applied onto base materials (93b, 92b) to produce the cathode catalyst layer (93a) and the anode catalyst layer (92a) which serve as catalyst layers for a fuel cell.
Description
Technical field
The present invention relates to the manufacturing approach of manufacturing approach, polyelectrolyte solution and polyelectrolyte solution of manufacturing installation, the catalyst for fuel cell layer of catalyst for fuel cell layer.
Background technology
Past, the existing fuel cell system that adopts the membrane electrode joint body (MEA:MembranceElectrode Assembly) 90 shown in the patent documentation 1.As shown in Figure 4; This MBA90 has that (registered trade mark, contact air fed negative electrode 93 also contacts fuel such as hydrogen supply also with another side with this dielectric film 91 anode 92 at the dielectric film 91 that the solid polymer membrane of (E.I.Du Pont Company's system) etc. constitutes with the one side of this dielectric film 91 by Nafion.
Also have, anode 92 is made up of above-mentioned base material 92b and the anode catalyst layer 92a that on the one side of this base material, forms.Part on the anode 92 except that anode catalyst layer 92a also is base material 92b, here in the non-electrolyte side, forms the anode diffusion layer of anode catalyst layer 932 diffused fuel.
As shown in Figure 5, cathode catalyst layer 93a and anode catalyst layer 92 be included in the carrier 81a that constitutes by carbon black upload the countless catalyst 18 of putting platinum catalyst metals particulate 81b such as (Pt) and with each catalyst 81 mutually combine simultaneously with figure in the polyelectrolyte 82 that combines of the base material of expression not.As polyelectrolyte 82, adopt the material identical with dielectric film 91.
Through utilizing this MEA90 of dividing plate clamping that does not represent among the figure, constitute the unit of the fuel cell of minimum generating unit, many this unit are stacked together, constitute fuel cell pack.Utilize the air feed mechanism,, utilize the hydrogen feed mechanism, anode catalyst layer 92a hydrogen supply to cathode catalyst layer 93a air supply.Like this, form fuel cell system.
In this MEA90,, from fuel, generate hydrogen ion (H through the electrochemical reaction among the anode catalyst layer 92a
+Proton) and electronics.Then, proton is with hydrone, with H
3O
+Form, move towards cathode catalyst layer 93a in the inside of dielectric film 91.Also have, the load of electronics through being connected with fuel cell system flows to cathode catalyst layer 93a.On the other hand, at cathode catalyst layer 93a, oxygen that contains in the air and proton, proton and electronics are in the same place, and generate water.Through this electrochemical reaction of continuous generation, fuel cell system can produce electromotive force continuously.
[patent documentation 1] Japanese Patent Laid is opened the 2009-104905 communique
Summary of the invention
But the MEA90 in above-mentioned past is under low humidification state, because the drying of the polyelectrolyte of dielectric film and each catalyst layer causes the reduction of performance.Also have, this MEA90 is under high humidification state, and the gas that hydropexis causes is supplied with the reduction that obstacle (water logging) can cause performance.Therefore, the problem that the fuel cell that has this MEA90 exists generating capacity to descend under above-mentioned each environment.
The present invention considers the practical problem in above-mentioned past, and purpose is to obtain smoothly to carry out the catalyst for fuel cell layer of electrochemical reaction.Also have, the object of the present invention is to provide the polyelectrolyte solution that can obtain this catalyst for fuel cell layer and the manufacturing approach of this polyelectrolyte solution.
The manufacturing installation of catalyst for fuel cell layer of the present invention is characterised in that,
As utilizing catalyst pulp to form the manufacturing installation of the catalyst for fuel cell layer of catalyst layer, have
Thereby will in solvent, dissolve water concentration in the preparation solution that polyelectrolyte with the side chain that comprises the hydrophily functional group forms reduce to the water removal body that obtains polyelectrolyte solution below the setting,
Thereby with the preparation slurry that will mix by catalyst and water, mix the rabbling mechanism (claim 1) that obtains above-mentioned catalyst pulp with this polyelectrolyte solution.
Knowledge according to the inventor; For cathode catalyst layer 93a or anode catalyst layer 92a; Between the layer of catalyst 81 and polyelectrolyte 82; Utilize the hydrophily functional group of side chain 101 ends of polyelectrolyte 82, form hydrophilic layer 83, thereby can carry out the counter diffusion and the discharge of moving and generating water of proton and companion's water smoothly.Then, this hydrophilic layer 83 continuous formation ground toward the direction forms catalyst layer, even under low humidification state, also can in hydrophilic layer 83, keep the generation water of generation in the negative electrode 93, prevents that it from inversely spreading to anode 92.Therefore, can prevent the drying of the polyelectrolyte 82 of dielectric film 11 and each catalyst layer, keep high-performance.Also have,, thereby can prevent that performance from reducing even, also can will generate water via hydrophilic layer 83 equally and send crossing under the humidification state.
Here, the inventor to the state of the polyelectrolyte in the polyelectrolyte solution 82, has found following rule in order entirely to form hydrophilic layer 83.That is, shown in Fig. 8 (A), (B), polyelectrolyte 82 has hydrophobic main chain 100 and the side chain 101 that contains the hydrophily functional group.The hydrophilic group functional group is by for example sulfuryl (SO
3 -) constitute.Then; Catalyst 81 is mixed with water as the preparation slurry; To prepare slurry and mix as catalyst pulp with polyelectrolyte solution, the water that hydrophily functional group is attracted on the catalyst 81 attracts, thereby on cathode catalyst layer 93a or anode catalyst layer 92a, forms hydrophilic layer 83.
The inventor finds that if reduce the water concentration in the polyelectrolyte solution, even the concentration of the polyelectrolyte 82 in the polyelectrolyte solution is identical, the viscosity of polyelectrolyte solution also can increase.Also have, the inventor finds that if increase the water concentration in the polyelectrolyte solution, the viscosity of polyelectrolyte solution will reduce.Therefore; The inventor thinks that when the water concentration in the polyelectrolyte solution was higher, water was adsorbed on the side chain 101 of polyelectrolyte 82; Shown in Fig. 8 (A); In polyelectrolyte solution, polyelectrolyte 82 is state of aggregation, thereby makes the viscosity of polyelectrolyte solution reduce.When the water concentration in the polyelectrolyte solution is low; Because the effect of the organic solvent in the polyelectrolyte solution is shown in Fig. 8 (B), in polyelectrolyte solution; Polyelectrolyte 82 scatters, thereby makes the viscosity increased of polyelectrolyte solution.
If mix the polyelectrolyte solution that contains the polyelectrolyte 82 that is condensing, prepare for example cathode catalyst layer 93a, then in this cathode catalyst layer 93a, can think state shown in Figure 9 to occur.That is, in this cathode catalyst layer 93a, because polyelectrolyte 82 is condensing, side chain 101 extends towards a plurality of directions.Because the water among this side chain 101 and the cathode catalyst layer 93a is attached together, therefore in cathode catalyst layer 93a, hydrophilic layer 83 can disperse to form.Like this, in this cathode catalyst layer 93a, in the place of polyelectrolyte 82 cohesions, because the ionic resistance among the cathode catalyst layer 93a, proton and shipwreck are to move in cathode catalyst layer 93a.So, under the low humidification state of zai,, crossing under the humidification state because the drying of the polyelectrolyte 82 in dielectric film 11 and each catalyst layer causes that performance reduces, because causing performance, water logging reduces.
The inventor is in order to address the above problem, and the manufacturing installation of battery of the present invention with catalyst layer invented in research through great efforts.That is, the water removal body that utilizes this manufacturing installation to have makes the water concentration in the polyelectrolyte solution that is obtained be lower than setting, thereby improves viscosity, and in polyelectrolyte solution, the side chain 101 of polyelectrolyte 82 is difficult to adsorbed water.Like this, this polyelectrolyte solution presents state shown in Figure 1, that is, in the polyelectrolyte solution, polyelectrolyte 82 is in released state.Therefore; In utilizing the catalyst pulp of rabbling mechanism and preparation slurry mixing gained; And in the catalyst for fuel cell layer that utilizes this catalyst pulp to obtain, the water in the hydrophily functional group of polyelectrolyte 82, for example sulfuryl and the preparation slurry is attached together.Like this, as shown in Figure 6, in this catalyst for fuel cell layer,, fitly form the hydrophilic layer 83 of polyelectrolyte 82 on the surface of catalyst 81.As stated, behind the water in the sulfuryl absorption preparation slurry, the hydrophily functional group of the side chain 101 of polyelectrolyte 82 is towards catalyst 81 sides (PFF structure), thereby on the catalyst 81 of calalyst layer of fuel cell, forms hydrophilic layer 83.Therefore, utilize in the catalyst for fuel cell layer of this manufacturing installation acquisition, as shown in Figure 5, the proton and the water capacity are prone to move, and electrochemical reaction can be carried out smoothly.So, adopt to have among the MEA90 of this catalyst for fuel cell layer, even, can both improve generating capacity in low humidification state or mistake humidification state.
So, utilize the manufacturing installation of catalyst for fuel cell layer of the present invention, can obtain smoothly to carry out the catalyst for fuel cell layer of electrochemical reaction.
In the manufacturing installation of catalyst for fuel cell layer of the present invention, hope that water removal body is for frying in shallow oil water type (claim 2).At this moment, the water concentration that will prepare solution easily is reduced to below the setting, obtains polyelectrolyte solution of the present invention easily.
Polyelectrolyte solution of the present invention forms by in solvent, having dissolved the polyelectrolyte with the side chain that comprises the hydrophily functional group, and water concentration is less than 10% (claim 3).
Because the water concentration of polyelectrolyte solution of the present invention is less than 10%, at state shown in Figure 1, be in the polyelectrolyte solution, polyelectrolyte 82 is in released state.In the polyelectrolyte 82 of such released state, main chain 100 extends to a direction.Therefore, in being mixed with the catalyst for fuel cell layer of this polyelectrolyte solution, hydrophily functional group is along a direction adsorbed water, and the hydrophilic layer 83 in the catalyst for fuel cell layer is continuous state toward the direction.Therefore, utilize the manufacturing installation of this catalyst for fuel cell layer, the proton and the water capacity are prone to move, and electrochemical reaction can be carried out smoothly.
So polyelectrolyte solution of the present invention is suitable as the polyelectrolyte solution that constitutes the catalyst for fuel cell layer.
According to inventor's result of the test, the water concentration of hoping polyelectrolyte solution is less than 5% (claim 4).At this moment, because the water concentration of polyelectrolyte solution is littler, the polyelectrolyte 82 of polyelectrolyte solution is in the state that separates more, realizes state shown in Figure 1 easily.
Hope that solvent contains at least a (claim 5) of the 2nd grade of alcohol and 3rd level alcohol at least.According to inventor's result of the test,,, can not increase the viscosity of polyelectrolyte solution even reduce moisture concentration if reagent contains just like methyl alcohol or the 1st grade of such alcohol of ethanol.If reagent contains 2nd grade alcohol or the tert-butyl alcohol (TBA) the such 3rd level alcohol such just like isopropyl alcohol (IPA), the polyelectrolyte 82 of polyelectrolyte solution is in the state that separates more.Also have, according to inventor's result of the test, if reagent contains the 2nd grade of alcohol and 3rd level alcohol, the polyelectrolyte 82 of polyelectrolyte solution is in the state of further separation.
The manufacturing approach of polyelectrolyte solution of the present invention is characterised in that, thus have polyelectrolyte that in solvent dissolving has a side chain that comprises the hydrophily functional group prepare the preparation solution preparatory construction of preparation solution,
With from this preparation solution, thereby water concentration is reduced to below 10% the solution modulation engineering (claim 6) that obtains polyelectrolyte solution at least.
Utilize the manufacturing approach of polyelectrolyte solution of the present invention, can stably make polyelectrolyte solution with above-mentioned characteristic.
The manufacturing approach of catalyst for fuel cell layer of the present invention is characterised in that,
As utilizing catalyst pulp to form the manufacturing approach of the catalyst for fuel cell layer of catalyst layer, have
Thereby will in solvent, dissolve water concentration in the preparation solution that polyelectrolyte with the side chain that comprises the hydrophily functional group forms reduce to the engineering that dewaters that obtains polyelectrolyte solution below 10%,
The preparation slurry modulation engineering of mixed catalyst and water, manufacturing preparation slurry,
Thereby with the stirring engineering (claim 7) of in above-mentioned preparation slurry, mixing above-mentioned polyelectrolyte solution acquisition catalyst pulp.
Utilize manufacturing approach of the present invention, in the engineering that dewaters, the water concentration in the polyelectrolyte solution is reduced to below 10%.Therefore, this polyelectrolyte solution has above-mentioned characteristic.Therefore, utilize the formed catalyst for fuel cell layer of catalyst pulp to have above-mentioned characteristic through stirring the engineering acquisition.
So, utilize the manufacturing approach of catalyst for fuel cell layer of the present invention, can obtain smoothly to carry out the catalyst for fuel cell layer of electrochemical reaction.
Description of drawings
Fig. 1 is the simulation drawing of the state of the polyelectrolyte in the polyelectrolyte solution of expression low moisture concentration.
Fig. 2 is the simulation drawing of manufacturing engineering of the polyelectrolyte solution of expression experimental example 1.
Fig. 3 is the simulation drawing of manufacturing engineering of the catalyst pulp of expression embodiment 1,2.
Fig. 4 is the model configuration figure of the EMA of expression past and embodiment 1,2.
Fig. 5 is the simulation amplification sectional view of the EMA of past and embodiment 1,2.
Fig. 6 is the VI simulation amplification sectional view partly of the EMA of embodiment 1,2.
Fig. 7 is the curve of variation of voltage and current density of the battery unit of expression experimental example 2.
Fig. 8 is the simulation drawing of the state of the polyelectrolyte in the expression polyelectrolyte solution in the past.
Fig. 9 is the simulation amplification sectional view of cathode catalyst layer in the past.
Symbol description
42 catalyst pulps, 92a, 93a catalyst layer (92a anode catalyst layer, 93a cathode catalyst layer), 101 side chains, 82 polyelectrolytes, 41 polyelectrolyte solution, 81 catalyst, 40 preparation slurries
Execution mode
Below, with reference to accompanying drawing, embodiment 1,2 and experimental example 1,2 after the present invention specializes are described.
(embodiment 1)
At the cathode catalyst layer 93a and the anode catalyst layer 92a that make embodiment 1,2 shown in Figure 4 and when having the MEA90 of these each catalyst layer 93a, 92a, test at first as follows.In experimental example 1, prepare 6 kinds of polyelectrolyte solution of different structure and manufacturing engineering, measure the viscosity of each polyelectrolyte solution.In addition, the polyelectrolyte solution that in embodiment 1,2 and experimental example 1, is adopted all is ionomer solution.
(manufacturing of sample A)
During the polyelectrolyte solution of perparation of specimen A, at first prepare DE2020 (E.I.Du Pont Company's system) as preparation solution.In container, get the DE2020 of 10g, shown in Fig. 2 (A), fry in shallow oil water, water and normal propyl alcohol (NPA) among the evaporation DE2020 as solvent at 85 ℃.Fry in shallow oil water through this, water among the DE2020 and the content of NPA are all reduced to 2g.Like this, water among the DE2020 and the content of NPA are converted into the concentration in the polyelectrolyte solution of sample A, are equivalent to 5%.
Then, mix the water (with reference to Fig. 2 (B)) of 6.8g among the DE2020 after frying in shallow oil water, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring (with reference to Fig. 2 (C)).In addition, as rotation/revolution formula centrifugal blender 35, adopt " Ha イ Block リ Star De ミ キ サ one HM-500 " of KEYENCE Japan manufactured.
Then, shown in Fig. 2 (D), in the mixture of DE2020 and water, add the NPA of 7.2g.Then, utilize rotation/revolution formula centrifugal blender 35 to stir (with reference to Fig. 2 (E)).Then, shown in Fig. 2 (F), in the mixture of the DE2020 that obtains like this and water and NPA, add the IPA of 20g as organic solvent.Then, utilize rotation/revolution formula centrifugal blender 35 to stir (with reference to Fig. 2 (G)).Thereby obtain the polyelectrolyte solution (with reference to Fig. 2 (H)) of sample A.
(manufacturing of sample B)
During the polyelectrolyte solution of perparation of specimen B, the same with the manufacturing of the polyelectrolyte solution of sample A, the DE2020 of 10g is fried in shallow oil water at 85 ℃, make water and the content of NPA among the DE2020 all reduce to 2g.Like this, water among the DE2020 and the content of NPA are converted into the concentration in the polyelectrolyte solution of sample B, are equivalent to 5%.
Then, mix the IPA of 20g among the DE2020 after frying in shallow oil water, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring.In the mixture of DE2020 that obtains like this and IPA, add the NPA of 7.2g, utilize rotation/revolution formula centrifugal blender 35 to stir.In the mixture of the DE2020 that obtains like this and IPA and NPA, add the water of 6.8g, utilize rotation/revolution formula centrifugal blender 35 to stir.Thereby obtain the polyelectrolyte solution of sample B.
(manufacturing of sample C)
During the polyelectrolyte solution of perparation of specimen C, in the DE2020 of 10g, mix the IPA of 20g, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring.In the mixture of DE2020 that obtains like this and IPA, add the NPA of 4.7g, utilize rotation/revolution formula centrifugal blender 35 to stir.In the mixture of the DE2020 that obtains like this and IPA and NPA, add the water of 5.3g, utilize rotation/revolution formula centrifugal blender 35 to stir.Thereby obtain the polyelectrolyte of sample C.When the polyelectrolyte solution of perparation of specimen C, do not fry in shallow oil water, so the water content among the DE2020 is converted into the concentration in the polyelectrolyte solution of sample C, be equivalent to 9% approximately.Also have, the NPA content among the DE2020 is converted into the concentration in the polyelectrolyte solution of sample C, is equivalent to 11% approximately.
(manufacturing of sample D)
During the polyelectrolyte solution of perparation of specimen D, also the DE2020 with 10g fries in shallow oil water at 85 ℃, makes water and the content of NPA among the DE2020 all reduce to 2g.Like this, water among the DE2020 and the content of NPA are converted into the concentration in the polyelectrolyte solution of sample D, are equivalent to 5%.Then, in this DE2020, mix the NPA of 34g, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring.Thereby obtain the polyelectrolyte solution of sample D.
(manufacturing of sample E)
During the polyelectrolyte solution of perparation of specimen E, also the DE2020 with 10g fries in shallow oil water at 85 ℃, makes water and the content of NPA among the DE2020 all reduce to 2g.Like this, water among the DE2020 and the content of NPA are converted into the concentration in the polyelectrolyte solution of sample E, are equivalent to 5%.Then, in this DE2020, mix the IPA of 34g, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring.Thereby obtain the polyelectrolyte solution of sample E.
(manufacturing of sample F)
During the polyelectrolyte solution of perparation of specimen F, also the DE2020 with 10g fries in shallow oil water at 85 ℃, makes water and the content of NPA among the DE2020 all reduce to 2g.Like this, water among the DE2020 and the content of NPA are converted into the concentration in the polyelectrolyte solution of sample F, are equivalent to 5%.Then, in this DE2020, mix the IPA of 34g: TBA=1: 1 solution, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring.Thereby obtain the polyelectrolyte solution of sample F.
(manufacturing of sample G)
During the polyelectrolyte solution of perparation of specimen G, also the DE2020 with 10g fries in shallow oil water at 85 ℃.But, make the content of water, NPA and polyelectrolyte 82 among the DE2020 be about 33% respectively.Then,, add the NPA of 7.2g, utilize rotation/revolution formula centrifugal blender 35, carry out 3 minutes stirring frying in shallow oil DE2020 behind the water.Then, add the water of 6.8g again, stir, add the IPA of 20g at last, stir, thereby obtain sample G.
For the polyelectrolyte solution of these each sample A-G, measured 20 ℃ viscosity.Mensuration result is as shown in table 1.In addition, in table 1, be benchmark with the viscosity of sample A, represent the ratio of viscosities of each sample B-G with respect to sample A.Also have, in table 1, represent polyelectrolyte, IPA, NPA, H in the polyelectrolyte solution of each sample A-G simultaneously
2Each component ratio of O, TBA and the interpolation of solvent order.
Table 1
As shown in table 1, though each polyelectrolyte solution of sample A-C is same component ratio, difference appears in viscosity.Hence one can see that, and the order of mixed solvent can make viscosity change in DE2020.In more detail, the polyelectrolyte solution of polyelectrolyte solution through comparative sample A and sample B, C can be known through mixing water in DE2020 earlier, can reduce viscosity.Also have, through the polyelectrolyte solution of comparative sample B and the polyelectrolyte solution of sample C, can know before hybrid IP A, promptly the ratio as water among the DE2020 of preparation solution and NPA is big more, and the viscosity of polyelectrolyte solution reduces many more.
In addition, the mensuration result of the polyelectrolyte solution of D per sample, when in DE2020, only sneaking into NPA, viscosity descends.On the other hand, the mensuration result of the polyelectrolyte solution of E and sample F per sample, when in DE2020, sneaking into IPA and when sneaking into IPA and TBA, viscosity raises.Owing to the ratio of the water in the polyelectrolyte solution, be that water concentration is low more, viscosity is then high more, so the polyelectrolyte 82 of the polyelectrolyte solution of sample E and sample F is as shown in Figure 1, main chain 100 is in the state that separates with side chain 101.That is, IPA, IPA and TBA have the effect of the polyelectrolyte 82 that separates in the polyelectrolyte solution.On the contrary, water or NPA have the effect of the polyelectrolyte 82 in the cohesion polyelectrolyte solution.Also have, the effect of the polyelectrolyte 82 in the cohesion polyelectrolyte solution of NPA is higher.
Like this, the 1st grade of alcohol of NPA, ethanol etc. and glassware for drinking water have the effect of cohesion polyelectrolyte, and the 2nd grade of alcohol and the such 3rd level alcohol of TBA that IPA is such have the effect of separating polyelectrolyte.Can think that the above-mentioned effect of the 2nd grade of alcohol and 3rd level alcohol is from dielectric constant.Dielectric constant has the effect of higher cohesion polyelectrolyte less than 20 solvent.
(embodiment 1)
< manufacturing of cathode catalyst layer 93a and anode catalyst layer 92a >
Based on above-mentioned experimental result, made the MEA90 of embodiment shown in Figure 41.The negative electrode 93 of this MEA90 as stated, battery constitutes with the cathode catalyst layer 93a of catalyst layer and the anode catalyst layer 92a of gas diffusion layers base material by acting as a fuel.
At first, make the catalyst pulp 42 that constitutes cathode catalyst layer 93a.When making this catalyst pulp 42, at first be ready to carry the catalyst 81 that obtains behind the Pt particulate of putting as catalyst metals particulate 82 putting density according to carrying of 50wt% on the carrier 81a that constitutes by carbon black.Then, according to the ratio of 1g catalyst 81 with the 5g water yield, mixed catalyst 81 and water utilize rotation/revolution formula centrifugal blender 35, stir, and obtain preparation slurry 40 (with reference to Fig. 3 (A)).
Then, prepare the polyelectrolyte solution 41 mix with this preparation slurry 40.The polyelectrolyte solution of making as sample B in the structure of this polyelectrolyte solution 41 and the above-mentioned experimental example 1 is identical.That is, the water concentration of this polyelectrolyte solution 41 is 22%.In addition, carry out in order to obtain polyelectrolyte solution 41 fry in shallow oil water, promptly, the engineering that dewaters in the manufacturing approach of frying in shallow oil water removal body and catalyst for fuel cell layer of the present invention in the manufacturing installation that water is equivalent to catalyst for fuel cell layer of the present invention during the polyelectrolyte solution of perparation of specimen B.
Then, in above-mentioned preparation slurry 40, mix the polyelectrolyte solution 41 of 10g, shown in Fig. 3 (B), utilize rotation/revolution formula centrifugal blender 35, stir.Like this, make catalyst pulp 42 (with reference to Fig. 3 (C)).In addition, the rabbling mechanism that this rotation/revolution formula centrifugal blender 35 is equivalent in the manufacturing installation of catalyst for fuel cell layer of the present invention.Also have, this rotation/revolution formula centrifugal blender 35 is equivalent to the stirring engineering in the manufacturing approach of catalyst for fuel cell layer of the present invention.
Above-mentioned catalyst pulp 42 is coated to base material 93b, forms cathode catalyst layer 93a.To through carbon black that refusing water treatment and have the cloth lamination as base material of electronic conductivity, obtain base material 93b.In addition, also can be on carbon paper etc., the water repellent layer that the mixture by carbon black and PTFE constitutes is set, obtain base material 93b.Also have, the method as coating catalyst slurry 42 on base material 93b can adopt silk screen printing, spraying process, ink-jet method etc.
After the cathode catalyst layer 93a drying on this base material 93b, obtain negative electrode 93.Also have, anode catalyst layer 92a and negative electrode 92 also obtain through same engineering.
< manufacturing of MEA90 >
According to the order of anode 92, dielectric film (Nafion:NR211) 91 and negative electrode 93, carry out lamination, 140 ℃, utilize the 40kgf/cm that exerts pressure
2Under hot pressing combine.Like this, make MEA90.
Among this MEA90, when make constituting the catalyst pulp 42 of cathode catalyst layer 93a and anode catalyst layer 92a, with the water concentration in the polyelectrolyte solution 41 5% polyelectrolyte solution 41 and prepare slurry 40 and mix.Shown in Fig. 3 (A), in this polyelectrolyte solution 41, polyelectrolyte 82 is in released state.In the polyelectrolyte 82 of such released state, main chain 100 extends to a direction.Therefore, shown in Fig. 3 (C), sulfuryl is adsorbed on one with the water for preparing in the slurry 40.Therefore, as shown in Figure 6, in the cathode catalyst layer 93a and anode catalyst layer 92a that utilize this catalyst pulp 42 to obtain,, fitly form the layer of polyelectrolyte 82 on the surface of catalyst 81.As stated; Behind the water in the sulfuryl absorption preparation slurry 40, in cathode catalyst layer 93a and anode catalyst layer 92a, as shown in Figure 6; The hydrophily functional group of the side chain 101 of polyelectrolyte 82 is towards catalyst 81 sides (PFF structure), thereby on catalyst 81, forms hydrophilic layer 83.Therefore, utilize among the cathode catalyst layer 93a and anode catalyst layer 92a of this manufacturing approach acquisition, as shown in Figure 5, the proton and the water capacity are prone to move, and electrochemical reaction can be carried out smoothly.So, adopt among the MEA90 of cathode catalyst layer 93a with above-mentioned acquisition and anode catalyst layer 92a, even, can both improve generating capacity in low humidification state or mistake humidification state.
So, utilize the manufacturing approach of this embodiment 1, can obtain smoothly to carry out the cathode catalyst layer 93a and the anode catalyst layer 92a of electrochemical reaction, thereby obtain smoothly to carry out the MEA90 of electrochemical reaction.
(embodiment 2)
The MEA90 of embodiment 2 constitutes cathode catalyst layer and anode catalyst layer for the catalyst pulp of polyelectrolyte solution (water concentration 5%) the mixing gained of the sample E of utilization preparation slurry 40 and above-mentioned experimental example 1.Other structure is identical with embodiment 1 with manufacturing approach.
Then, in order to grasp the voltage characteristic of the MEA90 among the embodiment 1,2, utilize the battery unit that has the battery unit of MEA90 and have the MEA of following comparative example, mensuration experimentizes.In addition, the structure of battery unit is identical with well-known structure and method with manufacturing approach.
(comparative example)
The MEA90 of comparative example constitutes cathode catalyst layer and anode catalyst layer for the catalyst pulp of polyelectrolyte solution (water concentration 22%) the mixing gained of the sample A of utilization preparation slurry 40 and above-mentioned experimental example 1.Other structure is identical with embodiment 1,2 with manufacturing approach.
In this experimental example 2; To the battery unit of MEA90 with embodiment 1,2 with have the battery unit of the MEA of comparative example; The setup unit temperature is that 50 ℃, humidity are 100% mensuration environment respectively; Anode 92 flows into hydrogen, and negative electrode 93 flows into air, measures the variation of the electric current and the voltage of each battery unit.Mensuration result is as shown in Figure 7.
Among Fig. 7, transverse axis is represented the current density (A/cm2) of battery unit, and the longitudinal axis is represented battery cell voltage (V).As shown in Figure 7, the reduction of the current density when reducing for voltage is minimum in the battery unit of the MEA90 with embodiment 2.That is, the generating capacity of the MEA90 of embodiment 2 is for the highest.
According to this result of implementation, the viscosity of polyelectrolyte solution is high more, and the generating capacity of MEA90 is also high more.That is, electrochemical reaction is carried out smoothly.In addition, comparative examples and embodiment 1 find that the viscosity of polyelectrolyte solution is big more under the identical situation of water concentration in polyelectrolyte solution, and the generating capacity of MEA is also high more.
In above-mentioned, utilize embodiment 1,2 that the present invention has been described, but the present invention is not limited to the foregoing description 1,2.Under the prerequisite of the scope that does not break away from it, can carry out suitable change.
Utilize possibility on the industry
The present invention can be applied to electric automobile etc. mobile with power supply, or fixedly use power supply.
Claims (7)
1. the manufacturing installation of a catalyst for fuel cell layer is characterized in that,
As utilizing catalyst pulp to form the manufacturing installation of the catalyst for fuel cell layer of catalyst layer, have
Thereby will in solvent, dissolve water concentration in the preparation solution that polyelectrolyte with the side chain that comprises the hydrophily functional group forms reduce to the water removal body that obtains polyelectrolyte solution below the setting,
Thereby with the preparation slurry that will mix by catalyst and water, mix the rabbling mechanism that obtains above-mentioned catalyst pulp with this polyelectrolyte solution.
2. the manufacturing installation of the described catalyst for fuel cell layer of claim 1 is characterized in that:
Above-mentioned water removal body is for frying in shallow oil the water type.
3. polyelectrolyte solution is characterized in that:
Form by in solvent, having dissolved the polyelectrolyte with the side chain that comprises the hydrophily functional group, water concentration is less than 10%.
4. the described polyelectrolyte solution of claim 3 is characterized in that,
Water concentration is less than 5%.
5. claim 3 or 4 described polyelectrolyte solution is characterized in that:
Above-mentioned solvent contains at least a in the 2nd grade of alcohol and the 3rd level alcohol at least.
6. the manufacturing approach of a polyelectrolyte solution is characterized in that:
Thereby have in solvent polyelectrolyte that dissolving has a side chain that comprises the hydrophily functional group prepare the preparation solution preparatory construction of preparation solution,
With from this preparation solution, thereby water concentration is reduced to below 10% the solution modulation engineering that obtains polyelectrolyte solution at least.
7. the manufacturing approach of a catalyst for fuel cell layer is characterized in that:
As utilizing catalyst pulp to form the manufacturing approach of the catalyst for fuel cell layer of catalyst layer, have
Thereby will in solvent, dissolve water concentration in the preparation solution that polyelectrolyte with the side chain that comprises the hydrophily functional group forms reduce to the engineering that dewaters that obtains polyelectrolyte solution below 10%,
The preparation slurry modulation engineering of mixed catalyst and water, manufacturing preparation slurry,
Thereby with the stirring engineering of in above-mentioned preparation slurry, mixing above-mentioned polyelectrolyte solution acquisition catalyst pulp.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010002362 | 2010-01-07 | ||
| JP2010-002362 | 2010-01-07 | ||
| JP2010-288034 | 2010-12-24 | ||
| JP2010288034 | 2010-12-24 | ||
| JP2010-291730 | 2010-12-28 | ||
| JP2010291730A JP5565305B2 (en) | 2010-01-07 | 2010-12-28 | Fuel cell catalyst layer manufacturing apparatus, fuel cell catalyst layer manufacturing method, polymer electrolyte solution, and polymer electrolyte solution manufacturing method |
| PCT/JP2011/050169 WO2011083842A1 (en) | 2010-01-07 | 2011-01-07 | Apparatus for production of catalyst layer for fuel cell, method for production of catalyst layer for fuel cell, polyelectrolyte solution, and process for production of polyelectrolyte solution |
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| CN102598377A true CN102598377A (en) | 2012-07-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105591140A (en) * | 2014-11-10 | 2016-05-18 | 丰田自动车株式会社 | Method of producing dispersion liquid of gelatinous electrolyte |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06260170A (en) * | 1993-03-01 | 1994-09-16 | Agency Of Ind Science & Technol | Electrode catalyst composition and highpolymer film type electrode |
| CN1744360A (en) * | 2004-09-01 | 2006-03-08 | 中国科学院大连化学物理研究所 | Composite catalytic layer proton exchange membrane fuel cell electrode and manufacture method thereof |
| JP2006066309A (en) * | 2004-08-30 | 2006-03-09 | Gs Yuasa Corporation:Kk | Method of manufacturing catalyst for solid polymer type fuel cell |
| JP2008300160A (en) * | 2007-05-31 | 2008-12-11 | Hitachi Maxell Ltd | Forming method of coating film, manufacturing method of fuel cell, and application device |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06260170A (en) * | 1993-03-01 | 1994-09-16 | Agency Of Ind Science & Technol | Electrode catalyst composition and highpolymer film type electrode |
| JP2006066309A (en) * | 2004-08-30 | 2006-03-09 | Gs Yuasa Corporation:Kk | Method of manufacturing catalyst for solid polymer type fuel cell |
| CN1744360A (en) * | 2004-09-01 | 2006-03-08 | 中国科学院大连化学物理研究所 | Composite catalytic layer proton exchange membrane fuel cell electrode and manufacture method thereof |
| JP2008300160A (en) * | 2007-05-31 | 2008-12-11 | Hitachi Maxell Ltd | Forming method of coating film, manufacturing method of fuel cell, and application device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105591140A (en) * | 2014-11-10 | 2016-05-18 | 丰田自动车株式会社 | Method of producing dispersion liquid of gelatinous electrolyte |
| CN105591140B (en) * | 2014-11-10 | 2018-06-19 | 丰田自动车株式会社 | The manufacturing method of the dispersion liquid of gel-like electrolyte |
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