CN1848503A - High polymer electrolyte type fuel cell and manufacturing method therefor - Google Patents
High polymer electrolyte type fuel cell and manufacturing method therefor Download PDFInfo
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- CN1848503A CN1848503A CNA2006100819403A CN200610081940A CN1848503A CN 1848503 A CN1848503 A CN 1848503A CN A2006100819403 A CNA2006100819403 A CN A2006100819403A CN 200610081940 A CN200610081940 A CN 200610081940A CN 1848503 A CN1848503 A CN 1848503A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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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Abstract
The invention discloses a macromolecular electrolytic fuel battery, which is composed of multiple single battery laminations, wherein the single battery possesses hydrogen ion conductive macromolecular electrolytic film, gas diffusing layer with porous material and catalyst layer; the catalyst layer contacts the gas diffusing layer with oxidant gas or fuel gas, which faces the external gap of hydrogen ion conductive macromolecular electrolytic film.
Description
The application is that international application no is PCT/JP 02/02045, and international filing date is that national applications number was the title of CN02800515.5 dividing an application for the Chinese patent application of " gas-diffusion electrode and used the fuel cell of this electrode " after the PCT international application on March 5th, 2002 entered China's stage.
Technical field
The present invention relates to can be used as the fuel cell of mobile device powers plant for emergency uses such as civilian power generation and waste heating system and automobile and used electrode thereof.
Background technology
In the polymer electrolyte fuel cells, oxidant gas such as fuel gas such as the hydrogen of supply and air carry out electrochemical reaction under the catalysis of catalyst such as platinum, produce electricity and hot simultaneously.Here, generally the electrode with fueling gas is called anode, and the electrode of supplying with oxidant gas is called negative electrode.Figure 1 shows that the simple sectional view of the single-cell structure of polymer electrolyte fuel cells in the past.
Among Fig. 1, on two surfaces of carrying hydrionic hydrogen polyelectrolyte membrane 11 selectively, be close to that to have disposed with the carbon dust that is loaded with platinum group metal catalysts be the catalyst layer 12 of main component, be close at the outer surface of catalyst layer 12 and disposed a pair of gas diffusion layers 13 that the leachy porous material of apparatus constitutes.This gas diffusion layers 13 and catalyst layer 12 have constituted diffusion electrode 14.
Disposed the electrolyte film-electrode joint that forms by gas-diffusion electrode 14 and hydrogen polyelectrolyte membrane 11 (below be also referred to as " MEA ") 15 in the outside of gas-diffusion electrode 14 by mechanical fixation, and made between adjacent MEA the dividing plate 17 of connected in electrical series mutually.Have on the surface of this dividing plate 17 gas-diffusion electrode 13 is supplied with as the fuel gas of reacting gas or oxidant gas and will react the water that produces and the gas passage 16 of unnecessary gas discharge.Other member is attached on the dividing plate 17 also can forms gas passage 16, but generally be to utilize cut groove to be set to form gas passage in baffle surface.
In the negative electrode of the fuel cell during work, spread to catalyst layer from gas passage through gas diffusion layers as oxidant gas such as the oxygen of reactivity material or air.What in addition, reaction generated discharges to outside batteries from the pore of gas diffusion layers with unnecessary gas to the excessive moisture of gas diffusion layers infiltration from catalyst layer.
In aforementioned polymer electrolyte fuel cells, therefore hydrogen polyelectrolyte membrane 11 must remain on moisture state with hydrogen polyelectrolyte membrane 11 owing to have the rerum natura that makes the ionic conductance increase along with the increase of moisture content.For this reason, the general method that adopts is in advance to the reacting gas humidification, makes its temperature with regulation, in supply response gas, can guarantee that the hydrogen polyelectrolyte membrane keeps wettability like this.
In addition, the water that electrode reaction generates is with the reacting gas of the gas passage that flows through dividing plate, flows to outlet side from the entrance side of gas passage, discharges to the outside of fuel cell at last.Therefore, the contained water yield of fuel cell reaction gases is different because of the position of gas passage reaction gases flow direction, compare with the reacting gas of gas passage entrance side, the reacting gas of outlet side has only comprised the moisture that is equivalent to the water generation reaction amount, thereby the humidity height.
So, near the outlet side of gas passage, discharge the function reduction of moisture from gas diffusion layers, the problem that produces under opposite extreme situations is, the pore of gas diffusion layers is stopped up by redundant moisture, thereby has hindered the diffusivity of reacting gas, causes cell voltage sharply descend (flooding).In addition, if be suppressed at the flooding that outlet side produces, and supply with the reacting gas reduce humidity in advance from entrance side, then the problem of Chan Shenging is, near owing to the hydrogen polyelectrolyte membrane entrance side moisture content reduces, therefore hydrionic conduction resistance increases, and causes that cell voltage descends.These tendencies are remarkable more when electrode area is big more, and are also remarkable more when the gas passage of dividing plate is long more.
Therefore, the present invention is the invention of finishing in view of aforementioned technical problem in the past, and its purpose is to provide the gas-diffusion electrode that can carry out uniform water management at the Zone Full of MEA, and fuel cell that can long-term stable operation.
In addition, the catalyst layer of gas-diffusion electrode generally utilizes following method to form.Comprise the micro fine carbon dust that is loaded with noble metal and have the solution of polyelectrolyte of hydrogen ion conductivity or dispersion liquid in sneak into dispersants such as water or isopropyl alcohol, obtain catalyst pulp.Utilize silk screen print method or gunite to be coated on the porous materials as electrode base material such as carbon paper or carbon fabric this catalyst pulp, form catalyst layer through super-dry or sintering.Two gas-diffusion electrodes with the above gas diffusion layers that obtains and catalyst layer are engaged by hot pressing across dielectric film, obtain electrolyte film-electrode bond (MEA).In addition, it is also conceivable that a kind of method, promptly on macromolecule membrane, utilize photogravure or coating process painting catalyst slurry, make its dry catalyst layer that forms, then catalyst layer is transferred on the dielectric film.
In order to improve the utilance of catalyst, the catalyst for fuel cell layer should be fine and close as much as possible, in the face of catalyst layer, do not produce spaces such as crack, therefore, can in the catalyst layer slurry, add surfactant etc., suppress the cohesion of carbon granules, improve the dispersiveness of the carbon granules that is loaded with catalyst, reduce the particle diameter of carbon granules as far as possible.For example, utilize planetary ball mill etc. to grind the stronger grinding mechanism of power and can reduce particle diameter of carbon granules etc.In addition, low temperature and long-time reposefully the catalyst pulp of coating is carried out drying produces to suppress the crack as far as possible.
In addition, in order in catalyst layer, to carry out electrode reaction smoothly, must be to catalyst layer supply response gas effectively.For this reason, can adopt following method, promptly use the catalyst layer slurry that contains pore creating material,, form catalyst layer with fine aperture with its coating and sintering.
Add surfactant to improve dispersiveness in catalyst pulp, reduce to be loaded with the particle diameter of the carbon granules of catalyst particle, form catalyst layer as far as possible densely, this angle from the utilance of catalyst itself is effective.But in the catalyst layer of densification, particularly the gas diffusibility of thickness direction is poor.When polymer electrolyte fuel cells is moved with high current density, produce and delay as the water of reaction product is a large amount of.Therefore, exist the obstruction reacting gas in catalyst layer, to spread, can not obtain the problem of gratifying battery performance.
In addition, add under the situation of surfactant, must carry out sintering behind painting catalyst layer slurry, operation just increases like this, and it is complicated that technology will become.Though must adopt method such as planetary ball mill to reduce the particle diameter of carbon granules, otherwise if too small, then as aforementioned, catalyst layer will be too fine and close, battery performance will descend.
Also have in addition and add the method that pore creating material etc. improves gas diffusibility in the catalyst layer slurry, but after catalyst layer coating drying, must carry out sintering, operation increases like this, and the technology complexity that becomes is unfavorable equally.Also having a problem when adding pore creating material is that catalyst layer will be thickeied.
For a long time the catalyst layer slurry of coating is carried out drying with low temperature as far as possible, this needs large-scale drying equipment, from reducing cost and the angle of technology miniaturization considers it is unfavorable.
According to afore-mentioned, require a kind of catalyst utilization that can not reduce as far as possible in the catalyst layer, and keep the manufacture method of the catalyst layer of gas diffusibility.
The announcement of invention
The problem to be solved in the present invention is, in the polymer electrolyte fuel cells field, provides the gas-diffusion electrode that can carry out even water management at the Zone Full of MEA, and polymer electrolyte fuel cells that can long-term stable operation.
The present invention relates to gas-diffusion electrode, this electrode possesses gas diffusion layers and the catalyst layer that comprises porous material, can evenly keep moisture in face.
In the aforementioned gas-diffusion electrode, on the surface of aforementioned catalyst layer one side of aforementioned gas diffusion layers, the stomatal size of aforementioned gas diffusion layers increases to the other end gradually from an end of aforementioned gas-diffusion electrode.
In addition, comprise the macromolecular material with electroconductive particle in the pore of aforementioned gas diffusion layers, the amount of the macromolecular material that comprises in the aforementioned gas holes reduces to the other end gradually from an end of aforementioned gas-diffusion electrode.
In addition, between aforementioned gas diffusion layers and aforementioned catalyst layer, have the electroconductive polymer layer that comprises electroconductive particle and macromolecular material at least, the thickness of aforementioned electroconductive polymer layer reduces to the other end gradually from an end of aforementioned gas-diffusion electrode.
Between aforementioned gas diffusion layers and aforementioned catalyst layer, have the electroconductive particle that comprises 2 kinds of different-grain diameters and the electroconductive polymer layer of macromolecular material, the containing ratio of the electroconductive particle that particle diameter is less reduces to the other end gradually from an end of aforementioned gas-diffusion electrode.
The invention still further relates to the manufacture method of gas-diffusion electrode, this method comprises mixes the step that carbon material, macromolecular material and solvent make solution, aforementioned solution of coating and step that solution amount is gradually changed to the other end from an end of gas diffusion layers on gas diffusion layers, and to being coated with the gas diffusion layers step of heat treatment of aforementioned solution.
The invention still further relates to the manufacture method of gas-diffusion electrode, this method comprises the step that carbon material that average grain diameter is different and solvent make the 1st solution and the 2nd solution, with aforementioned the 1st solution from an end of gas diffusion layers step to other end coating, aforementioned the 2nd solution of coating and step that solution amount is gradually changed to the other end from an end of gas diffusion layers on the gas diffusion layers that has been coated with aforementioned the 1st solution, and to being coated with the gas diffusion layers step of heat treatment of aforementioned solution.
The invention still further relates to polymer electrolyte fuel cells, the feature of this battery is, constitute by a plurality of monocells are stacked, aforementioned monocell possesses the hydrogen polyelectrolyte membrane, have the gas diffusion layers that comprises porous material and catalyst layer and aforementioned catalyst layer towards aforementioned hydrogen polyelectrolyte membrane and the 1st gas-diffusion electrode and the 2nd gas-diffusion electrode of clamping aforementioned hydrogen polyelectrolyte membrane, has the 1st dividing plate from the gas passage of oxidant gas to aforementioned the 1st gas-diffusion electrode that supply with and distribute, has the 2nd dividing plate from the gas passage of fuel gas to aforementioned the 2nd gas-diffusion electrode that supply with and distribute, aforementioned the 1st gas-diffusion electrode is made of aforementioned gas-diffusion electrode, one end of aforementioned the 1st gas-diffusion electrode is positioned at the entrance side of the gas passage of aforementioned the 1st dividing plate, and the other end is positioned at outlet side.
The present invention relates to polymer electrolyte fuel cells, the feature of this battery is, constitute by a plurality of monocells are stacked, aforementioned monocell possesses the hydrogen polyelectrolyte membrane, have the gas diffusion layers that comprises porous material and catalyst layer and aforementioned catalyst layer towards aforementioned hydrogen polyelectrolyte membrane and the 1st gas-diffusion electrode and the 2nd gas-diffusion electrode of clamping aforementioned hydrogen polyelectrolyte membrane, has the 1st dividing plate from the gas passage of oxidant gas to aforementioned the 1st gas-diffusion electrode that supply with and distribute, have the 2nd dividing plate from the gas passage of fuel gas to aforementioned the 2nd gas-diffusion electrode that supply with and distribute, aforementioned catalyst layer has makes aforementioned oxidant gas or fuel gas use the space from the gaseous diffusion towards aforementioned catalyst layer internal circulation that contacts with aforementioned gas diffusion layers.
Aforementioned polymer electrolyte fuel cells can be made by following method, this method comprises that coating comprises the step of the catalyst pulp of the carbon granules, hydrogen polyelectrolyte and the solvent that are loaded with catalyst particle, and the step that makes aforementioned catalyst pulp heat drying formation catalyst layer under temperature different more than 2 kinds of coating.
The meta particle diameter of aforementioned carbon granules is 0.1～10 μ m.
Simple declaration to accompanying drawing
Fig. 1 is the simple sectional view of the single-cell structure of macromolecule electricity Electrolyte type fuel cell in the past.
Fig. 2 is the simple schematic perspective view of the gas-diffusion electrode of embodiment of the present invention 1.
Fig. 3 is the simple stereogram of the structure of gas-diffusion electrode in the past.
Fig. 4 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts Fig. 2 and gas-diffusion electrode shown in Figure 3 and make.
Fig. 5 is the simple schematic perspective view of the gas-diffusion electrode of embodiment of the present invention 2.
Fig. 6 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts Fig. 3 and gas-diffusion electrode shown in Figure 5 and make.
Fig. 7 is the simple schematic perspective view of the gas-diffusion electrode of embodiment of the present invention 3.
Fig. 8 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts Fig. 3 and gas-diffusion electrode shown in Figure 7 and make.
Fig. 9 is the simple schematic perspective view of the gaseous diffusion battery of embodiment of the present invention 4.
Figure 10 is the simple main body schematic diagram of the electroconductive polymer layer 52 of Fig. 9.
Figure 11 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts Fig. 3 and gas-diffusion electrode shown in Figure 9 and make.
Figure 12 is the structure chart of catalyst layer in the past.
Figure 13 is the structure chart of the catalyst layer of the present invention's formation.
Figure 14 is the structure chart of the apparatus for coating that uses among the present invention.
Figure 15 is the performance plot of the fuel cell of the embodiment of the invention 5.
Figure 16 is the performance plot of the fuel cell of the embodiment of the invention 5.
Figure 17 is the performance plot of the fuel cell of the embodiment of the invention 6.
Embodiment
The present invention relates to possess gas diffusion layers and the catalyst layer that comprises porous material, the gas-diffusion electrode that can in face, evenly keep moisture.Thereby gas-diffusion electrode of the present invention can make it can evenly keep moisture in face by various forms.
Execution mode 1
The feature of the gas-diffusion electrode of embodiment of the present invention 1 is, possesses the gas diffusion layers that comprises porous material and the catalyst layer on top thereof, and the stomatal size in the gaseous diffusion aspect increases to the other end gradually from an end of gas-diffusion electrode.Utilize this structure, can carry out uniform water management at the Zone Full of MEA.This is that the more little permeable amount of stomatal size is few more because the permeable amount of gas diffusion layers is relevant with the area of pore, otherwise stomatal size is big more, and then permeable amount is many more.Thereby, when adopting gas-diffusion electrode of the present invention to constitute MEA, can control permeable amount in the MEA face by the area of control pore.
Fig. 2 is the simple schematic perspective view of the gas-diffusion electrode 24a of embodiment of the present invention 1.
As shown in Figure 2, gas-diffusion electrode 24a forms like this, and it disposes the catalyst layer 23 that is made of the carbon granules that is loaded with platinum in the single side surface of the gas diffusion layers 22 that comprises the porous material that is made of carbon fiber 21.Carbon fiber 21 forms pore 211, and shown in arrow among Fig. 2, the area of pore 211 is from the end (R of gas-diffusion electrode 24a
1The end of side) to the other end (L
1The end of side) increases gradually.
In addition, Fig. 3 is the simple stereogram of the structure of gas-diffusion electrode 24b in the past.Though its basic structure is identical with electrode 24a, R
1Side and L
1The structure of side is identical, and the area of pore 211 is basic homogeneous in the face of gas-diffusion electrode.
Fig. 4 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts Fig. 2 and gas-diffusion electrode shown in Figure 3 and make.Be close to configuration gas-diffusion electrode 24a at a side surface of hydrogen polyelectrolyte membrane 25, be close to configuration gas-diffusion electrode 24b on the opposite side surface, make their catalyst layer 23 sides separately to hydrogen polyelectrolyte membrane 25 sides.
Formed the dividing plate 37 of gas passage 26 at its outside configuration one side surface, made air flow to gas-diffusion electrode 24a side, and the hydrogen stream that makes the gas that acts as a fuel is to gas-diffusion electrode 24b side from this gas passage 26 as oxidant gas.
Adopt the polymer electrolyte fuel cells of aforementioned gas-diffusion electrode 24a formation can realize the long-term stability of voltage by negative electrode.This is that the permeable amount at outlet side increases on the contrary because the permeable amount of gas passage entrance side reduces in the negative electrode, has suppressed the cell voltage that drying or flooding because of the hydrogen polyelectrolyte membrane cause and has descended.
The gas-diffusion electrode of embodiment of the present invention 2 possesses the gas diffusion layers that comprises porous material and the catalyst layer on top thereof, have the macromolecular material that comprises electroconductive particle in the pore of gas diffusion layers, the amount of macromolecular material reduces to the other end gradually from an end of gas-diffusion electrode.By adopting this structure, can carry out uniform water management at the Zone Full of MEA.This is because can utilize the macromolecular material amount that exists in the pore to come stomatal size in the control gaseous diffusion electrode face, utilizes the effect identical with execution mode 1, can control the interior permeable amount of MEA face.
Fig. 5 is the simple schematic perspective view of structure of the gas-diffusion electrode 34a of embodiment of the present invention 2.
As shown in Figure 5, gas-diffusion electrode 34a forms like this, and it disposes the catalyst layer 33 that is made of the carbon granules that is loaded with platinum in the single side surface of the gas diffusion layers 32 that comprises the porous material that is made of carbon fiber 31.Carbon fiber 31 forms uniform pore 313 in the gaseous diffusion aspect, have the mixture of electroconductive particle 311 and macromolecular material 312 in this pore, and shown in arrow among Fig. 5, the amount of this macromolecular material 312 is from the end (R of gas-diffusion electrode 34a
2The end of side) to the other end (L
2The end of side) reduces gradually.
Fig. 6 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts aforementioned gas-diffusion electrode 34a and make.Be close to configuration gas-diffusion electrode 34a at a side surface of hydrogen polyelectrolyte membrane 35, be close to the gas-diffusion electrode 24b in the arrangement embodiments 1 on the opposite side surface, make they separately catalyst layer 23 and 33 sides to hydrogen polyelectrolyte membrane 35 sides.
Formed the dividing plate 37 of gas passage 36 at its outside configuration one side surface, made air flow to gas-diffusion electrode 34a side, and the hydrogen stream that makes the gas that acts as a fuel is to gas-diffusion electrode 24b side from this gas passage 36 as oxidant gas.
Adopt the polymer electrolyte fuel cells of aforementioned gas-diffusion electrode 34a formation can realize the long-term stability of voltage by negative electrode.This is that the permeable amount at outlet side increases on the contrary because the permeable amount of gas passage entrance side reduces in the negative electrode, has suppressed the cell voltage that drying or flooding because of the hydrogen polyelectrolyte membrane cause and has descended.
Execution mode 3
The gas-diffusion electrode of embodiment of the present invention 3 possesses the gas diffusion layers of the electroconductive polymer layer that comprises porous material and be made of electroconductive particle and macromolecular material at least at an upper portion thereof and at the catalyst layer on aforementioned electroconductive polymer layer top.In other words, gas-diffusion electrode air inclusion diffusion layer, electroconductive polymer layer and the catalyst layer of embodiment of the present invention 3.And the thickness of aforementioned electroconductive polymer layer reduces to the other end gradually from an end of gas-diffusion electrode, by adopting this structure, can carry out uniform water management at the Zone Full of MEA.This is that this permeable path is long more because permeable amount depends on that water sees through the length in the needed path of gas diffusion layers (permeable path), and permeable amount is few more, otherwise permeable path is short more, and permeable amount is many more.In addition, because the change of the thickness that the length in permeable path can be by gas diffusion layers changes, therefore can easily control the permeable amount in the MEA face.
Fig. 7 is the simple main body schematic diagram of structure of the gas-diffusion electrode 44a of embodiment of the present invention 3.
As shown in Figure 7, gas-diffusion electrode 44a forms like this, the top of the porous material 41 that constitutes at carbon fiber forms the electroconductive polymer layer 42 that is made of electroconductive particle and macromolecular material as gas diffusion layers, the catalyst layer 43 that is made of the carbon particle that is loaded with bat in its surface configuration.Shown in arrow among Fig. 7, the thickness of electroconductive polymer layer 42 is from an end (R of gas-diffusion electrode 44
3The end of side) to the other end (L
3The end) reduce gradually.
In addition, Fig. 8 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts this gas-diffusion electrode 44a and make.Be close to configuration gas-diffusion electrode 44a at a side surface of hydrogen polyelectrolyte membrane 45, be close to arrangement embodiments 1 described gas-diffusion electrode 24b on the opposite side surface, make separately catalyst layer 23 and 43 sides to hydrogen polyelectrolyte membrane 45 sides.
Formed the dividing plate 47 of gas passage 46 at its outside configuration one side surface, made air flow to gas-diffusion electrode 44a side, and the hydrogen stream that makes the gas that acts as a fuel is to gas-diffusion electrode 24b side from this gas passage 46 as oxidant gas.
Adopt the polymer electrolyte fuel cells of aforementioned gas-diffusion electrode 44a formation can realize the long-term stability of voltage by negative electrode.The permeable amount of the entrance side of gas passage reduces in the negative electrode, and the permeable amount at outlet side increases on the contrary, has therefore suppressed the cell voltage that drying or flooding because of the hydrogen polyelectrolyte membrane cause and has descended.
Execution mode 4
The gas-diffusion electrode of embodiment of the present invention 4 has the gas diffusion layers that formed by porous material and the electroconductive polymer layer that is made of different 2 kinds of electroconductive particles of particle diameter and macromolecular material at an upper portion thereof and at the catalyst layer of the top of gas diffusion layers setting.In other words, also air inclusion diffusion layer, electroconductive polymer layer and catalyst layer of the gas-diffusion electrode of embodiment of the present invention 4.And in the aforementioned electroconductive particle, the ratio that the electroconductive particle that particle diameter is little accounts for whole electroconductive particle amounts reduces to the other end gradually from the end of gas-diffusion electrode 44a.By adopting this structure, can carry out uniform water management at the Zone Full of MEA.
In aforementioned gas diffusion layers, mainly be to work as pore in the slit that forms between electroconductive particle, but when adopting the different electroconductive particle of particle diameter, the electroconductive particle that has than small particle diameter enters the slit that forms between the electroconductive particle with greater particle size, with this as pore.Therefore,, then can change the stomatal size in the gaseous diffusion aspect, utilize and execution mode 1 described identical effect, can control the permeable amount in the MEA face if change the ratio that both exist.
Fig. 9 is the simple schematic perspective view of structure of the gas-diffusion electrode 54a of embodiment of the present invention 4.In addition, Figure 10 is the simple schematic perspective view of structure of the electroconductive polymer layer 52 of Fig. 9.
As shown in Figure 9, gas-diffusion electrode 54a forms like this, and it forms electroconductive polymer layer 52 as gas diffusion layers on the surface of the porous material 51 that is made of carbon fiber, the catalyst layer 53 that is made of the carbon particle that is loaded with platinum in its surface configuration.
As shown in figure 10, in electroconductive polymer layer 52, be mixed with the different electroconductive particle of particle diameter 511 and 512.Among Figure 10 shown in the arrow, the combined amount of the electroconductive particle 511 that particle diameter is less is from an end (R of gas-diffusion electrode 54 for another example
4The end of side) to the other end (L
4The end of side) reduces gradually.
In addition, Figure 11 is the simple sectional view of the single-cell structure of the polymer electrolyte fuel cells that adopts this gas-diffusion electrode 54a and make.
Be close to configuration gas-diffusion electrode 54a at a side surface of hydrogen polyelectrolyte membrane 55, be close to arrangement embodiments 1 described gas-diffusion electrode 24b on the opposite side surface, make separately catalyst layer 53 and 23 sides to hydrogen polyelectrolyte membrane 55 sides.
Dispose the dividing plate 57 that a side surface has formed gas passage 56 in its outside, make the air as oxidant gas flow to gas-diffusion electrode 54a side from this gas passage 56, the hydrogen stream that makes the gas that acts as a fuel is to gas-diffusion electrode 24b side.
Adopt the polymer electrolyte fuel cells of aforementioned gas-diffusion electrode 54a formation can realize the long-term stability of voltage by negative electrode.Therefore the entrance side of gas passage has limited permeable amount in the negative electrode, has increased permeable amount at outlet side on the contrary, has suppressed the cell voltage that drying or flooding because of the hydrogen polyelectrolyte membrane cause and has descended.
In the gas-diffusion electrode of aforementioned embodiments 2～4, the particle that electroconductive particle is preferably formed by carbon.Can access the better conductivity gas-diffusion electrode by this structure.This is because carbon has good conductivity.
In the gas-diffusion electrode of aforementioned embodiments 1～4, porous material preferably adopts the carbon paper that is made of carbon fiber, can form the good gas-diffusion electrode of conductivity like this.This is because carbon has good conductivity.
In the gas-diffusion electrode of aforementioned embodiments 2～4, macromolecular material preferably adopts fluorine resin, can obtain the gas-diffusion electrode that can steady in a long-term carry out water management like this.This is because the electrochemical properties of fluorine resin is extremely stable.
Above gas-diffusion electrode can be applicable to polymer electrolyte fuel cells.Thereby, the invention still further relates to polymer electrolyte fuel cells, the feature of this battery is, constitute by a plurality of monocells are stacked, aforementioned monocell possesses the hydrogen polyelectrolyte membrane, have the gas diffusion layers that comprises porous material and catalyst layer and aforementioned catalyst layer towards aforementioned hydrogen polyelectrolyte membrane and the 1st gas-diffusion electrode and the 2nd gas-diffusion electrode of clamping aforementioned hydrogen polyelectrolyte membrane, has the 1st dividing plate from the gas passage of oxidant gas to aforementioned the 1st gas-diffusion electrode that supply with and distribute, has the 2nd dividing plate from the gas passage of fuel gas to aforementioned the 2nd gas-diffusion electrode that supply with and distribute, aforementioned the 1st gas-diffusion electrode is made of the wantonly a kind of gas-diffusion electrode in the aforementioned embodiments 1～4, one end of aforementioned the 1st gas-diffusion electrode is positioned at the entrance side of the gas passage of aforementioned the 1st dividing plate, and the other end is positioned at outlet side.
Execution mode 5
In addition, the invention still further relates to polymer electrolyte fuel cells, the feature of this battery is, constitute by a plurality of monocells are stacked, aforementioned monocell possesses the hydrogen polyelectrolyte membrane, have the gas diffusion layers that comprises porous material and catalyst layer and aforementioned catalyst layer towards aforementioned hydrogen polyelectrolyte membrane and the 1st gas-diffusion electrode and the 2nd gas-diffusion electrode of clamping aforementioned hydrogen polyelectrolyte membrane, has the 1st dividing plate from the gas passage of oxidant gas to aforementioned the 1st gas-diffusion electrode that supply with and distribute, have the 2nd dividing plate from the gas passage of fuel gas to aforementioned the 2nd gas-diffusion electrode that supply with and distribute, aforementioned catalyst layer has makes aforementioned oxidant gas or fuel gas use the space from the gaseous diffusion towards aforementioned catalyst layer internal circulation that contacts with aforementioned gas diffusion layers.
In this fuel cell, owing to be provided with the space that can improve the gaseous diffusion ability in the face of catalyst layer, therefore compare with the battery that possesses fine and close catalyst layer, battery performance increases.When particularly moving with high current density, the raising of performance is more remarkable.
In addition, the present inventor also finds, makes the ratio in this space reach at 0.1～30% o'clock, and the decline of the utilance of catalyst is also not obvious.This space can form by the drying condition of controlling the catalyst pulp that is coated with on the porous material, does not need special in addition device.
When the meta particle diameter that is loaded with the carbon granules of catalyst particle is 0.1～10 μ m, the carbon granules of formation can be especially not little can be not big especially yet, can make catalyst layer with stable space.
Aforementioned catalyst layer forms by following 2 steps, i.e. coating comprises the step of catalyst pulp of the carbon granules, hydrogen polyelectrolyte and the solvent that are loaded with catalyst particle and the aforementioned catalyst pulp that will be coated with carries out heat drying formation catalyst layer under temperature different more than 2 kinds step.By adopting the different baking temperatures in 2 stages, can under the condition that does not add pore creating material etc., in the catalyst aspect, form the space.
Figure 13 is the structure of the catalyst layer of the present invention's formation, and Figure 12 is the structure of catalyst layer in the past.Figure 12 (a) is the vertical view of catalyst layer in the past, and Figure 12 (b) is the X-X line sectional view in (a).As shown in Figure 12, do not have the space in the catalyst aspect in the past, obtain very fine and close filming.
Different therewith is, Figure 13 (a) is the vertical view of catalyst layer of the present invention, and Figure 13 (b) is the Y-Y line sectional view in (a).As shown in Figure 13, have the space at random in the catalyst aspect of the present invention, the space is through the thickness direction of catalyst layer.The gas diffusibility of catalyst layer thickness direction is compared with the past to increase.Void shape can also be fracture shape or circle etc. except shape shown in Figure 13.
Following to the present invention will be described in more detail by embodiment, but the present invention is not limited only to this.
Embodiment 1
(1) manufacturing of gas-diffusion electrode
In the present embodiment, make the gas-diffusion electrode of aforementioned embodiments shown in Figure 21.At first, carbon fiber is placed in the mould with definite shape, changes its amount in face, apply uniform pressure forming, make the porous material a of stomatal size with change in location in the face.
Utilize optics to show the surface that the emblem mirror is observed the porous material a that obtains, consequently, average stomatal size is (R at one end
1Side) be 5.23 * 10
-9m
2, at the other end (L
1Side) be 2.08 * 10
-8m
2, thickness is 360 μ m.
In addition, porous material a is divided into R with mid portion in the face
1Side and L
1Side utilizes gravimetric method (JISZO 208) to measure each permeable amount, consequently, and R
1Side is 1.0 * 10
4G/m
224h, L
1Side is 2.8 * 10
4G/m
224h, i.e. R
1The permeable amount of side reduces L
1The permeable amount of side increases.
Then, be that the carbon dust (the furnace black EC that Dutch AKZO chemie company produces) of 3 μ m is immersed in the chloroplatinic acid aqueous solution with particle diameter, utilize reduction to handle the caltalyst that obtains being loaded with platinum catalyst on the carbon dust surface, the weight ratio of carbon and contained platinum is 1: 1.
Then, the caltalyst that obtains is dispersed in the alcohol dispersion liquid (the Off レ ミ オ Application that Asahi Glass (strain) is produced) of polyelectrolyte, obtain slurry, this slurry is uniformly coated on the one side of the aforementioned porous material a that constitutes gas diffusion layers, form catalyst layer, obtain gas-diffusion electrode a.
In addition, except the amount that makes carbon fiber in face certain, other operate the identical porous material b that obtains.The average stomatal size of porous material b is evenly in face, is 1.08 * 10
-8m
2, thickness is 360 μ m.In addition, permeable amount is 1.8 * 10
4G/m
224h.A is identical with gas-diffusion electrode, obtains gas-diffusion electrode b by porous material b.
(2) manufacturing of polymer electrolyte fuel cells
The gas-diffusion electrode a of identical size and gas-diffusion electrode b are arranged on the two sides of the hydrogen polyelectrolyte membrane (Nafion 112 that du pont company is produced) than the big circle of these electrode sizes, make that the face with catalyst layer is relative with the hydrogen polyelectrolyte membrane respectively.Again with the silicon rubber gasket of thick 250 μ m after the aligned position of two sides, with 130 ℃ of hot pressing of carrying out 5 minutes, obtain MEA.
Then,, make monocell at the both sides of MEA configuration dividing plate, 4 monocells are stacked, obtain battery pack (polymer electrolyte fuel cells of the present invention).As dividing plate, adopt the bubble-tight carbon dividing plate of having of thick 4mm.In addition, on the surface that contacts with gas-diffusion electrode, utilize cut to form the gas passage of wide 2mm, dark 1mm.
Top and bottom configuration SUS 304 system metal end plates in battery pack are fixed.In gas-diffusion electrode a, make its R
1Side is positioned at the gas passage entrance side of dividing plate, L
1Side is positioned at the gas passage outlet side.
Then, from the gas passage entrance side of the dividing plate of gas-diffusion electrode a side to the outlet side air supply, in addition from the gas passage entrance side of the dividing plate of gas-diffusion electrode b side to the outlet side hydrogen supply, under the condition of 75 ℃ of coefficient of oxygen utilization 40%, hydrogen utilance 70%, 85 ℃ of hydrogen humidification bubbler temperature, 65 ℃ of air wetting bubbler temperature and battery temperatures, make fuel cell operation.
Consequently, polymer electrolyte fuel cells is still kept initial voltage behind the long-play that continues more than 3000 hours, and operation work is highly stable.This is because the polymer electrolyte fuel cells of present embodiment can remain on moisture state with polyelectrolyte, in addition can be safely and promptly get rid of because of generating the excessive moisture that water produces.
In addition, stomatal size is not limited to the described size of embodiment, as long as L
1Side is greater than R
1Side just can make polymer electrolyte fuel cells stable operation.
(1) manufacturing of gas-diffusion electrode
In the present embodiment, make the gas-diffusion electrode of aforementioned embodiments shown in Figure 52.At first, acetylene black 10g, fluorine resin (D-1 of Daikin Industries (strain)) 2g and ethanol 50g are mixed stirring, modulate the dispersion liquid a that is dispersed with acetylene black in the fluorine resin.
Then, carry out silk screen printing to the other end, form the different state of dispersion liquid a amount from the end of the used porous material b of embodiment 1.The amount of dispersion liquid a is by from the end of porous material b the adjusting by downforce of squeegee when the other end changes printing.By printing, dispersion liquid a infiltrates among the porous material b.
Then, the porous material b that flooded dispersion liquid a is carried out sintering in 350 ℃, obtain gas diffusion layers c.With the surface of observation by light microscope gas diffusion layers c, consequently, maintain fluorine resin in its pore, in fluorine resin, be dispersed with acetylene black.Confirm in addition, from an end (R of gas diffusion layers
2Side) to the other end (L
2Side) the acetylene black and the amount of fluorine resin increase gradually.
The gas diffusion layers c that obtains is divided into R
2Side and L
2Side is measured its permeable amount respectively, at R
2Side is 0.8 * 10
4G/m
224h, L
2Side is 1.8 * 10
4G/m
224h.Hence one can see that, R
2The permeable amount of side reduces L
2The permeable amount of side increases.
Then, (the furnace black EC that Dutch AKZO chemie company produces) is immersed in the chloroplatinic acid aqueous solution with the carbon dust of particle diameter below 3 μ m, utilizes reduction to handle, and obtains being loaded with on the carbon dust surface caltalyst of platinum catalyst.The weight ratio of carbon and contained platinum is 1: 1.
Then, the caltalyst that obtains is dispersed in the alcohol dispersion liquid (the Off レ ミ オ Application that Asahi Glass (strain) is produced) of polyelectrolyte, obtains slurry, this slurry is uniformly coated on the one side of aforementioned gas diffusion layers c, form catalyst layer, obtain gas-diffusion electrode c.
(2) manufacturing of polymer electrolyte fuel cells
The gas-diffusion electrode c of identical size and gas-diffusion electrode b are arranged on the two sides of the hydrogen polyelectrolyte membrane (Nafion 112 that du pont company is produced) than the big circle of these electrode sizes, make that the face with catalyst layer is relative with the hydrogen polyelectrolyte membrane respectively.Again with the silicon rubber gasket of thick 250 μ m after the aligned position of two sides, with 130 ℃ of hot pressing of carrying out 5 minutes, obtain MEA.
Then,, make monocell at the both sides of MEA configuration dividing plate, 4 monocells are stacked, obtain battery pack (polymer electrolyte fuel cells of the present invention).As dividing plate, adopt the bubble-tight carbon system dividing plate of having of thick 4mm.In addition, on the surface that contacts with gas-diffusion electrode, utilize cut to form the gas passage of wide 2mm, dark 1mm.
In the top and the bottom of battery pack, configuration SUS 304 system metal end plates are fixed.In gas-diffusion electrode c, make its R
2Side is positioned at the gas passage entrance side of dividing plate, L in addition
2Side is positioned at the gas passage outlet side.
Then, from the gas passage entrance side of the dividing plate of gas-diffusion electrode c side to the outlet side air supply, in addition from the gas passage entrance side of the dividing plate of gas-diffusion electrode b side to the outlet side hydrogen supply, under the condition of 75 ℃ of coefficient of oxygen utilization 40%, hydrogen utilance 70%, 85 ℃ of hydrogen humidification bubbler temperature, 65 ℃ of air wetting bubbler temperature and battery temperatures, make fuel cell operation.
Consequently, polymer electrolyte fuel cells is continuing still to keep initial voltage more than 3000 hours behind the long-play, and operation work is highly stable.This be because polymer electrolyte fuel cells of present embodiment can remain on moisture state with polyelectrolyte, in addition can be safely and promptly get rid of because of generating the excessive moisture that water produces.
Embodiment 3
(1) manufacturing of gas-diffusion electrode
In the present embodiment, make the gas-diffusion electrode of aforementioned embodiments shown in Figure 73.At first, with acetylene black (electrolysis of electrochemical industry (strain) black) 10g, mix stirring, be modulated into the dispersion liquid b that is dispersed with acetylene black in the fluorine resin as fluorine resin (D-1 of Daikin Industries (the strain)) 2g of solid constituent.
Then, carry out silk screen printing to the other end, make the coating weight difference of dispersion liquid b by changing by downforce from the end of the used porous material b of embodiment 1.Dispersion liquid b not exclusively infiltrates porous material b, is kept at top as filming.
Then, the porous material b after the coating is carried out sintering with 350 ℃, obtain gas diffusion layers d.Surface with observation by light microscope gas diffusion layers d, the result can confirm to form the thin layer that comprises acetylene black and fluorine resin on the top of porous material b, utilize the thickness of this layer of height difference measuring in addition, the result can confirm that gas diffusion layers d is from one end (R
3Side) to the other end (L
3Side) thickness reduces (d gradually
1→ d
2).
In addition, the gas diffusion layers d that obtains is divided into R
3Side and L
3Side is measured its permeable amount respectively, R
3The permeable amount of side is 0.8 * 10
4G/m
224h, L
3Side is 1.8 * 10
4G/m
224h.Hence one can see that, R
3The permeable amount of side reduces L
3The permeable amount of side increases.
Then, (the furnace black EC that Dutch AKZO chemie company produces) is immersed in the chloroplatinic acid aqueous solution with the carbon dust of particle diameter below 3 μ m, utilizes reduction to handle, and obtains being loaded with on the carbon dust surface caltalyst of platinum catalyst.The weight ratio of carbon and contained platinum is 1: 1.
Then, the caltalyst that obtains is dispersed in the alcohol dispersion liquid (the Off レ ミ オ Application that Asahi Glass (strain) is produced) of polyelectrolyte, obtains slurry, this slurry is uniformly coated on the one side of aforementioned gas diffusion layers d, form catalyst layer, obtain gas-diffusion electrode d.
(2) manufacturing of polymer electrolyte fuel cells
The gas-diffusion electrode d of identical size and gas-diffusion electrode b are arranged on the two sides of the hydrogen polyelectrolyte membrane (Nafion 112 that du pont company is produced) than the big circle of these electrode sizes, make that the face with catalyst layer is relative with the hydrogen polyelectrolyte membrane respectively.Again with the silicone rubber gasket of thick 250 μ m after the aligned position of two sides, with 130 ℃ of hot pressing of carrying out 5 minutes, obtain MEA.
Then,, make monocell at the both sides of MEA configuration dividing plate, 4 monocells are stacked, obtain battery pack (polymer electrolyte fuel cells of the present invention).As dividing plate, adopt the bubble-tight carbon system dividing plate of having of thick 4mm.In addition, on the surface that contacts with gas-diffusion electrode, utilize cut to form the gas passage of wide 2mm, dark 1mm.
In the top and the bottom of battery pack, configuration SUS 304 system metal end plates are fixed.In gas-diffusion electrode d, make its R
3Side is positioned at the gas passage entrance side of dividing plate, L in addition
3Side is positioned at the gas passage outlet side.
Then, from the gas passage entrance side of the dividing plate of gas-diffusion electrode d side to the outlet side air supply, supply with hydrogen from the gas passage entrance side of the dividing plate of gas-diffusion electrode b side to outlet side in addition, under the condition of 75 ℃ of coefficient of oxygen utilization 40%, hydrogen utilance 70%, 85 ℃ of hydrogen humidification bubbler temperature, 65 ℃ of air wetting bubbler temperature and battery temperatures, make fuel cell operation.
Consequently, polymer electrolyte fuel cells is continuing still to keep initial voltage more than 3000 hours behind the long-play, and operation work is highly stable.This be because polymer electrolyte fuel cells of present embodiment can remain on moisture state with polyelectrolyte, in addition can be safely and promptly get rid of because of generating the excessive moisture that water produces.
Embodiment 4
(1) manufacturing of gas-diffusion electrode
In the present embodiment, make the gas-diffusion electrode of aforementioned embodiments shown in Figure 94.At first, the acetylene black of average grain diameter 4 μ m (electrolysis of electrochemical industry (strain) is black) 10g and fluorine resin (D-1 of Daikin Industries (strain)) 2g are mixed stirring, be modulated into the dispersion liquid c that is dispersed with acetylene black in the fluorine resin.In addition, the acetylene black of average grain diameter 1 μ m (electrolysis of electrochemical industry (strain) is black) 10g and fluorine resin (D-1 of Daikin Industries (strain)) 2g are mixed stirring, be modulated into the dispersion liquid d that is dispersed with acetylene black in the fluorine resin.
With dispersion liquid c on the porous material b with certain carry out silk screen printing by downforce after, then with dispersion liquid d on porous material b from one end to the other side one side change by downforce to change the coating weight of dispersion liquid d, one side is carried out silk screen printing.
Then, the porous material b after the coating is carried out sintering with 350 ℃, obtain gas diffusion layers e.Surface with observation by light microscope gas diffusion layers d, the result can confirm, the thin layer that comprises acetylene black and fluorine resin is formed at the top at porous material b, the acetylene black of average grain diameter 4 μ m evenly exists in the face of gas diffusion layers e in this layer, and the acetylene black of average grain diameter 1 μ m is then from the end (R of gas diffusion layers e
4Side) to the other end (L
4Side) reduces gradually.
In addition, the gas diffusion layers e that obtains is divided into R
4Side and L
4Side is measured its permeable amount respectively, R
4The permeable amount of side is 0.8 * 10
4G/m
224h, L
4The permeable amount of side is 1.8 * 10
4G/m
224h.Hence one can see that, R
4The permeable amount of side reduces L
4The permeable amount of side increases.
Then, (the furnace black EC that Dutch AKZO chemie company produces) is immersed in the chloroplatinic acid aqueous solution with the carbon dust of particle diameter below 3 μ m, utilizes reduction to handle, and obtains being loaded with on the carbon dust surface caltalyst of platinum catalyst.At this moment, the weight ratio of carbon and contained platinum is 1: 1.
Then, the caltalyst that obtains is dispersed in the alcohol dispersion liquid of polyelectrolyte, obtains slurry, this slurry is uniformly coated on the one side of aforementioned gas diffusion layers e, form catalyst layer, obtain gas-diffusion electrode e.
(2) manufacturing of polymer electrolyte fuel cells
The gas-diffusion electrode e of identical size and gas-diffusion electrode b are arranged on the two sides of the hydrogen polyelectrolyte membrane (Nafion 112 that du pont company is produced) than the big circle of these electrode sizes, make that the face with catalyst layer is relative with the hydrogen polyelectrolyte membrane respectively.Again with the silicone rubber gasket of thick 250 μ m after the aligned position of two sides, with 130 ℃ of hot pressing of carrying out 5 minutes, obtain MEA.
Then,, make monocell at the both sides of MEA configuration dividing plate, 4 monocells are stacked, obtain battery pack (polymer electrolyte fuel cells of the present invention).As dividing plate, adopt the bubble-tight carbon system dividing plate of having of thick 4mm.In addition, on the surface that contacts with gas-diffusion electrode, utilize cut to form the gas passage of wide 2mm, dark 1mm.
In the top and the bottom of battery pack, configuration SUS 304 system metal end plates are fixed.In gas-diffusion electrode e, make its R
4Side is positioned at the gas passage entrance side of dividing plate, L in addition
4Side is positioned at the gas passage outlet side.
Then, from the gas passage entrance side of the dividing plate of gas-diffusion electrode e side to the outlet side air supply, in addition from the gas passage entrance side of the dividing plate of gas-diffusion electrode b side to the outlet side hydrogen supply, under the condition of 75 ℃ of coefficient of oxygen utilization 40%, hydrogen utilance 70%, 85 ℃ of hydrogen humidification bubbler temperature, 65 ℃ of air wetting bubbler temperature and battery temperatures, make fuel cell operation.
Consequently, polymer electrolyte fuel cells is continuing still to keep initial voltage more than 3000 hours behind the long-play, and operation work is highly stable.This be because polymer electrolyte fuel cells of present embodiment can remain on moisture state with polyelectrolyte, in addition can be safely and promptly get rid of because of generating the excessive moisture that water produces.
Comparative example
Except gas-diffusion electrode being changed into two gas-diffusion electrode b, other operations are same as the previously described embodiments, make polymer electrolyte fuel cells.This polymer electrolyte fuel cells is moved under the described condition of embodiment, and its voltage descends with the ratio of about 1mV/1h, the operation job insecurity.
This is that the hydrogen polyelectrolyte membrane drying of entrance side or the flooding of outlet side have hindered gaseous diffusion because the water management of the MEA inside of this polymer electrolyte fuel cells is ineffective.
Embodiment 5
At first, Nafion solution (U.S.'s aldrich corp is produced) and the water ratio in accordance with regulations of 5 weight % are mixed with the carbon dust (platinum is 50 weight %) that carries platinum, make the catalyst layer slurry.This catalyst layer slurry is divided into 5 parts, (German GETZMANN company produces: Dispermat SL-C12Z), obtaining containing the meta particle diameter respectively is 5 kinds of catalyst layer slurry A, B, C, D and E that carry the platinum carbon dust such as 0.05 μ m, 0.1 μ m, 5 μ m, 10 μ m and 20 μ m with bead grinding dispersion machine.
These slurries are coated on the base material 104 with apparatus for coating shown in Figure 14 101.Use PETG (PET) film (thick 50 μ m, wide 250mm) as base material 104.At first, the catalyst layer slurry is packed in the batch can 102, send the PET film, be coated with by the reel feeding part 103 of apparatus for coating 101.In addition, catalyst layer slurry 106 is coated on the film through slot-shaped nozzle 107 from batch can 102.At this moment, the gap between nozzle and the film is set at 50～250 μ m, send tape speed to be set at the 1m/ branch.The PET film that has been coated with catalyst layer is sent into the hothouse 108 that temperature is set at 60 ℃, take this on film, to form catalyst layer.
Then, measure the catalyst layer A that makes with catalyst layer slurry A, the catalyst layer B that makes with catalyst layer slurry B, the catalyst layer C that makes with the catalyst layer slurry C, the catalyst layer D that makes with catalyst layer slurry D and the face internal pore rate of the catalyst layer E that makes with catalyst layer slurry E.(handle, and handles the about 30mm of measuring range by 2 values by image processing for voidage
2, Image Analyger V10: Toyo Boseki K.K) try to achieve.Table 1 is depicted as the voidage of catalyst layer A～E.
Table 1
| Meta particle diameter (μ m) | Voidage (%) | |
| Catalyst layer A | 0.05 | 0.05 |
| Catalyst layer B | 0.1 | 1.5 |
| Catalyst layer C | 5 | 4 |
| Catalyst layer D | 10 | 15 |
| Catalyst layer E | 20 | 18 |
Clamp polyelectrolyte membrane (Nafion 112, and E.I.Du Pont Company produces) with these catalyst layers A～E, utilize pad to press and obtain conjugant A～E.Then, clamp these conjugants across pad with carbon paper (TGP-H-120 that Dongli Ltd. produces) again, make monocell (fuel cell of the present invention) A～E that comprises electrolyte film-electrode bond A～E.They are placed the monocell experimental rig, test each battery behavior.In the monocell of making, fuel electrodes is supplied with modification analog gas (carbon dioxide 25%, carbon monoxide 50ppm, hydrogen balance gas), to the air pole air supply, carry out humidification at 80 ℃ of battery temperatures, fuel availability 80%, air utilization ratio 40%, to the modification analog gas to make its dew point be 75 ℃ and air carried out humidification to make its dew point be to make fuel cell operation under 60 ℃ the condition.
Figure 15 shows that the I-E characteristic of these batteries.As shown in Figure 15, adopt the performance of the monocell A of the minimum catalyst layer A of voidage to compare, in the characteristic decline of areas of high current density with other batteries.Also know in addition, adopt the entire cell characteristic of the monocell E of the highest catalyst layer E of voidage to descend.
In addition, Figure 16 shows that the current density among Figure 15 is 0.7A/cm
2The time the cell voltage of each battery and the relation of the voidage of the catalyst layer of each used in battery.As shown in Figure 16, the face internal pore rate of catalyst layer is crossed low or too high, and battery performance all can descend.In addition we know, the face internal pore rate of catalyst layer can provide high performance battery about 0.1～15%.
Then, use the catalyst layer slurry C, baking temperature is set at 40 ℃, 60 ℃ and 80 ℃ respectively, as hereinbefore, make catalyst layer C1, C2 and C3, carry out voidage and measure.Consequently, voidage is that 4% the voidage of C1 when baking temperature is 40 ℃ is 2% in the time of 60 ℃, and the voidage of the C3 that baking temperature is 80 ℃ is 6%.The performance that adopts the monocell that these catalyst layers make is tested, and the result shows identical with the performance of aforementioned monocell C.
As mentioned above, adopt the little catalyst layer of voidage,, hindered the diffusion of reacting gas, so battery behavior descends owing to when high current density moves, generate hydropexis in catalyst layer.In addition, adopt the high catalyst layer of voidage, because the integral thickness of catalyst layer increases, near the catalyst polyelectrolyte is not enough, and response area reduces.
Catalyst layer with above-mentioned voidage, can think owing to preserved suitable voidage (0.1～15%), therefore near the catalytic amount the polyelectrolyte is enough, the water that generates because of cell reaction is discharged to the carbon paper as gas diffusion layers rapidly from this space, do not hinder the diffusion of reacting gas, so demonstrate higher battery behavior.
If adopt this method, by the face internal pore rate that the meta particle diameter that changes the catalyst layer slurry comes the control catalyst layer, the utilance that just can suppress catalyst reduces, and obtains high performance battery.In addition, by the control baking temperature, also can change voidage.Have, by the control voidage, use that can fuel cell designs again.
In addition, in the present embodiment, base material adopts the PET film, but also can adopt polypropylene (PP) film etc.Base material is not limited to these materials, also can make forming on the carbon paper of gas diffusion layers directly painting catalyst layer slurry.The composition of catalyst layer slurry, the composition of electrode slurry and drying condition etc. also are not limited to previous embodiment, under the prerequisite of not damaging effect of the present invention different choice can be arranged.
Embodiment 6
At first, the hothouse in the apparatus for coating 101 that change embodiment 5 uses is divided into leading portion and back segment 2 parts with it, the baking temperature of independent respectively control the 1st hothouse and the 2nd hothouse.
Then, with the catalyst layer slurry B that embodiment 5 uses, other conditions are identical with embodiment 5, are coated with above-mentioned improved apparatus for coating 101.At this moment, change drying condition, make catalyst layer B 1～B4, identical with embodiment 5, measure the voidage in the catalyst aspect.Table 2 is depicted as the baking temperature of this moment and the relation of catalyst aspect internal pore rate.
Table 2
| Baking temperature (℃) | Voidage (%) | ||
| The 1st hothouse | The 2nd hothouse | ||
| Catalyst layer B1 | 40 | 80 | 0.06 |
| Catalyst layer B2 | 60 | 80 | 2.0 |
| Catalyst layer B3 | 80 | 80 | 7.5 |
| Catalyst layer B4 | 95 | 80 | 16 |
Hence one can see that, even adopt identical catalyst layer slurry, and also can be by controlling the face internal pore rate that baking temperature comes the control catalyst layer.This is because by changing drying condition, the coherency of polyelectrolyte and the carbon granules of institute's carried catalyst in the catalyst layer is changed, thereby cause the slot-shaped space in the catalyst aspect variation to occur.
With these catalyst layers B1～B4,, measure battery behavior with the embodiment 5 identical monocell B1～B4 that make.The experimental condition of battery is identical with embodiment 5.Figure 17 shows that the current-voltage battery behavior of these monocells.
As shown in Figure 17, among the monocell B1 of the catalyst layer B1 that the voidage in adopting the catalyst aspect is little, the characteristic of areas of high current density descends.Under the situation of having used catalyst layer B1,, therefore has the advantage that can form the low catalyst layer of voidage because the leading portion baking temperature is low, but when moving with high current density, owing to generate hydropexis in catalyst layer, hindered the diffusion of reacting gas, so battery performance descends.
In contrast, under the situation of having used catalyst layer B4, because the leading portion baking temperature than back segment height, rapid solvent evaporates occurs at leading portion, the voidage in the catalyst aspect becomes greatly.Though it is big that voidage becomes, the whole thickening of catalyst layer, near the catalyst the polyelectrolyte is not enough, and response area reduces, so battery performance descends.
Employing has the catalyst layer B2 and the B3 of above-mentioned voidage, because its leading portion baking temperature is lower than back segment, can obtain having the catalyst layer of suitable voidage, therefore the generation water of cell reaction is discharged to the carbon paper as gas diffusion layers rapidly from this space, so just can not hinder the diffusion of reacting gas, demonstrate higher battery behavior.
If adopt method of the present invention, the baking temperature by after the coating of control catalyst layer slurry can access the catalyst layer with suitable voidage, and can further obtain performance and be higher than in the past battery.
The possibility of utilizing on the industry
As above aforementioned, structure for the gas diffusion layers that adopts porous material, the stomatal size that for example makes porous material increases to the other end gradually from an end of gas diffusion layers, so just can adjust the pervious function in the gas diffusion layers face, keep the polyelectrolyte in the MEA to be in moisture state, can get rid of rapidly in addition the excessive moisture that forms because generating water. In addition, utilize this gas diffusion layers to consist of gas-diffusion electrode, and make polymer electrolyte fuel cells, can realize manifesting for a long time like this polymer electrolyte fuel cells of steady-working state.
Claims (2)
1. polymer electrolyte fuel cells, it is characterized in that, constitute by a plurality of monocells are stacked, aforementioned monocell possesses the hydrogen polyelectrolyte membrane, have the gas diffusion layers that comprises porous material and catalyst layer and aforementioned catalyst layer towards aforementioned hydrogen polyelectrolyte membrane and the 1st gas-diffusion electrode and the 2nd gas-diffusion electrode of clamping aforementioned hydrogen polyelectrolyte membrane, has the 1st dividing plate from the gas passage of oxidant gas to aforementioned the 1st gas-diffusion electrode that supply with and distribute, have the 2nd dividing plate from the gas passage of fuel gas to aforementioned the 2nd gas-diffusion electrode that supply with and distribute, aforementioned catalyst layer has makes aforementioned oxidant gas or fuel gas use the space from the gaseous diffusion towards aforementioned catalyst layer internal circulation that contacts with aforementioned gas diffusion layers.
2. the manufacture method of polymer electrolyte fuel cells as claimed in claim 9, it is characterized in that, comprise that coating comprises the step of the catalyst pulp of the carbon granules, hydrogen polyelectrolyte and the solvent that are loaded with catalyst particle, and the step that makes aforementioned catalyst pulp heat drying formation catalyst layer under temperature different more than 2 kinds of coating.
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| WO1998029916A1 (en) * | 1996-12-27 | 1998-07-09 | Japan Storage Battery Co., Ltd. | Gas diffusion electrode, solid polymer electrolyte membrane, method of producing them, and solid polymer electrolyte type fuel cell using them |
| KR100201572B1 (en) * | 1997-04-18 | 1999-06-15 | 최수현 | Method producing electrode for fuel cell with method mixing coating and rolling |
| JP4528386B2 (en) * | 1999-08-18 | 2010-08-18 | 株式会社東芝 | Solid polymer fuel cell and manufacturing method thereof |
-
2001
- 2001-03-08 JP JP2001064573A patent/JP4876318B2/en not_active Expired - Lifetime
-
2002
- 2002-03-05 CN CNB2006100819403A patent/CN100438185C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110050371A (en) * | 2016-09-27 | 2019-07-23 | 凯得内株式会社 | Gas diffusion layer for fuel cell including porous carbon film layer |
| CN111834638A (en) * | 2019-04-19 | 2020-10-27 | 东泰高科装备科技有限公司 | Gas diffusion electrode, preparation method and electrolysis device |
| CN111834638B (en) * | 2019-04-19 | 2022-04-15 | 紫石能源有限公司 | Gas diffusion electrode, preparation method and electrolysis device |
| CN112886042A (en) * | 2021-01-29 | 2021-06-01 | 郑州大学 | Electrolyte structure and method for improving long-term stability of solid oxide fuel cell by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4876318B2 (en) | 2012-02-15 |
| CN100438185C (en) | 2008-11-26 |
| JP2002270187A (en) | 2002-09-20 |
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