CN1770518A - Polymer electrolyte fuel cell and production method of the same - Google Patents
Polymer electrolyte fuel cell and production method of the same Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
A polymer electrolyte type fuel cell comprising a hydrogen ion-conductive polymer electrolyte film, an anode and a cathode between which the electrolyte film is sandwiched, an anode-side conductive separator having a gas passage for feeding a fuel gas to the anode, and a cathode-side conductive separator having a gas passage for feeding a gaseous oxidizing agent to the cathode, wherein the anode and the cathode each comprises a catalyst layer in contact with the electrolyte film and a gas diffusion layer in contact with the catalyst layer and the separator, and at least one of the anode and the cathode contains a compound represented by the formula (1): R1-O-{(C2H4O)n-(C3H6O)m}-R2 (wherein R1 and R2 each is C5-15 alkyl or hydrogen and n and m each is an integer satisfying the relationships 0 = n = 5, 0 = m = 5, and 1 = n + m = 5, provided that when neither n nor m is 0, then the at least one ethylene oxide unit and at least one propylene oxide unit are randomly arranged).
Description
The application be that March 5, application number in 2002 are 02801513.4 the applying date, denomination of invention divides an application for the patent application of " polymer electrolyte fuel cells and preparation method thereof ".
Technical field
The present invention relates to directly to use liquid fuels such as gaseous fuels such as hydrogen or methyl alcohol, ethanol, dimethyl ether and oxidants such as air, oxygen polymer electrolyte fuel cells, be particularly related to its electrode.
Background technology
The general structure of polymer electrolyte fuel cells in the past at first is described.
The fuel cell that uses polyelectrolyte is by making the fuel gas that contains hydrogen and air etc. contain the oxidant gas generation electrochemical reaction of aerobic, making it produce electric power and heat simultaneously.
Fig. 1 illustrates the section sketch map of the electrolyte film-electrode joint (MEA) 15 of polymer electrolyte fuel cells.MEA constitutes by hydrogen polyelectrolyte membrane 11 with in the pair of electrodes 14 of dielectric film 11 both sides configurations.And each electrode is by constituting with the adjacent catalyst layer 12 of dielectric film 11 with the adjacent gas diffusion layers 13 of catalyst layer 12.Catalyst layer 12 is to have the carbon particle of platinum group metal catalysts particle and the mixture of hydrogen polyelectrolyte to form by load.
At present, the following structural formula of general use in the dielectric film 11:
Change I
Shown perfluorocarbon sulfonic acid and the copolymer of polytetrafluoroethylene (hereinafter referred to as perfluorocarbon sulfonic acid), Na Feiang (Nafion) film that for example well-known Dupont (Du Pont) company makes or the like.
In the gas diffusion layers 13, employing carbon paper etc. has the conductivity porous matter base material of gas permeability.Also can carry out hydrophobic treatment to conductivity porous matter base material.
Dispose encapsulants such as pad around the electrode 14, its clamping dielectric film 11.Encapsulant is in order to prevent that fuel gas and the oxidant gas of supplying with electrode from leaking into outside or mixing mutually.Encapsulant and MEA form an integral body.
Fig. 2 illustrates the section sketch map of the monocell 23 of polymer electrolyte fuel cells.Monocell 23 is to constitute by MEA15 with at the pair of conductive dividing plate 21 of MEA both sides configurations.Conducting diaphragm 21 has the effect of mechanical fixation MEA.Dividing plate 21 with the adjacent face of MEA15 on be formed with gas flow path 22 so as to electrode fueling gas or oxidant gas, and the water and the unnecessary gas that generate in electrode reaction carried out.Gas flow path 22 also can be arranged with dividing plate in 21 minutes, but generally was to adopt the mode that forms gas flow path 22 at the baffle surface fluting.By to side's gas flow path fueling gas, supply with oxidant gas to the opposing party's gas flow path, from a monocell 23, can produce the electromotive force about 0.8V.
Usually, for obtain the three ten-day period of hot season～voltage of hundreds of volts, a plurality of monocells 23 are together in series.Therefore, the two sides of dividing plate 21 all is formed with gas flow path 22, according to the order of dividing plate/MEA/ dividing plate/MEA monocell is coupled together.
In the gas flow path, by the manifold supply gas.Manifold has two types.A kind of is that a plurality of branches head of supply air line directly is linked in the gas flow path, and such manifold is called external manifold.Another kind is through hole to be set as supply air line being provided with on the dividing plate of gas flow path, and the gateway of gas flow path and through hole are communicated with, and such manifold is called internal manifold.
Three kinds of functions of gas diffusion layers below are described.
The first, gas diffusion layers has the even fueling gas of catalyst particle in catalyst layer or the diffusion gas function of oxidant gas.
The second, gas diffusion layers has the function that the water that generates at catalyst layer is transported to gas flow path rapidly.
The 3rd, gas diffusion layers has the function that the electronics of reaction is participated in transmission.
As mentioned above, gas diffusion layers must have excellent gas permeability, permeable steam and conductivity.Therefore, the conductivity porous matter base material that the past uses the more carbon paper in space, carbon cloth, carbon felt etc. to constitute is always made gas diffusion layers, to guarantee gas permeability.Adopt in gas diffusion layers the high molecular method of dispersing hydrophobic to guarantee permeable steam in addition.Also by in gas diffusion layers, using conductive materials such as carbon fiber, metallic fiber, micropowder to guarantee electric conductivity.
Four kinds of functions of catalyst layer below are described.
The first, catalyst layer has the function that fuel gas or oxidant gas from the gas diffusion layers supply are supplied to reactive site.
The second, catalyst layer has the function that the hydrogen ion of participating in reaction is transferred to dielectric film rapidly.
The 3rd, catalyst layer has the function that the electronics of reaction is participated in transmission.
The 4th, catalyst layer has the response area and active high catalyst, the function that redox reaction is carried out rapidly that provides big.
More than narration clearlys show that catalyst layer must have excellent gas permeability, saturating hydrogen ion, conductivity, and also must have excellent performance as reacting environment.Therefore, from beginning just to form the catalyst layer precursor very early, remove the method for pore-forming material then and guarantee gas permeability by mixture with space carbon particle how and pore-forming material.Guarantee hydrogen ion by near formation hydrogen ions travel net polyelectrolyte being dispersed in catalyst particle.Also further guarantee conductivity by constituting catalyst carrier with conductive materials such as carbon particle, carbon fibers.Also, improve the dispersive property of catalyst particle in the catalyst layer, good reacting environment is provided by the big fine catalyst particle of several nm that load is made up of the high platinum metal of activity on carrier.
So far, in the electrode of fuel cell in the past, have following problem.
At first, gas permeability, water vapor permeability and the conductivity that has an electrode is the problem of opposite characteristic each other respectively.For example, in order to improve the gas permeability of electrode, use the less carbon fiber of diameter to form the voidage of gas diffusion layers or raising gas diffusion layers, so, the conductivity of gas diffusion layers will descend.In addition,, in gas diffusion layers, add hydrophobic polymer, can reduce the gas permeability and the conductivity of gas diffusion layers like this in order to improve the performance of permeable steam.So gas diffusion layers just can not constitute with single material, but form the layer that forms by carbon fiber and by carbon particle and hydrophobic polymer form layer composite construction take into account opposite performance.Simultaneously, in order to obtain the fine dispersion state of carbon particle and hydrophobic polymer, surfactant has been used in research.For example studied modulation by the hydrophobic printing ink (イ Application Network) that carbon particle, hydrophobic polymer, surfactant and decentralized medium constitute, hydrophobic printing ink has been coated to the method for preparing gas diffusion layers on the conductivity porous matter base material.But the example that relevant surfactant studies in great detail but seldom.
Te Kaiping 11-335886 communique, spy open flat 11-269689 communique, spy and open flat 11-50290 communique, spy and open flat 10-092439 communique and the flat 6-116774 communique of Te Kai and announced that octyl phenol ethylate (Octyl phenolethoxylate) with induced by alkyl hydroxybenzene is as the situation that hydrophobic polymer is dispersed in the surfactant in the hydrophobic printing ink.Also have special fatty acid soaps, alkylbenzenesulfonate, alkylallyl sulfonate and the alkylnaphthalene sulfonate that flat 6-036771 communique has been announced anion system of opening; Alkylamine salt, amido link amidic-salt, ester bond amine salt, alkylammonium salt, amido link ammonium salt, ester bond ammonium salt, ehter bond ammonium salt, Fixanol and the ester bond pyridiniujm of cation system; The chain alkyl amino acid of amphion system; Alkyl allyl ether, alkyl ether, alkylamine fatty glyceride, anhydrous D-sorbite fatty acid ester, polyethylene imide and the fatty acid alkyl alcohol amide of nonionic system.But, in the embodiment of above-mentioned document, only studied the octyl phenol ethylate of induced by alkyl hydroxybenzene.Therefore, above-mentioned document has just extensively been introduced various general surfactants, and relevant these surfactants is used for the effect of fuel cell electrode, is unclear.
The induced by alkyl hydroxybenzene surfactant is the environmental hormone that causes the endocrine disturbance effect that has under a cloud.Therefore, might reduce remaining fail safe and the fail safe when discarded goods are handled when micro-alkyl phenol is arranged in fail safe in electrode and the MEA production process, the end article.In order to ensure above-mentioned fail safe, must carry out solvent extraction to surfactant and handle.But equipment such as essential configuration liquid waste processing, washer device, thereby have the problem that increases cost.
On the other hand, if do not use surfactant, then following problem can appear.At first, the hydrophobic polymer in the electrode can not fully disperse, and produces and deposits partially, so moisture content that can not control electrode can not be guaranteed enough pole strengths.Simultaneously, the stability of hydrophobic printing ink reduces, and can cause that solid shape concentration of component is inhomogeneous, perhaps problems such as the pipeline of the hydrophobic printing ink obstruction of meeting formation coating unit and pump in the preparation section of gas diffusion layers.The result can cause hydrophobic printing ink film inhomogeneous or film quality bad, reduce the discharge performance of electrode.
Secondly, the electrode of fuel cell in the past has the problem that moisture content increased with service time.This is because generate water in electrode reaction, and owing to humidification, also contains the reason of moisture in the reacting gas.The moisture content one of catalyst layer and gas diffusion layers increases, and the pore that moves path as gas is blocked, can not supply with enough gas to electrode, and battery performance is reduced.On the other hand, if reduce gas humidity, or stop humidification for a long time, then the moisture content of polyelectrolyte among the MEA and dielectric film reduces, hydrogen ions travel net deterioration, and battery performance reduces.The reason that produces these phenomenons is because the water-retaining property of electrode used therein is relatively poor in the past, is difficult to the reason of control electrode moisture content.
So the spy opens flat 10-334922 communique and has proposed to make the water-loss reducer that contains sulfuric acid or phosphoric acid composition in the touching agent layer.But,, be difficult to the control moisture content because sulfuric acid and phosphoric acid splash easily.Use sulfuric acid and phosphoric acid to have the etching problem of fuel cell system structure parts again if add.In addition, the spy opens the 2000-251910 communique, and the spy opens 2001-15137 communique, the special flat 10-52242 communique of table and Te Kai 2000-340247 communique and announced the method for using macromolecule water uptake sheet material moisture content from the external control catalyst layer of electrode or catalyst layer and gas diffusion layers.But, from the method for external control catalyst layer and gas diffusion layers moisture content, can not the control catalyst layer and the moisture content of the trickle part of gas diffusion layers.
Secondly, the fuel cell in past has the problem that is difficult to the equally distributed catalyst layer of preparation catalyst particle.For catalyst layer, require to have higher gas diffusibility, conductivity, catalyst activity and hydrogen ion permeability simultaneously, but will satisfy these performance requirements simultaneously, catalyst particle is evenly distributed on the face direction of catalyst layer.
Catalyst layer generally is that the method by catalyst ink forms.Painting method has silk screen print method, spraying process, intaglio method, coating machine method or the like.Catalyst ink is to mix by decentralized media such as the carbon particle that load is had catalyst particle, hydrogen polyelectrolyte, water and ethanol to modulate.In the catalyst ink, generally also to be mixed with the thickener that helps apply again.
Generally measure the viscosity of catalyst ink, and in the catalyst ink field of fuel cell, almost also do not study the thixotropy situation when changing shear rate in great detail with single shear rate.
Open in the flat 8-235122 communique the spy,, used such as the high viscosity thickener that contains the fluorine atom alcohols for the viscosity of control catalyst printing ink.The method of using the contour viscosity thickener of glycerine is also arranged simultaneously.But, must from catalyst layer, remove thickener, so, must heat formed catalyst layer with high temperature so if use thickener.Therefore have hydrogen polyelectrolyte in the catalyst ink and be subjected to the problem of thermal degradation when, and since heating-up temperature up to more than 100 ℃, so also have the problem that increases the electrode cost of manufacture.
When also opening modulation catalyst printing ink shown in the flat 11-16586 communique, do not add thickener, but regulate gained catalyst ink method of viscosity by heating just like the spy.But, in this method, be difficult to grasp the volatile quantity of decentralized medium, nor adjust viscosity easily.Also have the hydrogen polyelectrolyte sex change in when heating catalyst ink or the problem of cohesion.
Summary of the invention
The objective of the invention is to, the fail safe that the optimum state of the surfactant that uses by hydrophobic polymer dispersive property in the gas diffusion layers that is controlled to be the electrode that improves fuel cell improves fuel cell goods and preparation section thereof reduces in the preparation section hydrophobic printing ink simultaneously and films inhomogeneous and the bad defective of film quality.
Another object of the present invention is the optimum moisture content by the control fuel cell electrode, further improves the performance of battery.
The present invention also aims to neither use thickener, also do not heat, but, obtain to have the fuel cell of the catalyst layer of even distribution catalyst particle on the face direction with this by solid shape concentration of component control catalyst ink viscosity.
Just, the present invention relates to a kind of polymer electrolyte fuel cells, it is to possess the hydrogen polyelectrolyte membrane is arranged, the anode and the negative electrode of clamping aforesaid electrolyte film, has anode side conductive dividing plate to the gas flow path of aforesaid anode fueling gas, has the polymer electrolyte fuel cells of cathode side conducting diaphragm from the gas flow path of oxidant gas to aforementioned negative electrode that supply with, aforesaid anode and aforementioned negative electrode contain the catalyst layer adjacent with the aforesaid electrolyte film respectively at least, with aforementioned catalyst layer and the adjacent gas diffusion layers of aforementioned separator plate, at least one side of aforesaid anode and aforementioned negative electrode is contained general formula 1:
R
1-O-{(C
2H
4O)
n-(C
3H
6O)
m}-R
2
(in the formula, R
1And R
2Be the carbon number alkyl below 15 or hydrogen atom more than 5, n and m are the integers that satisfies 0≤n≤5,0≤m≤5 and 1≤n+m≤5 conditions, and when n and m were not 0 simultaneously, it was random having the arrangement of an Oxyranyle and at least one expoxy propane base at least.) shown in compound.
At least one side in aforesaid anode and the aforementioned negative electrode is preferably also contained at least a oxide, and this oxide contains at least a metal that is selected from silicon, titanium, aluminium, zirconium, magnesium and the chromium.
Among at least one side of aforesaid anode and aforementioned negative electrode, the content of aforementioned metal oxide is preferably 1～10000ppm.
The invention still further relates to a kind of method for preparing polymer electrolyte fuel cells, it comprises that modulation contains at least a in carbon particle and the carbon fiber, hydrophobic polymer, the operation A of the hydrophobic printing ink of surfactant and decentralized medium, modulation contains the carbon particle of supported catalyst particle, the process B of the catalyst ink of hydrogen polyelectrolyte and decentralized medium, on conductivity porous matter base material, apply aforementioned hydrophobic printing ink, then make the operation C of the decentralized medium evaporation formation gas diffusion layers in the aforementioned hydrophobic printing ink, form the step D of catalyst layer with aforementioned catalyst ink, use aforementioned gas diffusion layers, the operation E of aforementioned catalyst layer and hydrogen polyelectrolyte membrane assembling monocell, used aforementioned surfactants is by general formula 1 among the operation A:
R
1-O-{(C
2H
4O)
n-(C
3H
6O)
m}-R
2
(in the formula, R
1And R
2Be the carbon number alkyl below 15 or hydrogen atom more than 5, n and m are the integers that satisfies 0≤n≤5,0≤m≤5 and 1≤n+m≤5 conditions, when n and m are not 0 simultaneously, the arrangement of at least one Oxyranyle and at least one expoxy propane base is random) shown in compound constitute, aforementioned catalyst ink is a non-newtonian fluid, when shear rate 0.1 (l/sec), its viscosity is more than the 10Pas; When shear rate was 100 (l/sec), its viscosity was below the 1Pas.
Aforementioned step D comprises preferably under the temperature below 100 ℃ more than 40 ℃, from aforementioned catalyst ink form film make the operation of aforementioned decentralized medium evaporation.
In the aforementioned catalyst ink weight ratio of contained aforementioned catalyst particle and aforementioned carbon particle and aforementioned polyelectrolyte preferred actual be 1: 1: 1.
The simple declaration of accompanying drawing
Fig. 1 is the section sketch map of the MEA of polymer electrolyte fuel cells.
Fig. 2 is the section sketch map of the monocell of polymer electrolyte fuel cells.
Fig. 3 is the ideograph of the used coating unit of the present invention.
Fig. 4 is the voltage-operating time performance plot that adds the hydrogen-air-fuel battery of metal oxide in electrode.
Fig. 5 is the voltage-operating time performance plot that adds the direct type methanol fuel cell of metal oxide in electrode.
Fig. 6 is the voltage of the hydrogen-air-fuel battery of interpolation metal oxide in the expression electrode and the graph of a relation of metal oxide concentration.
Fig. 7 is the voltage of the direct type methanol fuel cell of interpolation metal oxide in the expression electrode and the graph of a relation of metal oxide concentration.
Fig. 8 is the viscosity of expression catalyst ink and the graph of a relation of shear rate.
Fig. 9 is the I-E characteristic figure of expression monocell A-E.
Figure 10 is the outward appearance (a) of expression catalyst layer C1～C5 and the sketch map of section (b).
Figure 11 is the I-E characteristic figure of expression monocell C1～C5.
Implement best mode of the present invention
Polymer electrolyte fuel cells of the present invention possesses the hydrogen polyelectrolyte membrane is arranged, the anode and the negative electrode of clamping aforesaid electrolyte film, have anode side conductive dividing plate to the gas flow path of aforesaid anode fueling gas, have cathode side conducting diaphragm from the gas flow path of oxidant gas to aforementioned negative electrode that supply with.
Aforesaid anode and aforementioned negative electrode are respectively by constituting with the adjacent catalyst layer of aforesaid electrolyte film with the adjacent gas diffusion layers of aforementioned catalyst layer and aforementioned separator plate.
At least one side is contained general formula 1 in aforesaid anode and the aforementioned negative electrode:
R
1-O-{(C
2H
4O)
n-(C
3H
6O)
m}-R
2
(in the formula, R
1And R
2For carbon number more than 5 the alkyl below 15 or hydrogen atom, n and m be the integer that satisfies 0≤n≤5,0≤m≤5 and 1≤n+m≤5 conditions, when n and m were not 0 simultaneously, the arrangement of at least one Oxyranyle and at least one expoxy propane base was random.) shown in the alkylene oxide compound.
Aforementioned alkylene oxide compound helps the dispersion of contained hydrophobic polymer in the gas diffusion layers of at least one side's electrode.Aforementioned alkylene oxide compound also helps the dispersion of contained adhesive sometimes in side's electrode at least.Aforementioned alkylene oxide compound does not cause the endocrine disturbance effect, and, use the electrode of this alkylene oxide compound to have excellent characteristic.
Can obtain to have the reasons are as follows of excellent specific property electrode.
Gas diffusion layers is to be coated on the conductivity porous matter base materials such as carbon paper, carbon felt and to make containing at least a hydrophobic printing ink in hydrophobic polymer, carbon particle and the carbon fiber.Contain aforementioned alkylene oxide compound in the aforementioned hydrophobic printing ink as surfactant if make, then hydrophobic polymer and carbon particle can be well dispersed in the printing ink, can not occur depositing partially.So the moisture content in the energy height control electrode, and can guarantee enough pole strengths.Also have, hydrophobic polymer does not produce partially in printing ink and deposits, so the stability of hydrophobic printing ink is also very high.As a result, in operations such as the coating of printing ink, printing, the solid shape component blocking pipeline of printing ink and the phenomenon of pump and the variation of printing ink rerum natura are arranged seldom, thereby reduce the problem inhomogeneous and that coating quality is bad that applies.
The amount of contained hydrophobic polymer is preferably in the hydrophobic printing ink, and it is 5～40 weight portions with respect to material with carbon elements such as per 100 weight portion carbon particles and carbon fibers.Hydrophobic polymer preferably uses fluororesin such as polytetrafluoroethylene (hereinafter referred to as PTFE), tetrafluoroethene one hexafluoropropylene copolymer.
Contained aforementioned alkylene oxide compound is preferably in the hydrophobic printing ink, and it is 1～20 weight portion with respect to the aforementioned material with carbon element of per 100 weight portions.
Hydrophobic printing ink, preferably the ratio with 5～40g/m2 is coated on the conductivity porous matter base material.
In the widely used in the past surfactant, under a cloud have the material major part that causes the chaotic effect of endocrine and belong to the induced by alkyl hydroxybenzene material.In the molecule of these materials phenylol is arranged.And used aforementioned alkylene oxide compound does not contain phenylol, does not cause the effect of endocrine confusion among the present invention.If so, then can improve the fail safe in the gentle body diffused layer preparation section of hydrophobic printing ink according to the present invention.Also have, when use has possibility and causes the surfactant of the chaotic effect of endocrine,, must need the equipment such as solvent extraction processing, liquid waste processing, wash mill of surfactant in order to ensure fail safe, in contrast to this, if use the inventive method then do not need these.Therefore can reduce preparation cost.And the environmental hormone of trace also can not remainingly be arranged in end article,, there is no need discarded goods are handled especially so can guarantee the fail safe of goods.
For the moistening degree that makes electrode is in optimum state, at least one side in aforesaid anode and the aforementioned negative electrode preferably also will have and contains the oxide that is selected from least a metal in silicon, titanium, aluminium, zirconium, magnesium and the chromium.Aforesaid oxides also can be the composite oxides that contain multiple metal.And, both can be used alone oxide, also can be used multiple oxide.
The amount of the aforementioned metal oxide among at least one side of aforesaid anode and aforementioned negative electrode is preferably 1～10000ppm.
Because aforesaid oxides has water-retaining property,, come the moisture state of control electrode so can be distributed to the method for the minute aperture inside that catalyst layer and gas diffusion layers have by making the aforesaid oxides particle.Just, because oxide absorbs remaining moisture, so by supplying to the steam in the reacting gas and in electrode reaction, generating water and cause in catalyst layer and the gas diffusion layers controlled as the blocked phenomenon of the pore of gas flow path.On the other hand, even reduce the moisture content in the reacting gas or stop humidification for a long time, the moisture that is kept in the metal oxide also can supply in the polyelectrolyte and dielectric film in the electrode, and therefore, the reduction of hydrogen is also controlled.So can obtain in long-time, bringing into play high performance fuel cell.
And different with the method for using the sheet material control electrode moisture state that constitutes by absorbent polymer in the past, if use the moisture state that aforesaid oxides then can the trickle part of control electrode.Thereby can prevent the part drying of electrode, so can keep the high gas diffusibility and the hydrogen of electrode for a long time.
Metal oxide is more likely made minuteness particle than macromolecular materials such as the polyamide that uses in the past, cotton, polyester/regenerated cellulose, polyester/propylene system, regenerated cellulose/ripple Rec Le Er (material that vinyl alcohol-vinyl chloride copolymer and polyvinyl alcohol mix mutually), Sodium Polyacrylates.So can more effectively make oxide particle be distributed to the minute aperture inside that catalyst layer and gas diffusion layers have.For example, can contact with catalyst particle and must dispose oxide particle near the polyelectrolyte of humidification.Simultaneously near the electrode interior fine holes that has as the reaction gas flow paths function, also can dispose oxide particle, so superfluous water oxide particle absorbs.Therefore can prevent that gas flow path from stopping up.
The chemical property of oxides such as silicon dioxide, titanium dioxide, aluminium oxide, zirconia, magnesium oxide, chromium oxide is highly stable, be not dissolved in the decentralized medium the macromolecule particle so can not resemble, so the influence of used decentralized medium when being not easy to be made electrode.Simultaneously, when using oxide,, also can carry out the high-temperature process more than 300 ℃ even when removing the heat treatment of decentralized medium and surfactant.And if use the macromolecule particle, then can only macromolecule do not take place rotten or the low temperature that decomposes under handle.
When in catalyst layer, providing oxide, in advance the oxide of ormal weight is added in the catalyst ink to well.In addition, when in gas diffusion layers, providing oxide, in advance the oxide of ormal weight is added in the hydrophobic printing ink to well.
As mentioned above, the oxide with water-retaining property is suitable for the moisture state of control electrode on micrometer level most, and if use oxide, the scope of alternative condition also will enlarge in the preparation section.
The preparation method of fuel cell of the present invention below is described.
At first narrate the viscosity of relevant liquid with reference to " rheology is crossed the threshold " (write in little day on the ridge).General liquid is as long as it doesn't matter is stable for temperature one rule viscosity and shear rate.This liquid is called Newtonian fluid.In contrast, though some liquid under the certain condition of temperature, if change shear rate, its viscosity also changes, and this liquid is called non-newtonian fluid.
Be the viscosity of example explanation catalyst ink below with the process that adopts coating unit shown in Figure 3 31 coated catalysts 36 on base material 34.
Join the catalyst ink 36 in the ink tank 32, by nozzle 37, coated roller 35 is coated on the base material 34 of gas diffusion layers or polyelectrolyte membrane.Base material 34 is supplied with by unreeling part 33.What form on base material 34 films through hothouse 38 and deflector roll 39, in reeling end 30 places rolling.
When catalyst ink 36 is Newtonian fluid, if ink viscosity is low excessively, be easy to generate liquid bob phenomenon during coating or the undue broadening on Width of filming, be difficult to form the uniform catalyst layer.And when catalyst ink 36 viscosity were too high, at the head of nozzle 37, printing ink can take place to stop up or the middle mottled or streak that produces of filming, and is difficult to form the uniform catalyst layer.
But when catalyst ink was non-newtonian fluid, at the head of nozzle 37, because catalyst ink 36 passes through very narrow slit, so shear rate is accelerated, the viscosity of printing ink reduced, and becomes and flows easily.The shear rate of the printing ink after being applied on the base material 34 in addition is very little, so ink viscosity increases.Weigh down phenomenon thereby liquid can not occur, can broadening on Width yet, it is stable to keep filming on base material 34.
As mentioned above, not Newtonian fluid but, can stably form catalyst layer by using at the thixotropy non-newtonian fluid catalyst ink that viscosity under the high shear rates reduces, viscosity raises under low shearing speed.
According to above-mentioned viewpoint, among the present invention, there are carbon particle, hydrogen polyelectrolyte and the decentralized medium of catalyst particle to constitute in the operation of catalyst ink in modulation by load, modulate the catalyst ink of non-newtonian fluid, and make it when shear rate is 0.1 (l/sec), have viscosity more than the 10Pas, when shear rate during, has the following viscosity of 1Pas at 100 (l/sec).
When catalyst ink is when satisfying the non-newtonian fluid of above-mentioned condition, in nozzle 37 head shear rates part faster, the viscosity of catalyst ink 36 reduces, and can form thickness and film uniformly.The part that is not subjected to shear action that printing ink after being coated on the base material 34 is simultaneously filmed, viscosity raise, and film can not produce that liquid weighs down or the problem of broadening on Width.
Catalyst ink, preferably using by load has the mixture that catalyst particle carbon particle, hydrogen polyelectrolyte and decentralized medium constitute, the mixing stirring device that adopts ball mill (bead mill), ball mill (ball mill) etc. to have the grinding dispersion effect to be made.
The control of catalyst ink shear rate for example can be undertaken by the solid shape concentration of component of change catalyst ink and the ratio of decentralized medium.In addition, also can control shear rate by the composition that changes solid shape component.For example, 1～10 weight % in the preferred catalyst printing ink is that catalyst particle (for example platinum metal), 1～10 weight % are that carbon particle, 1～10 weight % as catalyst particle carriers is polyelectrolyte.Simultaneously in the catalyst ink weight ratio of contained catalyst particle, carbon particle and polyelectrolyte most preferably actual be 1: 1: 1.
Aforementioned catalyst ink is coated on the base materials such as hydrogen polyelectrolyte membrane, aforementioned gas diffusion layers, then makes the decentralized medium evaporation of aforementioned catalyst ink can form catalyst layer.Hydrogen macromolecule from prevent catalyst layer rotten or prevent to film in the angle that cracks consider that the evaporization process of decentralized medium preferably carries out under the temperature below 100 ℃ more than 40 ℃.
(i) make gas diffusion layers
As the acetylene carbon black of conductive carbon particle (electrochemical industry (strain) is made: electrochemical carbon black (デ Application カ Block ラ Star Network), particle diameter 35nm) 100 weight portions and following general formula:
R
1-O-{(C
2H
4O)
n-(C
3H
6O)
m}-R
2
180 μ m) on the surface, the coating ratio is 30g/m then aforementioned hydrophobic printing ink is coated to (east beautiful (strain) manufacturing: TGPH060H, voidage: thickness 75%: of carbon paper as the gas diffusion layers base material
2, make the hydrophobic printing ink of carbon paper impregnation.Then in air ambient, under 350 ℃, the carbon paper that contains hydrophobic printing ink is heat-treated, make gas diffusion layers with air drier.
(ii) form catalyst layer
(ii-1) cathode side
Making average primary particle diameter is that (Dutch AKZO Chemie company makes: triumphant money grace carbon black (ケ ッ チ エ Application Block ラ ッ Network) EC) the load average particle diameter is platinum particles 50 weight portions of 30 dusts in 100 weight portions for the conductive carbon particle of 30nm.Then, load there are the carbon particle of platinum particles and the alcohol dispersion liquid that contains 9 weight % hydrogen polyelectrolytes mix the catalyst ink of Wehnelt cathode side.At this moment, carry the mixing ratio of platinum carbon particle and hydrogen polyelectrolyte dispersion liquid, count 4: 96 with weight ratio.In the aforementioned hydrogen polyelectrolyte, (Asahi Glass (strain) is made: fluorine Lei Miweng (Off レ ミ オ Application)) to have used perfluorocarbon sulfonic acid.
Then, the catalyst ink of this cathode side is printed onto on the side surface of a side surface of above-mentioned gas diffusion layer and the hydrogen polyelectrolyte membrane that encloses than aforementioned gas diffusion layers also big (manufacturing of Dupont (Du Pont) company: Na Feiang 112), then dry under 70 ℃, form the cathode-side catalytic layer that thickness is 10 μ m respectively.
(ii-2) anode-side
Make load average particle diameter in the triumphant money grace carbon black EC100 weight portion be about platinum particles and each 25 weight portion of ruthenium particle of 30 dusts.Then, carbon particle that carries platinum and ruthenium and the alcohol dispersion liquid that contains 9 weight % hydrogen polyelectrolytes are mixed the catalyst ink of modulating anode side.At this moment, carry platinum and the carbon particle of ruthenium and the mixing ratio of hydrogen polyelectrolyte dispersion liquid, count 4: 96 by weight.In the aforementioned hydrogen polyelectrolyte, (Asahi Glass (strain) is made: fluorine Lei Miweng) to have used perfluorocarbon sulfonic acid.
Then, the anode-side catalyst ink is printed onto on the opposite side surface of the opposite side surface of above-mentioned gas diffusion layer and above-mentioned hydrogen polyelectrolyte membrane, then, forms the anode side catalyst layer that thickness is 15 μ m respectively 70 ℃ of dryings down.
(iii) make MEA
The gas diffusion layers clamping two sides that has catalyst layer with single face all has the hydrogen polyelectrolyte membrane of catalyst layer, and make between the above-mentioned cathode-side catalytic layer and between the anode side catalyst layer relatively, MEA is made in hot pressing.This MEA as MEA-1.
(iv) assembling fuel cell
Adhesive rubber packing ring around the dielectric film of MEA-1 forms cooling water, fuel gas and the general manifold hole of oxidant gas stream.
In addition, prepare the various dividing plates that the graphite cake by the phenolic resins impregnation constitutes, the overall dimensions of graphite cake are 20cm * 32cm, and thickness is that 1.3mm, gas flow path or the cooling water stream degree of depth are 0.5mm.
The cathode side of the gas stream trackside subtend MEA-1 of the dividing plate that is formed with the oxidant gas stream, the anode-side of the gas stream trackside subtend MEA-1 of the dividing plate that is formed with fuel gas channel, and make it form an integral body, constitute monocell.
Then laminated two monocells, be aforementioned two batteries of clamping medially with a pair of dividing plate that is formed with the cooling water stream with the cooling water flow trackside.Carry out the operation of this pattern repeatedly, make the laminated battery of 100 batteries, dispose the collector plate of stainless steel and the insulation board of electrical insulating material at the both ends of laminated battery, use end plates and banding rod again overall fixed.Banding pressure is every plate area 15kgf/cm
2The battery made from said method as battery 1.
(v) qualification test
Respectively to the anode of battery 1 supply with pure hydrogen, to the negative electrode air supply, making battery temperature is that 75 ℃, fuel gas utilance (Uf) are 70%, air utilization ratio (Uo) is 40%, carries out discharge tests.At this moment, make pure hydrogen pass through 60～70 ℃ bubbler (バ Block ラ one), make the bubbler of air by 45～70 ℃ carry out gas humidification.
The parameters R in the surfactant molecule formula used in the battery 1
1, R
2, m, n and battery 1 be 0.2mA/cm in current density
2The time cell voltage relation be shown in table 1～table 13.
Table 1
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 1 | 0 | 430 |
| 5 | 450 | |||
| 15 | 320 | |||
| 16 | 110 | |||
| 5 | 4 | 500 | ||
| 5 | 761 | |||
| 15 | 783 | |||
| 16 | 451 | |||
| 15 | 4 | 452 | ||
| 5 | 772 | |||
| 15 | 789 | |||
| 16 | 432 | |||
| 16 | 4 | 320 | ||
| 5 | 411 | |||
| 15 | 489 | |||
| 16 | 310 | |||
| H | 4 | 110 | ||
| 5 | 775 | |||
| 15 | 792 | |||
| 16 | 325 | |||
| 4 | 4 | 2 | 0 | 431 |
| 5 | 455 | |||
| 15 | 310 | |||
| 16 | 150 | |||
| 5 | 4 | 502 | ||
| 5 | 741 | |||
| 15 | 783 | |||
| 16 | 458 | |||
| 15 | 4 | 412 | ||
| 5 | 782 | |||
| 15 | 779 | |||
| 16 | 482 | |||
| 16 | 4 | 330 | ||
| 5 | 401 | |||
| 15 | 479 | |||
| 16 | 300 | |||
| H | 4 | 170 | ||
| 5 | 785 | |||
| 15 | 742 | |||
| 16 | 305 |
Table 2
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 3 | 0 | 320 |
| 5 | 321 | |||
| 15 | 110 | |||
| 16 | 115 | |||
| 5 | 4 | 450 | ||
| 5 | 772 | |||
| 15 | 755 | |||
| 16 | 320 | |||
| 15 | 4 | 210 | ||
| 5 | 786 | |||
| 15 | 750 | |||
| 16 | 455 | |||
| 16 | 4 | 325 | ||
| 5 | 321 | |||
| 15 | 441 | |||
| 16 | 120 | |||
| H | 4 | 150 | ||
| 5 | 758 | |||
| 15 | 786 | |||
| 16 | 450 | |||
| 4 | 4 | 4 | 0 | 401 |
| 5 | 321 | |||
| 15 | 220 | |||
| 16 | 149 | |||
| 5 | 4 | 420 | ||
| 5 | 765 | |||
| 15 | 772 | |||
| 16 | 325 | |||
| 15 | 4 | 402 | ||
| 5 | 758 | |||
| 15 | 754 | |||
| 16 | 452 | |||
| 16 | 4 | 369 | ||
| 5 | 485 | |||
| 15 | 481 | |||
| 16 | 210 | |||
| H | 4 | 189 | ||
| 5 | 756 | |||
| 15 | 774 | |||
| 16 | 298 |
Table 3
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 5 | 0 | 325 |
| 5 | 441 | |||
| 15 | 241 | |||
| 16 | 251 | |||
| 5 | 4 | 450 | ||
| 5 | 784 | |||
| 15 | 774 | |||
| 16 | 362 | |||
| 15 | 4 | 421 | ||
| 5 | 756 | |||
| 15 | 781 | |||
| 16 | 402 | |||
| 16 | 4 | 311 | ||
| 5 | 328 | |||
| 15 | 441 | |||
| 16 | 325 | |||
| H | 4 | 140 | ||
| 5 | 781 | |||
| 15 | 756 | |||
| 16 | 362 | |||
| 4 | 4 | 6 | 0 | 251 |
| 5 | 455 | |||
| 15 | 120 | |||
| 16 | 100 | |||
| 5 | 4 | 150 | ||
| 5 | 150 | |||
| 15 | 240 | |||
| 16 | 320 | |||
| 15 | 4 | 381 | ||
| 5 | 254 | |||
| 15 | 268 | |||
| 16 | 247 | |||
| 16 | 4 | 147 | ||
| 5 | 351 | |||
| 15 | 257 | |||
| 16 | 361 | |||
| H | 4 | 189 | ||
| 5 | 258 | |||
| 15 | 159 | |||
| 16 | 357 |
Table 4
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 1 | 1 | 358 |
| 5 | 145 | |||
| 15 | 352 | |||
| 16 | 234 | |||
| 5 | 4 | 481 | ||
| 5 | 751 | |||
| 15 | 756 | |||
| 16 | 458 | |||
| 15 | 4 | 551 | ||
| 5 | 735 | |||
| 15 | 728 | |||
| 16 | 458 | |||
| 16 | 4 | 368 | ||
| 5 | 325 | |||
| 15 | 451 | |||
| 16 | 321 | |||
| H | 4 | 325 | ||
| 5 | 745 | |||
| 15 | 776 | |||
| 16 | 451 | |||
| 4 | 4 | 2 | 1 | 325 |
| 5 | 410 | |||
| 15 | 352 | |||
| 16 | 251 | |||
| 5 | 4 | 254 | ||
| 5 | 768 | |||
| 15 | 751 | |||
| 16 | 451 | |||
| 15 | 4 | 440 | ||
| 5 | 754 | |||
| 15 | 752 | |||
| 16 | 251 | |||
| 16 | 4 | 352 | ||
| 5 | 245 | |||
| 15 | 256 | |||
| 16 | 100 | |||
| H | 4 | 152 | ||
| 5 | 754 | |||
| 15 | 745 | |||
| 16 | 362 |
Table 5
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 3 | 1 | 321 |
| 5 | 321 | |||
| 15 | 351 | |||
| 16 | 365 | |||
| 5 | 4 | 352 | ||
| 5 | 775 | |||
| 15 | 742 | |||
| 16 | 254 | |||
| 15 | 4 | 365 | ||
| 5 | 726 | |||
| 15 | 746 | |||
| 16 | 325 | |||
| 16 | 4 | 214 | ||
| 5 | 256 | |||
| 15 | 352 | |||
| 16 | 254 | |||
| H | 4 | 265 | ||
| 5 | 749 | |||
| 15 | 784 | |||
| 16 | 231 | |||
| 4 | 4 | 4 | 1 | 362 |
| 5 | 254 | |||
| 15 | 214 | |||
| 16 | 251 | |||
| 5 | 4 | 254 | ||
| 5 | 724 | |||
| 15 | 754 | |||
| 16 | 254 | |||
| 15 | 4 | 256 | ||
| 5 | 785 | |||
| 15 | 745 | |||
| 16 | 235 | |||
| 16 | 4 | 214 | ||
| 5 | 236 | |||
| 15 | 254 | |||
| 16 | 365 | |||
| H | 4 | 254 | ||
| 5 | 766 | |||
| 15 | 754 | |||
| 16 | 251 |
Table 6
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 5 | 1 | 321 |
| 5 | 325 | |||
| 15 | 321 | |||
| 16 | 251 | |||
| 5 | 4 | 324 | ||
| 5 | 225 | |||
| 15 | 321 | |||
| 16 | 352 | |||
| 15 | 4 | 324 | ||
| 5 | 325 | |||
| 15 | 321 | |||
| 16 | 352 | |||
| 16 | 4 | 325 | ||
| 5 | 412 | |||
| 15 | 215 | |||
| 16 | 251 | |||
| H | 4 | 325 | ||
| 5 | 214 | |||
| 15 | 251 | |||
| 16 | 325 | |||
| 4 | 4 | 1 | 2 | 326 |
| 5 | 325 | |||
| 15 | 321 | |||
| 16 | 352 | |||
| 5 | 4 | 324 | ||
| 5 | 756 | |||
| 15 | 784 | |||
| 16 | 125 | |||
| 15 | 4 | 235 | ||
| 5 | 746 | |||
| 15 | 754 | |||
| 16 | 325 | |||
| 16 | 4 | 265 | ||
| 5 | 341 | |||
| 15 | 254 | |||
| 16 | 321 | |||
| H | 4 | 210 | ||
| 5 | 765 | |||
| 15 | 785 | |||
| 16 | 365 |
Table 7
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 2 | 2 | 100 |
| 5 | 254 | |||
| 15 | 241 | |||
| 16 | 256 | |||
| 5 | 4 | 254 | ||
| 5 | 745 | |||
| 15 | 724 | |||
| 16 | 321 | |||
| 15 | 4 | 325 | ||
| 5 | 745 | |||
| 15 | 746 | |||
| 16 | 256 | |||
| 16 | 4 | 452 | ||
| 5 | 235 | |||
| 15 | 256 | |||
| 16 | 120 | |||
| H | 4 | 251 | ||
| 5 | 774 | |||
| 15 | 754 | |||
| 16 | 231 | |||
| 4 | 4 | 3 | 2 | 362 |
| 5 | 325 | |||
| 15 | 214 | |||
| 16 | 265 | |||
| 5 | 4 | 251 | ||
| 5 | 745 | |||
| 15 | 756 | |||
| 16 | 254 | |||
| 15 | 4 | 236 | ||
| 5 | 785 | |||
| 15 | 745 | |||
| 16 | 213 | |||
| 16 | 4 | 265 | ||
| 5 | 250 | |||
| 15 | 23 | |||
| 16 | 251 | |||
| H | 4 | 25 | ||
| 5 | 784 | |||
| 15 | 722 | |||
| 16 | 123 |
Table 8
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 4 | 2 | 235 |
| 5 | 124 | |||
| 15 | 23 | |||
| 16 | 251 | |||
| 5 | 4 | 235 | ||
| 5 | 114 | |||
| 15 | 123 | |||
| 16 | 156 | |||
| 15 | 4 | 231 | ||
| 5 | 251 | |||
| 15 | 325 | |||
| 16 | 214 | |||
| 16 | 4 | 214 | ||
| 5 | 25 | |||
| 15 | 321 | |||
| 16 | 20 | |||
| H | 4 | 325 | ||
| 5 | 36 | |||
| 15 | 251 | |||
| 16 | 20 | |||
| 4 | 4 | 1 | 3 | 251 |
| 5 | 254 | |||
| 15 | 23 | |||
| 16 | 214 | |||
| 5 | 4 | 251 | ||
| 5 | 754 | |||
| 15 | 745 | |||
| 16 | 251 | |||
| 15 | 4 | 236 | ||
| 5 | 774 | |||
| 15 | 745 | |||
| 16 | 231 | |||
| 16 | 4 | 10 | ||
| 5 | 25 | |||
| 15 | 325 | |||
| 16 | 241 | |||
| H | 4 | 365 | ||
| 5 | 745 | |||
| 15 | 785 | |||
| 16 | 245 |
Table 9
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 2 | 3 | 365 |
| 5 | 251 | |||
| 15 | 458 | |||
| 16 | 25 | |||
| 5 | 4 | 241 | ||
| 5 | 745 | |||
| 15 | 786 | |||
| 16 | 252 | |||
| 15 | 4 | 457 | ||
| 5 | 784 | |||
| 15 | 733 | |||
| 16 | 251 | |||
| 16 | 4 | 325 | ||
| 5 | 254 | |||
| 15 | 12 | |||
| 16 | 25 | |||
| H | 4 | 265 | ||
| 5 | 788 | |||
| 15 | 754 | |||
| 16 | 521 | |||
| 4 | 4 | 3 | 3 | 251 |
| 5 | 25 | |||
| 15 | 145 | |||
| 16 | 21 | |||
| 5 | 4 | 35 | ||
| 5 | 265 | |||
| 15 | 25 | |||
| 16 | 214 | |||
| 15 | 4 | 2 | ||
| 5 | 254 | |||
| 15 | 325 | |||
| 16 | 25 | |||
| 16 | 4 | 25 | ||
| 5 | 11 | |||
| 15 | 25 | |||
| 16 | 2 | |||
| H | 4 | 244 | ||
| 5 | 214 | |||
| 15 | 2 | |||
| 16 | 35 |
Table 10
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 1 | 4 | 2 |
| 5 | 25 | |||
| 15 | 56 | |||
| 16 | 23 | |||
| 5 | 4 | 25 | ||
| 5 | 745 | |||
| 15 | 748 | |||
| 16 | 65 | |||
| 15 | 4 | 244 | ||
| 5 | 754 | |||
| 15 | 712 | |||
| 16 | 251 | |||
| 16 | 4 | 212 | ||
| 5 | 25 | |||
| 15 | 15 | |||
| 16 | 356 | |||
| H | 4 | 32 | ||
| 5 | 754 | |||
| 15 | 774 | |||
| 16 | 25 | |||
| 4 | 4 | 2 | 4 | 32 |
| 5 | 542 | |||
| 15 | 25 | |||
| 16 | 21 | |||
| 5 | 4 | 35 | ||
| 5 | 325 | |||
| 15 | 21 | |||
| 16 | 25 | |||
| 15 | 4 | 2 | ||
| 5 | 26 | |||
| 15 | 2 | |||
| 16 | 251 | |||
| 16 | 4 | 25 | ||
| 5 | 251 | |||
| 15 | 11 | |||
| 16 | 235 | |||
| H | 4 | 21 | ||
| 5 | 114 | |||
| 15 | 253 | |||
| 16 | 21 |
Table 11
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 0 | 1 | 412 |
| 5 | 410 | |||
| 15 | 120 | |||
| 16 | 254 | |||
| 5 | 4 | 257 | ||
| 5 | 751 | |||
| 15 | 762 | |||
| 16 | 421 | |||
| 15 | 4 | 451 | ||
| 5 | 774 | |||
| 15 | 775 | |||
| 16 | 215 | |||
| 16 | 4 | 451 | ||
| 5 | 251 | |||
| 15 | 254 | |||
| 16 | 62 | |||
| H | 4 | 110 | ||
| 5 | 774 | |||
| 15 | 784 | |||
| 16 | 362 | |||
| 4 | 4 | 0 | 2 | 25 |
| 5 | 254 | |||
| 15 | 213 | |||
| 16 | 25 | |||
| 5 | 4 | 544 | ||
| 5 | 751 | |||
| 15 | 757 | |||
| 16 | 451 | |||
| 15 | 4 | 415 | ||
| 5 | 778 | |||
| 15 | 754 | |||
| 16 | 75 | |||
| 16 | 4 | 362 | ||
| 5 | 25 | |||
| 15 | 14 | |||
| 16 | 158 | |||
| H | 4 | 455 | ||
| 5 | 774 | |||
| 15 | 795 | |||
| 16 | 333 |
Table 12
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 0 | 3 | 325 |
| 5 | 315 | |||
| 15 | 152 | |||
| 16 | 14 | |||
| 5 | 4 | 455 | ||
| 5 | 778 | |||
| 15 | 754 | |||
| 16 | 320 | |||
| 15 | 4 | 215 | ||
| 5 | 777 | |||
| 15 | 769 | |||
| 16 | 451 | |||
| 16 | 4 | 325 | ||
| 5 | 322 | |||
| 15 | 41 | |||
| 16 | 45 | |||
| H | 4 | 455 | ||
| 5 | 755 | |||
| 15 | 751 | |||
| 16 | 444 | |||
| 4 | 4 | 0 | 4 | 451 |
| 5 | 251 | |||
| 15 | 25 | |||
| 16 | 45 | |||
| 5 | 4 | 255 | ||
| 5 | 774 | |||
| 15 | 771 | |||
| 16 | 485 | |||
| 15 | 4 | 444 | ||
| 5 | 754 | |||
| 15 | 758 | |||
| 16 | 458 | |||
| 16 | 4 | 362 | ||
| 5 | 451 | |||
| 15 | 211 | |||
| 16 | 251 | |||
| H | 4 | 154 | ||
| 5 | 712 | |||
| 15 | 722 | |||
| 16 | 296 |
Table 13
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 0 | 5 | 25 |
| 5 | 21 | |||
| 15 | 214 | |||
| 16 | 21 | |||
| 5 | 4 | 215 | ||
| 5 | 744 | |||
| 15 | 754 | |||
| 16 | 321 | |||
| 15 | 4 | 25 | ||
| 5 | 711 | |||
| 15 | 721 | |||
| 16 | 482 | |||
| 16 | 4 | 330 | ||
| 5 | 401 | |||
| 15 | 479 | |||
| 16 | 25 | |||
| H | 4 | 170 | ||
| 5 | 755 | |||
| 15 | 741 | |||
| 16 | 25 | |||
| 4 | 4 | 1 | 5 | 236 |
| 5 | 251 | |||
| 15 | 41 | |||
| 16 | 251 | |||
| 5 | 4 | 325 | ||
| 5 | 25 | |||
| 15 | 215 | |||
| 16 | 21 | |||
| 15 | 4 | 255 | ||
| 5 | 211 | |||
| 15 | 23 | |||
| 16 | 255 | |||
| 16 | 4 | 214 | ||
| 5 | 233 | |||
| 15 | 25 | |||
| 16 | 21 | |||
| H | 4 | 25 | ||
| 5 | 362 | |||
| 15 | 25 | |||
| 16 | 211 |
Above result shows R
1And R
2Be carbon number when the alkyl below 15 or hydrogen and n and m satisfy the condition of 0≤n≤5,0≤m≤5 and 1≤n+m≤5 more than 5, the discharge performance height can obtain the above cell voltage of 700mV.On the other hand, when each parameter was beyond above-mentioned scope, cell voltage was below 500mV.
Comparative example 1
In the production process of gas diffusion layers, surfactant (long rapids industry (strain) manufacturing: the surfactant of alternate collar siloxane compound type Te Laidun (ト ラ イ ト Application) X-100) with the octyl phenol ethylate, the D-1 that makes with Daikin Industries (strain) substitutes the D-1E of Daikin Industries (strain) manufacturing as the PTFE dispersion liquid, in addition, carry out 1 identical operations with embodiment, make MEA, this MEA as MEA-2.Substitute MEA-1 with MEA-2 simultaneously, in addition, carry out 1 identical operations, make the battery-2 that the laminated battery by 100 batteries constitutes with embodiment.
To battery 2 also carry out with embodiment 1 in identical discharge test, the result obtains the cell voltage of 735mV.
Embodiment 2
Methanol aqueous solution from 2mol/l to the anode of battery 1, the temperature of supplying with are 60 ℃, in addition, carry out 1 identical operations with embodiment, as direct type methanol fuel cell, carry out the discharge test of battery.At this moment the temperature that also makes battery is that 75 ℃, air utilization ratio (Uo) are 40%, and make air pass through 45～70 ℃ bubbler humidification.
The parameters R in the used surfactant molecule formula in the battery 1
1, R
2, m, n and battery 1 be 0.05mA/cm in current density
2The time cell voltage relation be shown in table 14～table 26.
Table 14
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 1 | 0 | 12 |
| 5 | 123 | |||
| 15 | 12 | |||
| 16 | 15 | |||
| 5 | 4 | 1 | ||
| 5 | 445 | |||
| 15 | 415 | |||
| 16 | 45 | |||
| 15 | 4 | 25 | ||
| 5 | 475 | |||
| 15 | 412 | |||
| 16 | 20 | |||
| 16 | 4 | 14 | ||
| 5 | 25 | |||
| 15 | 0 | |||
| 16 | 21 | |||
| H | 4 | 25 | ||
| 5 | 457 | |||
| 15 | 458 | |||
| 16 | 21 | |||
| 4 | 4 | 2 | 0 | 25 |
| 5 | 12 | |||
| 15 | 47 | |||
| 16 | 5 | |||
| 5 | 4 | 256 | ||
| 5 | 485 | |||
| 15 | 510 | |||
| 16 | 25 | |||
| 15 | 4 | 21 | ||
| 5 | 447 | |||
| 15 | 458 | |||
| 16 | 25 | |||
| 16 | 4 | 2 | ||
| 5 | 36 | |||
| 15 | 2 | |||
| 16 | 4 | |||
| H | 4 | 25 | ||
| 5 | 456 | |||
| 15 | 541 | |||
| 16 | 21 |
Table 15
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 3 | 0 | 25 |
| 5 | 1 | |||
| 15 | 2 | |||
| 16 | 14 | |||
| 5 | 4 | 25 | ||
| 5 | 485 | |||
| 15 | 445 | |||
| 16 | 52 | |||
| 15 | 4 | 25 | ||
| 5 | 455 | |||
| 15 | 521 | |||
| 16 | 52 | |||
| 16 | 4 | 54 | ||
| 5 | 52 | |||
| 15 | 3 | |||
| 16 | 54 | |||
| H | 4 | 25 | ||
| 5 | 458 | |||
| 15 | 574 | |||
| 16 | 25 | |||
| 4 | 4 | 4 | 0 | 21 |
| 5 | 52 | |||
| 15 | 32 | |||
| 16 | 4 | |||
| 5 | 4 | 25 | ||
| 5 | 456 | |||
| 15 | 512 | |||
| 16 | 47 | |||
| 15 | 4 | 251 | ||
| 5 | 458 | |||
| 15 | 455 | |||
| 16 | 25 | |||
| 16 | 4 | 52 | ||
| 5 | 14 | |||
| 15 | 3 | |||
| 16 | 25 | |||
| H | 4 | 25 | ||
| 5 | 455 | |||
| 15 | 566 | |||
| 16 | 25 |
Table 16
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 5 | 0 | 25 |
| 5 | 21 | |||
| 15 | 23 | |||
| 16 | 6 | |||
| 5 | 4 | 25 | ||
| 5 | 455 | |||
| 15 | 424 | |||
| 16 | 52 | |||
| 15 | 4 | 14 | ||
| 5 | 510 | |||
| 15 | 512 | |||
| 16 | 25 | |||
| 16 | 4 | 47 | ||
| 5 | 32 | |||
| 15 | 0 | |||
| 16 | 2 | |||
| H | 4 | 53 | ||
| 5 | 451 | |||
| 15 | 412 | |||
| 16 | 25 | |||
| 4 | 4 | 6 | 0 | 21 |
| 5 | 25 | |||
| 15 | 3 | |||
| 16 | 52 | |||
| 5 | 4 | 256 | ||
| 5 | 458 | |||
| 15 | 500 | |||
| 16 | 321 | |||
| 15 | 4 | 52 | ||
| 5 | 21 | |||
| 15 | 52 | |||
| 16 | 3 | |||
| 16 | 4 | 25 | ||
| 5 | 12 | |||
| 15 | 25 | |||
| 16 | 1 | |||
| H | 4 | 25 | ||
| 5 | 25 | |||
| 15 | 2 | |||
| 16 | 0 |
Table 17
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 1 | 1 | 25 |
| 5 | 12 | |||
| 15 | 25 | |||
| 16 | 2 | |||
| 5 | 4 | 152 | ||
| 5 | 451 | |||
| 15 | 410 | |||
| 16 | 25 | |||
| 15 | 4 | 14 | ||
| 5 | 421 | |||
| 15 | 411 | |||
| 16 | 25 | |||
| 16 | 4 | 321 | ||
| 5 | 25 | |||
| 15 | 21 | |||
| 16 | 25 | |||
| H | 4 | 24 | ||
| 5 | 451 | |||
| 15 | 410 | |||
| 16 | 25 | |||
| 4 | 4 | 2 | 1 | 25 |
| 5 | 32 | |||
| 15 | 25 | |||
| 16 | 25 | |||
| 5 | 4 | 1 | ||
| 5 | 455 | |||
| 15 | 410 | |||
| 16 | 25 | |||
| 15 | 4 | 325 | ||
| 5 | 451 | |||
| 15 | 456 | |||
| 16 | 25 | |||
| 16 | 4 | 214 | ||
| 5 | 2 | |||
| 15 | 1 | |||
| 16 | 0 | |||
| H | 4 | 255 | ||
| 5 | 458 | |||
| 15 | 475 | |||
| 16 | 254 |
Table 18
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 3 | 1 | 25 |
| 5 | 3 | |||
| 15 | 25 | |||
| 16 | 2 | |||
| 5 | 4 | 1 | ||
| 5 | 455 | |||
| 15 | 475 | |||
| 16 | 25 | |||
| 15 | 4 | 24 | ||
| 5 | 455 | |||
| 15 | 465 | |||
| 16 | 252 | |||
| 16 | 4 | 252 | ||
| 5 | 5 | |||
| 15 | 23 | |||
| 16 | 25 | |||
| H | 4 | 25 | ||
| 5 | 458 | |||
| 15 | 471 | |||
| 16 | 5 | |||
| 4 | 4 | 4 | 1 | 62 |
| 5 | 58 | |||
| 15 | 2 | |||
| 16 | 1 | |||
| 5 | 4 | 456 | ||
| 5 | 512 | |||
| 15 | 2 | |||
| 16 | 58 | |||
| 15 | 4 | 2 | ||
| 5 | 412 | |||
| 15 | 441 | |||
| 16 | 25 | |||
| 16 | 4 | 321 | ||
| 5 | 25 | |||
| 15 | 32 | |||
| 16 | 0 | |||
| H | 4 | 41 | ||
| 5 | 412 | |||
| 15 | 452 | |||
| 16 | 2 |
Table 19
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 5 | 1 | 6 |
| 5 | 2 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 5 | 4 | 0 | ||
| 5 | 25 | |||
| 15 | 2 | |||
| 16 | 3 | |||
| 15 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 25 | |||
| 16 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 35 | |||
| 16 | 0 | |||
| H | 4 | 0 | ||
| 5 | 47 | |||
| 15 | 2 | |||
| 16 | 5 | |||
| 4 | 4 | 1 | 2 | 25 |
| 5 | 21 | |||
| 15 | 2 | |||
| 16 | 47 | |||
| 5 | 4 | 261 | ||
| 5 | 455 | |||
| 15 | 421 | |||
| 16 | 41 | |||
| 15 | 4 | 25 | ||
| 5 | 412 | |||
| 15 | 432 | |||
| 16 | 25 | |||
| 16 | 4 | 0 | ||
| 5 | 2 | |||
| 15 | 1 | |||
| 16 | 0 | |||
| H | 4 | 0 | ||
| 5 | 485 | |||
| 15 | 547 | |||
| 16 | 20 |
Table 20
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 2 | 2 | 25 |
| 5 | 2 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 5 | 4 | 23 | ||
| 5 | 410 | |||
| 15 | 410 | |||
| 16 | 2 | |||
| 15 | 4 | 56 | ||
| 5 | 475 | |||
| 15 | 466 | |||
| 16 | 5 | |||
| 16 | 4 | 2 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 236 | ||
| 5 | 452 | |||
| 15 | 496 | |||
| 16 | 23 | |||
| 4 | 4 | 3 | 2 | 0 |
| 5 | 0 | |||
| 15 | 3 | |||
| 16 | 2 | |||
| 5 | 4 | 251 | ||
| 5 | 462 | |||
| 15 | 561 | |||
| 16 | 23 | |||
| 15 | 4 | 2 | ||
| 5 | 455 | |||
| 15 | 412 | |||
| 16 | 362 | |||
| 16 | 4 | 23 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 25 | ||
| 5 | 452 | |||
| 15 | 468 | |||
| 16 | 49 |
Table 21
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 4 | 2 | 23 |
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 5 | 4 | 15 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 15 | 4 | 25 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 25 | |||
| 16 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 25 | |||
| H | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 4 | 4 | 1 | 3 | 235 |
| 5 | 2 | |||
| 15 | 52 | |||
| 16 | 2 | |||
| 5 | 4 | 254 | ||
| 5 | 456 | |||
| 15 | 510 | |||
| 16 | 25 | |||
| 15 | 4 | 251 | ||
| 5 | 561 | |||
| 15 | 521 | |||
| 16 | 25 | |||
| 16 | 4 | 25 | ||
| 5 | 1 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 362 | ||
| 5 | 458 | |||
| 15 | 517 | |||
| 16 | 331 |
Table 22
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 2 | 3 | 21 |
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 25 | |||
| 5 | 4 | 2 | ||
| 5 | 451 | |||
| 15 | 482 | |||
| 16 | 213 | |||
| 15 | 4 | 25 | ||
| 5 | 469 | |||
| 15 | 458 | |||
| 16 | 214 | |||
| 16 | 4 | 23 | ||
| 5 | 25 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 256 | ||
| 5 | 475 | |||
| 15 | 496 | |||
| 16 | 51 | |||
| 4 | 4 | 3 | 3 | 23 |
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 5 | 4 | 41 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 25 | |||
| 15 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 251 | |||
| 16 | 0 | |||
| 16 | 4 | 0 | ||
| 5 | 25 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 0 | ||
| 5 | 32 | |||
| 15 | 0 | |||
| 16 | 0 |
Table 23
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 1 | 4 | 0 |
| 5 | 25 | |||
| 15 | 123 | |||
| 16 | 251 | |||
| 5 | 4 | 25 | ||
| 5 | 451 | |||
| 15 | 412 | |||
| 16 | 25 | |||
| 15 | 4 | 125 | ||
| 5 | 451 | |||
| 15 | 462 | |||
| 16 | 25 | |||
| 16 | 4 | 251 | ||
| 5 | 2 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 25 | ||
| 5 | 451 | |||
| 15 | 423 | |||
| 16 | 25 | |||
| 4 | 4 | 2 | 4 | 32 |
| 5 | 0 | |||
| 15 | 1 | |||
| 16 | 2 | |||
| 5 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 15 | 4 | 0 | ||
| 5 | 25 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 16 | 4 | 0 | ||
| 5 | 2 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 0 | ||
| 5 | 52 | |||
| 15 | 0 | |||
| 16 | 0 |
Table 24
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 0 | 1 | 11 |
| 5 | 13 | |||
| 15 | 20 | |||
| 16 | 0 | |||
| 5 | 4 | 48 | ||
| 5 | 441 | |||
| 15 | 410 | |||
| 16 | 25 | |||
| 15 | 4 | 23 | ||
| 5 | 410 | |||
| 15 | 421 | |||
| 16 | 36 | |||
| 16 | 4 | 32 | ||
| 5 | 25 | |||
| 15 | 15 | |||
| 16 | 32 | |||
| H | 4 | 25 | ||
| 5 | 455 | |||
| 15 | 412 | |||
| 16 | 36 | |||
| 4 | 4 | 0 | 2 | 36 |
| 5 | 56 | |||
| 15 | 121 | |||
| 16 | 56 | |||
| 5 | 4 | 254 | ||
| 5 | 455 | |||
| 15 | 500 | |||
| 16 | 25 | |||
| 15 | 4 | 62 | ||
| 5 | 410 | |||
| 15 | 485 | |||
| 16 | 26 | |||
| 16 | 4 | 69 | ||
| 5 | 3 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 25 | ||
| 5 | 440 | |||
| 15 | 444 | |||
| 16 | 21 |
Table 25
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 0 | 3 | 25 |
| 5 | 21 | |||
| 15 | 2 | |||
| 16 | 0 | |||
| 5 | 4 | 36 | ||
| 5 | 455 | |||
| 15 | 451 | |||
| 16 | 25 | |||
| 15 | 4 | 62 | ||
| 5 | 441 | |||
| 15 | 456 | |||
| 16 | 25 | |||
| 16 | 4 | 0 | ||
| 5 | 25 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 25 | ||
| 5 | 410 | |||
| 15 | 441 | |||
| 16 | 25 | |||
| 4 | 4 | 0 | 4 | 21 |
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 20 | |||
| 5 | 4 | 0 | ||
| 5 | 441 | |||
| 15 | 510 | |||
| 16 | 210 | |||
| 15 | 4 | 32 | ||
| 5 | 440 | |||
| 15 | 411 | |||
| 16 | 25 | |||
| 16 | 4 | 1 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 255 | ||
| 5 | 441 | |||
| 15 | 551 | |||
| 16 | 25 |
Table 26
| R 1Carbon number or H | R 2Carbon number | n | m | Cell voltage (mV) |
| 4 | 4 | 0 | 5 | 25 |
| 5 | 21 | |||
| 15 | 21 | |||
| 16 | 25 | |||
| 5 | 4 | 25 | ||
| 5 | 410 | |||
| 15 | 412 | |||
| 16 | 2 | |||
| 15 | 4 | 14 | ||
| 5 | 413 | |||
| 15 | 412 | |||
| 16 | 251 | |||
| 16 | 4 | 25 | ||
| 5 | 25 | |||
| 15 | 2 | |||
| 16 | 25 | |||
| H | 4 | 254 | ||
| 5 | 456 | |||
| 15 | 411 | |||
| 16 | 25 | |||
| 4 | 4 | 1 | 23 | |
| 5 | 0 | |||
| 15 | 1 | |||
| 16 | 0 | |||
| 5 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 5 | 14 | ||
| 15 | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| 16 | 4 | 25 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 0 | |||
| H | 4 | 0 | ||
| 5 | 0 | |||
| 15 | 0 | |||
| 16 | 2 |
Above result shows, works as R
1And R
2Be carbon number more than 5 the alkyl below 15 or hydrogen and n and m satisfy 0≤n≤5,0≤m≤5 and 1≤n+m≤5 o'clock discharge performance height, can obtain the above cell voltage of 400mV.On the other hand, when each parameter was beyond above-mentioned scope, cell voltage was below the 500mV.
Simultaneously, to using the battery 2 of general used in the past surfactant, also carry out same discharge test, the cell voltage that obtains is 415mV.
Above narration show, if use surfactant of the present invention, then can not damage hydrophobic polymer dispersiveness, and can guarantee to have and used the equal above battery behavior of the surfactant that might cause the endocrine confusion in the past.
Experimental example 1
Molecular formula: H-O-{ (C
2H
4O)
2-(C
3H
6O)
3}-C
5H
11
(long rapids industry (strain) is made: Te Laidun X-100) be warming up to 300 ℃ from room temperature respectively in air for shown alkylene oxide compound type surfactant and octyl phenol ethylate, at 300 ℃ of following constant temperature after 120 minutes, be heated to 400 ℃, then cooling, when carrying out this kind pattern thermal decomposition behavior analysis (TG-MS), residue is carried out infrared spectroscopic analysis (FT-IR).
The result is that alkylene oxide compound type surfactant and octyl phenol ethylate are about 0.09 weight % respectively and are about 1.1 weight % with respect to the residual quantity of primary quantity.
The residue of alkylene oxide compound type surfactant is simple hydrocarbon composition, in contrast to this, detects the composition that contains benzene ring structure from the residue of octyl phenol ethylate.This shows that remaining in the residue of octyl phenol ethylate have a phenylol.
This result shows that the surfactant in past (octyl phenol ethylate) can not decompose but residual problematic phenylol when generally heat-treating under 290～380 ℃ with air drier.Therefore, even the MEA and the electrode of surfactant carry out aforesaid general heat treatment to using in the past, also can not remove the environmental hormone composition fully.As a result, owing to the environmental hormone composition remains in the goods, when discarded goods are handled, for safe handling environmental hormone composition must adopt the special processing operation.
On the other hand, use the MEA and the electrode of alkylene oxide compound type surfactant of the present invention, just in the simple heat treatment operation, remove surfactant, do not have the residual of problem composition, so can guarantee the fail safe of goods.Also require no special processing operation when therefore goods are discarded, therefore can reduce the total cost of calculating according to life cycle.
Among the embodiment 1, used pure hydrogen to act as a fuel,, also can obtain same result even use the modification hydrogen that contains foreign bodys such as carbon dioxide gas, nitrogen, carbon monoxide.Also have in embodiment 2, used methanol solution to act as a fuel, though use liquid fuels such as ethanol, dimethyl ether with and composition thereof, also can obtain same result.Simultaneously, liquid fuel can also make its evaporation in advance, supplies with the form of steam and uses.Embodiment 1 and 2 gas diffusion layers are to use acetylene carbon black and carbon paper to make, but raw material is not limited to this, when using raw material such as carbon carbon black, carbon cloth, also can obtain same effect.In addition, formation of the present invention can not be limited with employed catalyst layer and dielectric film etc. among the embodiment, can use materials such as various catalyst layers and dielectric film.MEA of the present invention can be applied in all gases transducers such as gas generators such as oxygen, ozone, hydrogen, gas purifier, lambda sensor, ethanol sensor.
Reference example 1
(i) make gas diffusion layers
As the aqueous liquid dispersion of acetylene carbon black of conductive carbon particle (electrochemical industry (strain) is made: electrochemical carbon black, particle diameter are 35nm) and PTFE (Daikin Industries (strain) is made: D-1) mixing, modulate hydrophobic printing ink.Making the PTFE in the hydrophobic printing ink is 20 weight portions with respect to the content of per 100 weight portions of acetylene carbon black.
(make in east beautiful (strain): TGPH060H) surperficial, coating ratio is 30g/m then hydrophobic printing ink to be coated to carbon paper as the gas diffusion layers base material
2, make the hydrophobic printing ink of impregnation in the carbon paper.Then in air ambient, under 300 ℃, the carbon paper that contains hydrophobic printing ink is heat-treated, make gas diffusion layers with air drier.
(ii) form catalyst layer
Making average grain diameter is that (triumphant money grace carbon black international corporation (ケ ッ チ エ Application Block ラ ッ Network イ Application one Na シ ヨ Na Le) makes: Ketjen Black EC) the load average particle diameter is about platinum particles 50 weight portions of 30 dusts in 100 weight portions for the carbon particle of 30nm.
Then alcohol dispersion liquid of carrying platinum carbon particle, hydrogen polyelectrolyte and metal oxide powder are mixed modulation catalyst printing ink.At this moment, make the mixing ratio of carrying platinum carbon particle and hydrogen polyelectrolyte count 66: 33 with weight ratio.In the aforementioned hydrogen polyelectrolyte, (U.S. Alder Leech (Aldrich) company makes: the Na Feiang dispersion liquid of 5 weight %) to have used perfluorocarbon azochlorosulfonate acid ion cross-linked polymer.Simultaneously, in the metal oxide powder, having used average grain diameter respectively is the silicon dioxide (SiO of 0.8 μ m
2), titanium dioxide (TiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), magnesium oxide (MgO) also has chromium oxide (Cr
2O
3).In the catalyst ink, oxide powder is 1～10000ppm with respect to solid shape components contents.
Then, above-mentioned catalyst ink is printed onto a side surface of above-mentioned gas diffusion layer, then 70 ℃ dry down, forming thickness is the catalyst layer of 10 μ m.Make the electrode that constitutes by catalyst layer and gas diffusion layers like this.
(iii) make MEA
Use pair of electrodes, for the polyelectrolyte membrane of clamping hydrogen medially (du pont company manufacturing: Na Feiang 112), make MEA-a through hot pressing with catalyst layer.
(iv) assembling fuel cell
At MEA-a dielectric film peripheral part adhesive rubber packing ring, form cooling water, fuel gas and the general manifold hole of oxidant gas stream.
On the other hand, prepare the various dividing plates that are made of impregnation phenolic resins graphite cake, the overall dimensions of graphite cake are that 20cm * 32cm, thickness are that the degree of depth of 1.3mm, gas flow path or cooling water stream is 0.5mm.
Make the cathode side of the gas stream trackside subtend MEA-a of the dividing plate that is formed with the oxidant gas stream, make the anode-side of the gas stream trackside subtend MEA-a of the dividing plate that is formed with fuel gas channel, make it form an integral body, constitute monocell.
Then laminated two monocells, be aforementioned two batteries of clamping medially with a pair of dividing plate that is formed with the cooling water stream with the cooling water stream.Carry out the operation of this pattern repeatedly, make the laminated battery of 100 batteries.Dispose at the both ends of laminated battery the collector plate of stainless steel and electrical insulating material insulation board, use end plates and banding rod with overall fixed again.Banding pressure is every plate area 15kgf/cm
2The battery of making in order to the top method as battery A.
(v) qualification test
Respectively to the anode of battery A supply with pure hydrogen, to the negative electrode air supply, making battery temperature is that 75 ℃, fuel gas utilance (Uf) are 70%, air utilization ratio (Uo) is 40%, carries out the discharge test of battery.At this moment, make the bubbler of pure hydrogen by 70 ℃, make the bubbler of air by 50 ℃ carry out gas humidification.
Then, methanol aqueous solution from 2mol/l to the anode of battery A, the temperature of supplying with are 60 ℃, and making battery temperature is that 75 ℃, air utilization ratio (Uo) are 40%, carries out the discharge test of battery as direct type methanol fuel cell.At this moment, make the bubbler of air by 50 ℃ carry out gas humidification.
Reference example 2
(i) make gas diffusion layers
(Daikin Industries (strain) is made: D-1) with the metal oxide powder mixing, modulate hydrophobic printing ink as the acetylene carbon black (electrochemical industry (strain) is made: electrochemical carbon black, particle diameter 35nm) of conductive carbon particle, the aqueous liquid dispersion of PTFE.In the hydrophobic printing ink, PTFE is 20 weight portions with respect to the content of per 100 weight portions of acetylene carbon black.Simultaneously, having used average grain diameter in the metal oxide powder respectively is the silicon dioxide (SiO of 0.8 μ m
2), titanium dioxide (TiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), magnesium oxide (MgO) also has chromium oxide (Cr
2O
3).In the hydrophobic printing ink, oxide powder is 1～10000ppm with respect to solid shape components contents.
(make in east beautiful (strain): TGPH060H) surperficial, coating ratio is 30g/m then hydrophobic printing ink to be coated in carbon paper as the gas diffusion layers base material
2, make the hydrophobic printing ink of impregnation in the carbon paper.Then in air ambient, under 300 ℃, the carbon paper that contains hydrophobic printing ink is heat-treated, make gas diffusion layers with air drier.
(ii) form catalyst layer
Making average grain diameter is that (triumphant money grace carbon black international corporation makes: KetjenBlack EC) the load average particle diameter is about platinum particles 50 weight portions of 30 dusts in 100 weight portions for the carbon particle of 30nm.
Then, the alcohol dispersion liquid of carrying platinum carbon particle and hydrogen polyelectrolyte is mixed modulation catalyst printing ink.At this moment, make the mixing ratio of carrying platinum carbon particle 66 weight portions and hydrogen polyelectrolyte, count 66: 33 by weight.In the aforementioned hydrogen polyelectrolyte, (U.S. Alder Leech company makes: 5 weight % Na Feiang dispersion liquids) to have used perfluorocarbon azochlorosulfonate acid ion cross-linked polymer.
Then catalyst ink is printed onto a side surface of above-mentioned gas diffusion layer, dry under 70 ℃ then, forming thickness is the touching agent layer of 10 μ m, makes the electrode that is made of catalyst layer and gas diffusion layers like this.
(iii) make MEA
Use pair of electrodes, make catalyst layer be the polyelectrolyte membrane of clamping hydrogen medially (du pont company manufacturing: Na Feiang 112), MEA-b is made in hot pressing.
(iv) assembling fuel cell
Substitute MEA-a with MEA-b, in addition, carry out and reference example 1 identical operations, make the battery B that the laminated battery by 100 batteries constitutes.
(v) qualification test
Battery B is also carried out the discharge test identical with reference example 1.
Reference example 3
(i) make MEA
The hydrophobic printing ink that is used in modulation in the reference example 2 substitutes the hydrophobic printing ink of modulation in reference example 1, in addition, carries out and reference example 1 identical operations, makes MEA-c.Among the MEA-c, gas diffusion layers and catalyst layer both sides are contained metal oxide powder.But used metal oxide powder of the same race among each MEA-c.And make the content of metal oxide powder in the gas diffusion layers identical with the content of metal oxide powder in the catalyst layer.
(ii) assembling fuel cell
Substitute MEA-a with MEA-c, in addition, carry out and reference example 1 identical operations, make the battery C that the laminated battery by 100 batteries constitutes.
(iii) qualification test
Battery C is also carried out the discharge test identical with reference example 1.
Comparative example 2
(i) make MEA
Use the catalyst ink of modulating in the catalyst ink alternative reference example 1 of modulation in the reference example 2, in addition, carry out and reference example 1 identical operations, make MEA-x.Among the MEA-x, gas diffusion layers and catalyst layer both sides are not contained metal oxide powder.
(ii) assembling fuel cell
Substitute MEA-a with MEA-x, in addition, carry out and the reference example identical operations, make the battery X that the laminated battery by 100 batteries constitutes.
(iii) qualification test
Battery X is also carried out the discharge test identical with reference example.
The qualification test result of reference example 1～3
(i) hydrogen-air-fuel battery
Fig. 4 shows reference example battery A～C and comparative example battery X life characteristic one example as hydrogen-air-fuel battery.It is metal oxide powder in 10ppm, the gas diffusion layers characteristic when being 10ppm as the metal oxide powder in metal oxide powder, the catalyst layer that these life characteristics are to use silicon dioxide.
It is 300mA/cm that Fig. 4 illustrates current density
2The time, the operating time of battery and the relation of each single battery voltage.As shown in Figure 4, the average voltage of battery A, B, C and X monocell is respectively 759mV, 747mV, 768mV and 726mV in the early stage.After 2700 hours, their value is respectively 718mV, 706mV, 747mV and 528mV.Among the battery X of comparative example 2, the voltage deterioration is up to 198mV, and in contrast to this, among reference example battery A, B and the C, the voltage deterioration only is 41mV, 41mV and 21mV.
As mentioned above, in catalyst layer, add metal oxide powder and have more the effect that suppression characteristic reduces than in gas diffusion layers, adding metal oxide powder.All add in catalyst layer and gas diffusion layers both sides among the battery C of metal oxide powder simultaneously, voltage reduces minimum.Can think this be since in each layer the moisture content of polyelectrolyte reduce and the carbon particle hydrophobicity reduces and is inhibited, can keep the result of hydrogen, gas diffusibility and discharge generation outlet capacity for a long time.
(ii) direct type methanol fuel cell
Reference example battery A～C and comparative example battery X life characteristic one example as direct type methanol fuel cell has been shown among Fig. 5.These life characteristics are to use silicon dioxide as metal oxide powder and to make metal oxide powder in the catalyst layer be metal oxide powder in 10ppm, the gas diffusion layers life characteristic when being 10ppm.
But, in the MEA that direct methanol fuel cell is used, have the carbon particle of platinum particles and ruthenium particle to substitute with load and carry the platinum carbon particle, make the catalyst layer of anode-side.At this moment, the carbon particle of loaded with platinum particles and ruthenium particle is to be that (triumphant money grace carbon black international corporation makes: Ketjen Black EC) the load average particle diameter is about platinum particles 40 weight portions of 30 dusts and ruthenium particle 20 weight portions modulation that average grain diameter is about 30 dusts forms in 100 weight portions for the carbon particle of 30nm in average grain diameter.
It is 200mA/cm that Fig. 5 shows in current density
2The time operating time of battery and each single battery voltage relation.As shown in Figure 5, the average voltage of the monocell of battery A, B, C and X is respectively 621mV, 597mV, 635mV and 583mV in the early stage.Average voltage after 2700 hours is respectively 589mV, 568mV, 618mV and 210mV.Among the battery X of comparative example 2, the voltage deterioration is up to 373mV, and in contrast to this, the voltage deterioration is respectively at 32mV, 29mV and 17mV among reference example battery A, B and the C.
Can confirm by the above fact,,, bring into play the effect that suppression characteristic reduces owing in electrode, add metal oxide even in the middle of direct methanol fuel cell.
The (iii) content of metal oxide in hydrogen-air-fuel battery
Fig. 6 shows the relation of battery C as metal oxide powder content in the voltage of hydrogen-air-fuel battery and the electrode.The axis of abscissas of Fig. 6 is represented the content of metal oxide powder in the entire electrode, after the axis of ordinates of Fig. 6 is represented 2500 hours, is 280mA/cm in current density
2The time each monocell voltage.
Among Fig. 6, the content of metal oxide powder is kept high cell voltage in 1～10000ppm scope the time, can confirm to add the effect of metal oxide powder.Can think the metal oxide powder content reason that cell voltage reduces when 10000ppm is above owing to metal oxide is an insulating properties, so electrode electricity portion resistance increases.
Metal oxide powder is silicon dioxide (SiO in electrode
2), titanium dioxide (TiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), magnesium oxide (MgO) and chromium oxide (Cr
2O
3) time, the more preferably content of metal oxide powder is respectively 1～10000ppm, 3～4000ppm, 1～3000ppm, 1～10000ppm, 2～2000ppm and 1～2000ppm.
The content of metal oxide in the (iv) direct type methanol fuel cell
Fig. 7 shows the relation of battery C as metal oxide powder content in the voltage of direct type methanol fuel cell and the electrode.The axis of abscissas of Fig. 7 is represented the content of metal oxide powder in the entire electrode.The axis of ordinates of Fig. 7 represents that 2500 hours after-current density is 180mA/cm
2The time each monocell voltage.
But, in the MEA of direct type use for methanol fuel cells, use the carbon particle that carries platinum particles and ruthenium particle to substitute and carry platinum carbon particle making anode side catalyst layer.At this moment the carbon particle of loaded with platinum particles and ruthenium particle is that to make average grain diameter be that (triumphant money grace carbon black international corporation makes: Ketjen Black EC) in 100 weight portions, the load average particle diameter is about that 40 parts of the platinum particles of 30 dusts and ruthenium particle 20 weight portions modulation that average grain diameter is about 30 dusts form for the carbon particle of 30nm.
When metal oxide powder content is in 1～10000ppm scope among Fig. 7, keep high cell voltage, can confirm to add the metal oxide powder effect.Can think that the metal oxide powder content reason that cell voltage reduces when 10000ppm is above is an insulating properties because of metal oxide, so electrode interior resistance cause of increased.
In the electrode, metal oxide powder is silicon dioxide (SiO
2), titanium dioxide (TiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), magnesium oxide (MgO) and chromium oxide (Cr
2O
3) time, the more preferably content of metal oxide powder is respectively 1～10000ppm, 2～4000ppm, 1～10000ppm, 1～10000ppm, 1～2000ppm and 2～10000ppm.
Embodiment 3
(i) make gas diffusion layers
Be acetylene carbon black (electrochemical industry (strain) is made: electrochemical carbon black, particle diameter 35nm) and molecular formula as the conductive carbon particle:
H-O-{(C
2H
4O)
2-(C
3H
6O)
3}-C
5H
11
(Daikin Industries (strain) is made: D-1E) mix, modulate hydrophobic printing ink A for shown alkylene oxide compound type surfactant and the aqueous liquid dispersion of PTFE.In the hydrophobic printing ink, the content with respect to per 100 weight portion acetylene carbon blacks of surfactant and PTFE is respectively 10 weight portions and 20 weight portions.
(east beautiful (strain) manufacturing: surface TGPH060H), coating ratio are 30g/m then hydrophobic printing ink A to be coated to base material carbon paper as gas diffusion layers
2, make the hydrophobic printing ink A of carbon paper impregnation.Then in air ambient, under 350 ℃, gas diffusion layers is heat-treated, made to the carbon paper that contains hydrophobic printing ink A with air drier.
(ii) form catalyst layer
Making average grain diameter is that (triumphant money grace carbon black international corporation makes: KetjenBlack EC) in 100 weight portions, the load average particle diameter is about platinum particles 50 weight portions of 30 dusts for the carbon particle of 30nm.
Then alcohol dispersion liquid of carrying platinum carbon particle, hydrogen polyelectrolyte and metal oxide powder are mixed modulation catalyst printing ink.At this moment, carry the mixing ratio of platinum carbon particle and hydrogen polyelectrolyte, count 66: 33 by weight.In the aforementioned hydrogen polyelectrolyte, (U.S. Alder Leech company makes: 5 weight % Na Feiang dispersion liquids) to have used perfluorocarbon azochlorosulfonate acid ion cross-linked polymer.In the metal oxide powder, having used average grain diameter respectively is the silicon dioxide (SiO of 0.8 μ m
2), titanium oxide (TiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), magnesium oxide (MgO) also has chromium oxide (Cr
2O
3).In the catalyst ink, oxide powder is 1～10000ppm with respect to solid shape components contents.
Then, catalyst ink is printed onto on the side surface of above-mentioned gas diffusion layer, dry under 70 ℃, forming thickness is the catalyst layer of 10 μ m.Make the electrode that constitutes by catalyst layer and gas diffusion layers like this.
(iii) make MEA
Be the polyelectrolyte membrane of clamping hydrogen medially (du pont company manufacturing: Na Feiang 112) with pair of electrodes with catalyst layer, MEA-A is made in hot pressing.
(iv) assembling fuel cell
Use MEA-A to substitute MEA-a, in addition, carry out and reference example 1 identical operations, make the battery A ' that the laminated battery by 100 batteries constitutes.
(v) qualification test
Battery A ' is also carried out the discharge test identical with reference example 1.
Embodiment 4
(i) make gas diffusion layers
In the hydrophobic printing ink A with embodiment 3 modulation, further mixed metal oxide powders is modulated hydrophobic printing ink B.In the metal oxide powder, used the silicon dioxide (SiO of average grain diameter for difference 0.8 μ m
2), titanium dioxide (TiO
2), aluminium oxide (Al
2O
3), zirconia (ZrO
2), magnesium oxide (MgO) also has chromium oxide (Cr
2O
3).Among the hydrophobic printing ink B, oxide powder is 1～10000ppm with respect to solid shape components contents.
Then, (eastern beautiful manufacturing: surface TGPH060H), coating ratio are 30g/m hydrophobic printing ink B to be coated to carbon paper as the gas diffusion layers base material
2, make the hydrophobic printing ink B of carbon paper impregnation.Then in air ambient, the carbon that is soaked with the black B of hydrophobic oil is low heat-treats to containing under 350 ℃ with air drier, makes gas diffusion layers.
(ii) form catalyst layer
Making average grain diameter is that (triumphant money grace carbon black international corporation makes: KetjenBlack EC) in 100 weight portions, the load average particle diameter is about platinum particles 50 weight portions of 30 dusts for the carbon particle of 30nm.
Then the alcohol dispersion liquid of carrying platinum carbon particle and hydrogen polyelectrolyte is mixed modulation catalyst printing ink.At this moment, carry the mixing ratio of platinum carbon particle 66 weight portions and hydrogen polyelectrolyte, count 66: 33 with weight ratio.(U.S. Alder Leech company makes: 5 weight % Na Feiang dispersion liquids) to have used perfluorocarbon azochlorosulfonate acid ion cross-linked polymer in the aforementioned hydrogen polyelectrolyte.
Then catalyst ink being printed onto on the side surface of above-mentioned gas diffusion layer, is the catalyst layer of 10 μ m at 70 ℃ of dry down formation thickness.Make the electrode that constitutes by touching agent layer and gas diffusion layers like this.
(iii) make MEA
Be the polyelectrolyte membrane of clamping hydrogen medially (du pont company manufacturing: Na Feiang 112) with pair of electrodes with catalyst layer, MEA-B is made in hot pressing.
(iv) assembling fuel cell
Substitute MEA-a with MEA-B, in addition, carry out making the battery B ' that the laminated battery by 100 batteries constitutes with embodiment 1 identical operations.
(v) qualification test
Battery B ' is also carried out the discharge test identical with reference example 1.
Embodiment 5
(i) make MEA
Use the hydrophobic printing ink A that modulates in the hydrophobic printing ink B alternate embodiment 3 of modulation among the embodiment 4, in addition, carry out making MEA-C with embodiment 3 identical operations.In MEA-C, make gas diffusion layers and catalyst layer both sides all contain metal oxide powder, in each MEA-C, use metal oxide powder of the same race.Make the content of the metal oxide powder in the gas diffusion layers identical simultaneously with the content of metal oxide powder in the catalyst layer.
(ii) assembling fuel cell
Substitute MEA-a with MEA-C, in addition, advance and reference example 1 identical operations, make the battery C ' that the laminated battery by 100 batteries constitutes.
(iii) qualification test
Battery C ' is also carried out the discharge test identical with reference example 1.
The qualification test result of embodiment 3～5
(i) hydrogen-air-fuel battery
Test determination the life characteristic of embodiment battery A '～C ' as hydrogen-air fuel type battery.At this, having studied current density is 300mA/cm
2The time operating time of battery and the relation of each single battery voltage.
Use silicon dioxide as metal oxide powder, make metal oxide powder in the catalyst layer as 10ppm, when making metal oxide powder in the gas diffusion layers as 10ppm, the monocell average voltage of battery A ', B ' and C ' is respectively 757mV, 745mV and 765mV in the early stage.After 2700 hours, each magnitude of voltage is respectively 715mV, 702mV and 741mV.Like this, among battery A ', B ' and the C ', the degradation value of voltage is respectively at 42mV, 43mV and 24mV.
By above result as can be known, when using alkylene oxide compound type surfactant, also can obtain the effect that reduces with the equal suppression characteristic of reference example.
(ii) direct type methanol fuel cell
Test determination the endurance life characteristic of embodiment battery A '-C ' as direct methanol fuel cell.At this, having studied current density is 200mA/cm
2The time operating time of battery and each single battery voltage relation.
In the MEA of direct type use for methanol fuel cells, the carbon particle of the alternative loaded with platinum particles of the carbon particle of working load platinum particles and ruthenium particle is made the catalyst layer of anode-side.At this moment, the carbon particle of loaded with platinum particles and ruthenium particle is that to make average grain diameter be that (triumphant money grace carbon black international corporation makes: Ketjen Black EC) in 100 weight portions, the load average particle diameter is about that platinum particles 40 weight portions of 30 dusts and ruthenium particle 20 weight portions modulation that average grain diameter is about 30 dusts form for the carbon particle of 30nm.
Use silicon dioxide as metal oxide powder, make metal oxide powder in the catalyst layer as the metal oxide powder in 10ppm, the gas diffusion layers during as 10ppm, the average voltage of battery A ', B ' and C ' monocell value in the early stage is respectively 619mV, 595mV, 630mV and 579mV.After 2700 hours, these values are respectively 582mV, 562mV and 612mV.
This shows that among battery A ', B ' and the C ', the deterioration of voltage is respectively 37mV, 33mV and 18mV.
Can confirm by the above fact, in direct methanol fuel cell, when using alkylene oxide compound type surfactant, also can bring into play the effect that reduces with the equal suppression characteristic of reference example.
The (iii) content of metal oxide in hydrogen-air-fuel battery
Experimental study the relation of battery C ' as metal oxide powder content in the voltage of hydrogen-air-fuel battery and the electrode, be 280mA/cm in current density after the result shows 2500 hours
2The time each monocell voltage maintain with reference example 3 equal numerical value be that the metal oxide powder content range is 1～10000ppm.And the more preferably content range of metal oxide powder content is identical with reference example 3 in the electrode.
The content of metal oxide in the (iv) direct type methanol fuel cell
Experimental study the relation of battery C ' as metal oxide powder content in the voltage of direct methanol fuel cell and the battery, the result shows that after 2500 hours current density is 180mA/cm
2The time each monocell voltage maintain with reference example 3 equal numerical value be that the metal oxide powder content range is 1～10000ppm.The more preferably scope of metal oxide powder content is identical with reference example 3 in the electrode.
In reference example 1～3, use pure hydrogen or methyl alcohol to act as a fuel, even but when using the denatured fuel hydrogen that contains impurities such as carbon dioxide, nitrogen, carbon monoxide to act as a fuel, also can obtain same result.Simultaneously, even use instead of methanol such as ethanol, dimethyl ether and composition thereof, also can obtain equifinality.Liquid fuel also can make its evaporation supply with battery as steam in advance.
Reference example 4
(i) form catalyst layer
Make and have the conductive carbon particle that average primary particle diameter is 30nm that (Dutch AKZO Chemie company makes: triumphant money grace carbon black EC) in 50 weight portions, the load average particle diameter is about platinum particles 50 weight portions of 30 dusts.(German GETZMANN company makes: Dispermat SL-C12Z) water of the alcohol dispersion liquid of the carbon particle that carries platinum particles, hydrogen polyelectrolyte and ormal weight is mixed solid different catalyst ink A, B, C, D and the E of shape constituent content of modulation then to use pearl mill dispersion machine.Carry the carbon particle of platinum particles and the mixing ratio of hydrogen polyelectrolyte, count 100: 50 by weight.In the aforementioned hydrogen polyelectrolyte, (U.S. Alder Leech company makes: 5 weight % Na Feiang dispersion liquids) to have used perfluorocarbon sulfonic acid.
Here said solid shape constituent content be with the weight of catalyst ink divided by the total weight of conductive carbon particle, platinum particles and hydrogen polyelectrolyte in the catalyst, multiply by 100 resulting percent value.The solid shape constituent content of catalyst ink A is 20 weight %, and catalyst ink B is that 18 weight %, catalyst ink C are that 15 weight %, catalyst ink D are that 12 weight %, catalyst ink E are 5 weight %.
These catalyst inks are placed on the determination of viscoelasticity instrument, and (German HAAKE company makes: among this (レ オ ス ト レ ス) RS150 of Lay oersted Lay, use cone-plate (cone plate) type to measure head, change shear rate, measure ink viscosity.The relation of shear rate and viscosity is shown in table 8.
Can confirm that by Fig. 8 catalyst ink A, B, C and D present the shear rate non-newtonian fluid behavior that viscosity then reduces that raises.On the other hand, even presenting, catalyst ink E changes the Newtonian fluid behavior that shear rate also almost be can't see the viscosity variation.
Adopt coating unit shown in Figure 3 these ink coats to base material.Base material uses PETG (hereinafter referred to as PET) film (thickness is 50 μ m, width 250mm).After joining in the container for paint 32, send PET film 34 to catalyst layer printing ink 36, apply from the part 33 that unreels of coating unit.Catalyst ink is coated on the base material 34 by nozzle 37 from container 32.Make to be coated in filming on the base material and to be set at 60 ℃ hothouse 38 by temperature and to carry out drying, obtain catalyst layer.With on base material 34, forming catalyst layer A, B, C, D and E respectively with quadrat method.
When using catalyst ink A, because ink viscosity is too high, producing in filming has streak and mottled.When using catalyst ink E, begin just to produce the liquid opposite from nozzle head and weigh down phenomenon with base material moving direction.Simultaneously, filming of catalyst ink E flowed in the Width generation, applies extremely unstable.When using catalyst ink B, C and D, apply stable, do not exist film mottled.
Ink viscosity when table 27 has been summed up the kind of catalyst ink and shear rate and is 0.1 (l/sec) and 100 (l/sec) and apply stability relationship.
Table 27
| 0.1(l/s) | 100(l/s) | Stability | |
| Catalyst ink A | 250Pa·s | 5Pa·s | Bad |
| Catalyst ink B | 150Pa·s | 1Pa·s | Good |
| Catalyst ink C | 80Pa·s | 0.9Pa·s | Good |
| Catalyst ink D | 10Pa·s | 0.8Pa·s | Good |
| Catalyst ink E | 1Pa·s | 0.7Pa·s | Bad |
As shown in Table 27, viscosity can not form uniformly and film above the poor stability of the coating of the catalyst ink A of 1Pas when the catalyst ink E of the not enough 10Pas of viscosity and shear rate were 100 (l/sec) when shear rate was 0.1 (l/sec).
(ii) make monocell
With a pair of catalyst layer A clamping hydrogen polyelectrolyte membrane (du pont company manufacturing: Na Feiang 112), carry out hot pressing.Then with a pair of carbon paper (east beautiful (strain) manufacturing: the TGP-H-120) conjugant of clamping dielectric film and catalyst layer A, make monocell A.The same catalyst layer B～E that uses makes monocell B～E.
(iii) evaluate monocell
Monocell A～E is placed on the test instrument, tests the characteristic of each monocell.
Supply with modification analog gas (the hydrogen balance gas that contains carbon dioxide 25% and carbon monoxide 50ppm) to the anode of each battery respectively, negative electrode air supply to each battery, making battery temperature is that 80 ℃, fuel availability are 80%, air utilization ratio is 40%, carries out the discharge test of battery.At this moment, each gas is carried out humidification, make the dew point of modification analog gas reach 75 ℃, make the dew point of air reach 60 ℃.
Fig. 9 shows the I-E characteristic comparable situation of monocell A～E.As shown in Figure 9, use the catalyst ink A and the inhomogeneous catalyst layer A of E formation and monocell A and the E of catalyst layer E that apply poor stability, compare with other monocells, its battery behavior is low.
Like this, above, the non-newtonian fluid catalyst ink when shear rate is 100 (l/s) below the viscosity 1Pas of viscosity 10Pas can stably form uniform coating when being 0.1 (l/s) by the use shear rate.Simultaneously, use the fuel cell of the catalyst ink making of non-newtonian fluid to present good performance.
Reference example 5
(i) form catalyst layer
The catalyst ink C of use reference example 4 modulation is also the same with reference example, applies on base material.Also have 130 ℃ but the baking temperature of filming is set at 30 ℃, 40 ℃, 60 ℃, 100 ℃ respectively, formation catalyst layer C1, C2, C3, C4 also have C5.The outward appearance of catalyst layer C1～C4 much at one.But, can see the part crackle among the catalyst layer C5.The situation of the outward appearance of catalyst layer C1～C5 (a) and section (b) is shown in Figure 10.
(ii) make monocell
Use these catalyst layers C1～C5, carry out the operation same, make monocell C1～C5, the research battery behavior with reference example 4.
(iii) evaluate monocell
The experimental condition of setting monocell is identical with reference example 4.The I-E characteristic of these monocells is shown in Figure 11.
As shown in Figure 11, use the monocell C1 of catalyst layer C1 also lower than other monocell with the characteristic of the monocell C5 that uses catalyst layer C5.Can think that this is because in catalyst layer C1, baking temperature is lower, be 30 ℃, so remaining in the catalyst layer have a distributes ink medium.In addition, in catalyst layer C5, catalyst temperature is set higherly, is 130 ℃ that the rotten hydrogen that causes of hydrogen polyelectrolyte reduces in the catalyst layer, and crack in the catalyst layer and cause that battery behavior reduces.
By the baking temperature after the control catalyst ink coats, can stably prepare high performance fuel cell like this.In this reference example, adopt a stage seasoning to carry out drying, also can use the multistage segmentation seasoning that changes baking temperature to carry out drying.
Embodiment 6
(i) make gas diffusion layers
Conductive carbon particle acetylene carbon black (electrochemical industry (strain) make: electrochemical carbon black, particle diameter 35nm) 100 weight portions and following general formula:
H-O-{(C
2H
4O)
2-(C
3H
6O)
3}-C
5H
11
Shown alkylene oxide compound type surfactant 10 weight portions and PTFE amount are PTFE aqueous liquid dispersion (Daikin Industries (strain) manufacturing: D-1E) mix, modulate hydrophobic printing ink of 20 weight portions.
Then, (make in east beautiful (strain): TGP-H-120) go up on the surface, the coating ratio is 30g/m aforementioned hydrophobic printing ink to be coated to carbon paper as the gas diffusion layers base material
2, make the hydrophobic printing ink of impregnation in the carbon paper.Then in air ambient, heat-treat containing the carbon paper that is soaked with the hydrophobic oil China ink in 350 ℃, make gas diffusion layers with air drier.
(ii) make monocell
Use the above-mentioned gas diffusion layer to substitute carbon paper, in addition, carry out and reference example 5 identical operations, make the monocell C1 '～C5 ' that uses catalyst layer C1～C5.
(iii) evaluate monocell
The experimental condition of setting monocell is identical with reference example 4.Even the result shows in monocell C1 '～C5 ', also can obtain the I-E characteristic roughly the same with monocell C1～C5.
In said process, used the device of ball mill as the grinding dispersion catalyst ink, in addition, can also use devices such as edge runner, homogenizer, ball mill.In the said process, be the viscosity of adjusting printing ink by the method that changes the solid shape constituent content of catalyst ink simultaneously, can also immobilize by making solid shape constituent content, and the method for variation catalyst ink dispersity adjusted the viscosity of printing ink.In addition, can also use the method that changes solid shape component composition to adjust ink viscosity.In the painting method of catalyst ink, also can use methods such as silk screen printing, intaglio.In said method, used the base material of PET film as catalyst ink, also can directly apply polyelectrolyte membrane, gas diffusion layers.
Practicality on the industry
If according to the present invention, can be by being controlled to be the optimum state that improves the surfactant that hydrophobic polymer and adhesive dispersive property use in the gas diffusing layer of fuel cell electrode, in improving fuel cell goods and preparation section thereof in the security, reduce in the preparation section hydrophobic printing ink film inhomogeneous and film quality bad. If according to the present invention, can also by the optimum moisture content of control fuel cell electrode, further improve battery performance. The present invention neither adopts thickener, does not also heat, but passes through the method that the solid concentration of component is controlled catalyst ink viscosity, can obtain to have the fuel cell of catalyst particle equally distributed catalyst layer on the face direction.
Claims (3)
1. the method for preparing polymer electrolyte fuel cells, it is to comprise
Modulation contains the operation A of the hydrophobic printing ink of at least a, hydrophobic polymer, surfactant and decentralized medium in carbon particle and the carbon fiber,
Modulate the process B of the catalyst ink of the carbon particle, hydrogen polyelectrolyte and the decentralized medium that contain the supported catalyst particle,
Aforementioned hydrophobic printing ink is coated to the decentralized medium evaporation that on the conductivity porous matter base material, then makes aforementioned hydrophobic printing ink, the operation C that forms gas diffusion layers,
With aforementioned catalyst ink form catalyst layer step D and
Use the preparation method of polymer electrolyte fuel cells of the operation E of aforementioned gas diffusion layers, aforementioned catalyst layer and hydrogen polyelectrolyte membrane assembling monocell, wherein,
Used aforementioned surfactants is to be made of the compound shown in the general formula 1 among the operation A:
R
1-O-{(C
2H
4O)
n-(C
3H
6O)
m}-R
2
In the formula, R
1And R
2Be the carbon number alkyl below 15 or hydrogen atom more than 5, n and m are the integers that satisfies 0≤n≤5,0≤m≤5 and 1≤n+m≤5 conditions, and when n and m were not 0 simultaneously, the arrangement of at least one Oxyranyle and at least one expoxy propane base was random;
Aforementioned catalyst ink is when shear rate is 0.1 (1/sec), has the above viscosity of 10Pas, when shear rate is 100 (1/sec), the non-newtonian fluid with the following viscosity of 1Pas.
2. the method for preparing polymer electrolyte fuel cells according to claim 1, wherein, aforementioned step D include under the temperature below 100 ℃ more than 40 ℃ from form with aforementioned catalyst ink film make the operation of aforementioned decentralized medium evaporation.
3. the preparation method of polymer electrolyte fuel cells according to claim 1, wherein, in the aforementioned catalyst ink weight ratio of contained aforementioned catalyst particle and aforementioned carbon particle and aforementioned polyelectrolyte actual be 1: 1: 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057/2001 | 2001-03-07 | ||
| JP2001063057A JP2002270189A (en) | 2001-03-07 | 2001-03-07 | Manufacturing method for high polymer electrolyte type fuel cell and high polymer electrolyte type fuel cell using the same |
| JP73730/2001 | 2001-03-15 | ||
| JP84770/2001 | 2001-03-23 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028015134A Division CN1268016C (en) | 2001-03-07 | 2002-03-05 | Polymer electrolyte type fuel cell and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
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| CN1770518A true CN1770518A (en) | 2006-05-10 |
| CN100377397C CN100377397C (en) | 2008-03-26 |
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| CN113793962A (en) * | 2021-08-11 | 2021-12-14 | 广州市乐基智能科技有限公司 | High-performance fuel cell binder and preparation method and application thereof |
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| CA2771421C (en) * | 2009-09-10 | 2014-02-18 | Nissan Motor Co., Ltd. | Method for manufacturing gas diffusion layer for fuel cell, gas diffusion layer for fuel cell, and fuel cell |
| JP5609474B2 (en) * | 2010-09-17 | 2014-10-22 | 凸版印刷株式会社 | Method for producing fuel cell electrode catalyst layer |
| CN104685683A (en) | 2012-09-28 | 2015-06-03 | 日产自动车株式会社 | Coating device |
| JP5915517B2 (en) * | 2012-12-25 | 2016-05-11 | トヨタ自動車株式会社 | Manufacturing method of fuel cell electrode |
| JP6582390B2 (en) * | 2014-10-28 | 2019-10-02 | 東洋インキＳｃホールディングス株式会社 | Water repellent paste for gas diffusion layer, gas diffusion layer for fuel cell and fuel cell |
| JP6459429B2 (en) * | 2014-11-25 | 2019-01-30 | 凸版印刷株式会社 | Catalyst ink for forming electrode catalyst layer for polymer electrolyte fuel cell, and method for producing polymer electrolyte fuel cell |
| JP2020026044A (en) * | 2018-08-09 | 2020-02-20 | ローランドディー．ジー．株式会社 | Special printing decoration printer |
| JP7131269B2 (en) * | 2018-10-02 | 2022-09-06 | 凸版印刷株式会社 | Catalyst ink for electrode catalyst layer formation of polymer electrolyte fuel cells |
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| US3160530A (en) * | 1960-09-19 | 1964-12-08 | Union Carbide Corp | Fuel cell electrode conditioning |
| JPS6381706A (en) * | 1986-09-26 | 1988-04-12 | 三井金属鉱業株式会社 | Composition for copper based thick film |
| JPS63301274A (en) * | 1987-05-15 | 1988-12-08 | デユポンジヤパンリミテツド | Conductive paste composition |
| JPH08115727A (en) * | 1994-10-17 | 1996-05-07 | Tanaka Kikinzoku Kogyo Kk | Preparation of electrode for high-molecular solid electrolytic type electrochemistry cell |
| JPH09180727A (en) * | 1995-12-27 | 1997-07-11 | Tokyo Gas Co Ltd | Electrode for fuel cell, manufacture thereof, and apparatus therefor |
| US5945231A (en) * | 1996-03-26 | 1999-08-31 | California Institute Of Technology | Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof |
| JPH10126023A (en) * | 1996-10-22 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Copper paste for filling up via hole of printed board |
| JPH1140172A (en) * | 1997-07-14 | 1999-02-12 | Asahi Chem Ind Co Ltd | Method for producing film-electrode joined body for fuel cell |
| JP3577402B2 (en) * | 1997-07-28 | 2004-10-13 | 株式会社東芝 | Polymer electrolyte fuel cell |
| DE19909930B4 (en) * | 1999-03-06 | 2004-09-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Manufacture of tubular PEM fuel cells and ion exchange membranes |
-
2001
- 2001-03-07 JP JP2001063057A patent/JP2002270189A/en active Pending
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| CN113793962A (en) * | 2021-08-11 | 2021-12-14 | 广州市乐基智能科技有限公司 | High-performance fuel cell binder and preparation method and application thereof |
| CN113793962B (en) * | 2021-08-11 | 2023-09-19 | 广州市乐基智能科技有限公司 | Fuel cell adhesive and preparation method and application thereof |
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| JP2002270189A (en) | 2002-09-20 |
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