CN1842935A - Polyelectrolyte fuel cell-use separator, polyelectrolyte fuel cell, method of evaluating polyelectrolyte fuel cell-use separator, and production method of polyelectrolyte fuel cell-use separator - Google Patents

Polyelectrolyte fuel cell-use separator, polyelectrolyte fuel cell, method of evaluating polyelectrolyte fuel cell-use separator, and production method of polyelectrolyte fuel cell-use separator Download PDF

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CN1842935A
CN1842935A CNA2005800008657A CN200580000865A CN1842935A CN 1842935 A CN1842935 A CN 1842935A CN A2005800008657 A CNA2005800008657 A CN A2005800008657A CN 200580000865 A CN200580000865 A CN 200580000865A CN 1842935 A CN1842935 A CN 1842935A
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separator
polymer electrolyte
fuel cells
water droplet
electrolyte fuel
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CN100505401C (en
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羽藤一仁
神原辉寿
柴田础一
安本荣一
鹈木重幸
长崎达夫
寺西正俊
川岛勉
寿川彻
武部安男
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from PCT/JP2005/009875 external-priority patent/WO2005117180A1/en
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

A polyelectrolyte fuel cell-use separator having a surface excellent in condensed water discharging performance despite a low pressure loss of supply gas, a highly-reliable polyelectrolyte fuel cell capable of sufficiently controlling the occurrence of a flooding phenomenon despite a low pressure loss of supply gas, a method of evaluating a polyelectrolyte fuel cell-use separator capable of accurately evaluating a condensed water discharging performance, and a method of producing a polyelectrolyte fuel cell-use separator having a surface excellent in condensed water discharging performance despite a low pressure loss of supply gas. The polyelectrolyte fuel cell-use separator comprises conductive carbon and a binder solidifying the conductive carbon, wherein a water drop falling angle on the surface of a reaction gas flow path (30C, 40C) formed on at least one main surface is 5 deg. through 45 deg. when a water drop of 50 muL through 80 muL is dropped under conditions of an environmental temperature within a range of 50 DEG C through 90 DEG C and an environmental humidity within a range of absolute humidity of 70% through 100%.

Description

The manufacture method that polymer electrolyte fuel cells is used separator with separator, polymer electrolyte fuel cells, polymer electrolyte fuel cells with the evaluation method and the polymer electrolyte fuel cells of separator
Invention field
The present invention relates to the manufacture method that polymer electrolyte fuel cells is used separator with separator, polymer electrolyte fuel cells, polymer electrolyte fuel cells with the evaluation method and the polymer electrolyte fuel cells of separator.The evaluation method that the electroconductive polymer Electrolyte type fuel cell that particularly relates to the bonding agent that comprises conductive carbon and reinforce conductive carbon is estimated with the drainage of separator with separator, to polymer electrolyte fuel cells and polymer electrolyte fuel cells and the manufacture method of polymer electrolyte fuel cells usefulness separator.
Background technology
In the polymer electrolyte fuel cells, because of the phenomenon that causes battery performance instability or performance to reduce in the gas flow path of inside battery and phenomenons such as electrode interior generation dewfall, water slug, be overflow phenomena.In order to control this problem, various polymer electrolyte fuel cells have been implemented or have proposed with separator (being designated hereinafter simply as " separator ") or operation method.Particularly, implement to increase the supply pressure of anodic gas and cathode gas usually, drive away the operation method of the moisture of dewfall.
Yet the supply pressure that increases anodic gas and cathode gas is driven away the operation method of the moisture of dewfall, the supply mean of these reacting gass need be made the supply mean of high pressure, and the structure of polymer electrolyte fuel cells is made pressure-resistance structure.In addition, the high voltage supply of reacting gas is associated with the efficiency reduction that makes polymer electrolyte fuel cells.
Therefore, proposed the method for hydrophobic treatment/hydrophilic treated or the scheme of separator (referring to Patent Document 1～19) are carried out in the surface.In addition, proposed to constitute with the method for the contact angle that increases/reduce separator and moisture or the scheme (referring to Patent Document 20～30) of separator by the material that comprises water wetted material/hydrophobic material.The separator of structure of overflow or the scheme (referring to Patent Document 31～37) that separator and electrode are made up etc. have been proposed to prevent in addition.
Patent documentation 1: the spy opens the 2003-282087 communique
Patent documentation 2: the spy opens the 2003-257468 communique
Patent documentation 3: the spy opens the 2003-151585 communique
Patent documentation 4: the spy opens the 2003-151572 communique
Patent documentation 5: the spy opens the 2003-123780 communique
Patent documentation 6: the spy opens the 2003-112910 communique
Patent documentation 7: the spy opens the 2003-109619 communique
Patent documentation 8: the spy opens the 2002-313356 communique
Patent documentation 9: the spy opens the 2002-042830 communique
Patent documentation 10: the spy opens the 2002-020690 communique
Patent documentation 11: the spy opens the 2001-076740 communique
Patent documentation 12: the spy opens the 2000-251903 communique
Patent documentation 13: the spy opens the 2000-223131 communique
Patent documentation 14: the spy opens the 2000-100452 communique
Patent documentation 15: the spy opens the 2000-036309 communique
Patent documentation 16: the spy opens flat 09-298064 communique
Patent documentation 17: the spy opens flat 07-302600 communique
Patent documentation 18: the spy opens flat 05-251091 communique
Patent documentation 19: table 99/40642 communique again
Patent documentation 20: the spy opens the 2003-297385 communique
Patent documentation 21: the spy opens the 2003-217608 communique
Patent documentation 22: the spy opens the 2003-208905 communique
Patent documentation 23: the spy opens the 2003-208904 communique
Patent documentation 24: the spy opens the 2002-352813 communique
Patent documentation 25: the spy opens the 2001-283873 communique
Patent documentation 26: the spy opens the 2001-093539 communique
Patent documentation 27: the spy opens the 2000-31695 communique
Patent documentation 28: the spy opens flat 10-003931 communique
Patent documentation 29: the spy opens the 2001-509950 communique
Patent documentation 30: the spy opens flat 08-503100 communique
Patent documentation 31: the spy opens the 2003-197217 communique
Patent documentation 32: the spy opens the 2003-197203 communique
Patent documentation 33: the spy opens the 2003-168452 communique
Patent documentation 34: the spy opens the 2003-007312 communique
Patent documentation 35: the spy opens the 2002-343369 communique
Patent documentation 36: the spy opens the 2002-203571 communique
Patent documentation 37: the spy opens the 2001-110432 communique
Summary of the invention
The problem that invention is solved
Yet polymer electrolyte fuel cells power termination change power output as required is an output current usually.At this moment, if also change the supply gas flow according to output current, moving with roughly certain fuel availability and coefficient of oxygen utilization, then is high efficiency.Promptly when partial load run, the also corresponding minimizing of supply gas amount with it.Therefore at this moment, the pressure loss of supply gas is also low certainly, when partial load run, is easy to generate overflow phenomena, i.e. water slug phenomenon in separator more.Therefore, even under the little condition of the pressure loss of supply gas (for example in the condition below the 10kPa), also require to develop the separator on surface with dew discharging performance excellence.
Even in the prior art of in above-mentioned patent documentation 1～37, putting down in writing, even do not have to realize under the little condition of the pressure loss of supply gas (for example in the condition below the 10kPa), having the separator of excellent dew discharging performance yet yet, room for improvement still arranged.Particularly face the problem of the following stated, promptly under the situation of the separator (compression forming separator) that the mixture compression forming that will comprise conductive carbon and bonding agent forms, under the little condition of the pressure loss of supply gas (for example in the condition below the 10kPa), be difficult to obtain excellent dew discharging performance.
Therefore, the present invention finishes in view of the above problems, even its purpose is to provide the polymer electrolyte fuel cells separator that also has the surface of dew discharging performance excellence under the little condition of the pressure loss of supply gas.In addition, the present invention also aims to, the polymer electrolyte fuel cells separator of the invention described above is provided, even and provide under the little condition of the pressure loss of supply gas, also can fully suppress the polymer electrolyte fuel cells of reliability excellence of the generation of overflow phenomena.The present invention also aims to, the evaluation method of the polymer electrolyte fuel cells of the discharging performance that can accurately estimate dew with separator is provided.In addition, the objective of the invention is to, even the manufacture method of the polymer electrolyte fuel cells on the surface that also has dew discharging performance excellence under the little condition of the pressure loss of supply gas with separator is provided.
The inventor in order to achieve the above object, concentrate on studies repeatedly, according to the result that the dew discharging performance is verified, found following situation, promptly for the surface of polymer electrolyte fuel cells, under operating temperature under the condition when generating electricity with the separator stream, and under the condition of surface wettability, so far the angle initialization that the water droplet that does not have to pay attention to is fallen down is below the angle of regulation, then can obtain excellent dew discharging performance, thereby can realize the present invention.
Promptly the invention provides a kind of polymer electrolyte fuel cells separator, this separator comprises conductive carbon and reinforces the bonding agent of conductive carbon, at least on an interarea, form reaction gas flow paths, under the environment temperature and the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70% in 90 ℃ of following scopes more than 50 ℃, make under the situation of the following water droplet drippage of the above 80 μ L of 50 μ L, the water droplet drippage angle on the surface of described reaction gas flow paths is below 45 degree more than 5 degree (claim 1).
If make such formation, even then polymer electrolyte fuel cells also has the characteristic of dew discharging performance excellence with the surface of the reaction gas flow paths of separator under the little condition of the supply pressure loss of reacting gas, so can constitute the respond well polymer electrolyte fuel cells separator of overflow phenomena inhibition.Particularly as if the separator (compression forming separator) that above-mentioned formation is applied to comprise the mixture compression forming of conductive carbon and bonding agent and to form, even then under the little condition of the pressure loss of supply gas (for example condition below 10kPa) also can be easily and correctly obtain good dew discharging performance.In addition, polymer electrolyte fuel cells separator of the present invention is with the conductivity separator of conductive carbon as structural material.
Here, so-called reacting gas is meant oxidant gas (gas that comprises oxidant) and the reducing agent gas (gas that comprises reducing agent) that offers high-molecular electrolyte fuel battery among the present invention.In addition, among the present invention, so-called reaction gas flow paths is meant and is being formed at polymer electrolyte fuel cells with the stream of circulations such as the slot part of insulation surface, cavern part, the i.e. stream of reacting gas under the polymer electrolyte fuel cells assembled state.In addition, among the present invention, so-called " water droplet drop angle " is meant the angle of inclination on the surface of measuring object (separator etc.), just refers to be still in the angle of inclination that the water droplet on the surface of measuring object begins landing, refers to the angle [alpha] of obtaining by the method for measurement that illustrates with following Fig. 1 and Fig. 2.
Polymer electrolyte fuel cells of the present invention is following get final product (claims 2) of the above 4.0 μ m of 1.5 μ m with the roughness arithmetic average deviation value (Ra) of its reacting gas flow road surfaces of separator.If adopt such formation, the then not influence of durability of the separator that high-molecular electrolyte fuel battery is used, and can pass through oxygen plasma treatment seeks to improve the water droplet angle that drops more easily and correctly.Also have, according to same viewpoint, polymer electrolyte fuel cells of the present invention with the roughness arithmetic average deviation value (Ra) of its reacting gas flow road surfaces of separator more than 2.5 μ m 4.0 μ m with next better.Moreover, from making separator compact for the viewpoint of practical level size, promptly in fact fully reduce the viewpoint of the deviation of the size of gas flow path of manufacturing and design load, preferably the roughness arithmetic average deviation value (Ra) of reacting gas flow road surfaces is below 4.0 μ m.
In the roughness arithmetic average deviation value (Ra) of polymer electrolyte fuel cells of the present invention with its reaction gas flow paths of separator, the spacing between its trickle protuberance gets final product (claim 3) below about 5 μ m.If adopt such formation, even then under the little condition of the supply pressure loss of reacting gas, also can be easier and the vibration of supply pressure inhibitory reaction gas correctly loss, therefore can easier and correctly suppress the vibration of the generating power output of polymer electrolyte fuel cells.
From obtaining the viewpoint of effect of the present invention more reliably, polymer electrolyte fuel cells of the present invention also can form (claim 4) by the processing of sandblasting, laser processing or processing and forming with the surface of its described reaction gas flow paths of separator.
Polymer electrolyte fuel cells of the present invention has carried out the stage processing of sandblasting with separator to the surface of reaction gas flow paths and has got final product (claim 5).If adopt such formation, then form multistage sag and swell on the surface of reaction gas flow paths, specific surface is big, below above 45 degree of the angle adjustment to 5 that therefore can easier and correctly water droplet be dropped degree.Here, so-called specific surface is meant the long-pending surface area in per unit plane of separator stream.Here, the so-called stage processing of sandblasting is meant the multistage processing of sandblasting, and compares with the processing of sandblasting of front, and the particle diameter of its particle that adds the use in man-hour of sandblasting of processing that sandblasts of back is little.
Again, polymer electrolyte fuel cells of the present invention also can carry out oxygen plasma treatment (claim 6) with separator to the surface of reaction gas flow paths.If adopt such formation, then polymer electrolyte fuel cells can be adjusted to below 5 degree above 45 spend with the water droplet of the flow path surfaces of the separator angle [alpha] that drops.
Also have, polymer electrolyte fuel cells of the present invention preferably utilizes the formation (claim 7) of the mixture compression forming method that contains conductive carbon and bonding agent with separator.As mentioned above, if adopt such formation, even then under the little condition of the pressure loss of supply gas (for example in the condition below the 10kPa), also can be easily and correctly constitute compression forming separator with good dew discharging performance.The compression forming separator with to being that the separator that the hard tabular component of principal component carries out the type that cutting forming is processed to form is compared with the conductive carbon, can be easily and at low cost (for example about 1/100th) make, like this, by making it possess good drainage, can make very big contribution to a large amount of productions that realize polymer electrolyte fuel cells.
In addition, even polyelectrolyte type battery of the present invention also can be also can be the injection-molded compression forming separator that can utilize injection-molded forming technique to make in above-mentioned compression forming separator with separator, in this case, help carrying out greater amount production.
The invention provides the polymer electrolyte fuel cells that the polymer electrolyte fuel cells that possesses described in the claim 1 is used separator (claim 8) again.By making the structure of separator of the polymer electrolyte fuel cells with the invention described above, can fully suppress overflow phenomena, even therefore can be formed in the good polymer electrolyte fuel cells of reliability that the little condition of the pressure loss of supply gas also can be kept stable generating.
Also have, the invention provides according to polymer electrolyte fuel cells with the water droplet on the surface of the reaction gas flow paths that forms in the separator angle that drops, the dew discharging performance of this reaction gas flow paths is estimated the evaluation method of the polymer electrolyte fuel cells of (claim 9) with separator.If make such structure, then can estimate the discharging performance of polymer electrolyte fuel cells exactly with the surface sweating water of the reaction gas flow paths of separator.
From obtaining the viewpoint of effect of the present invention more reliably, polymer electrolyte fuel cells of the present invention is dropped in the surface of described reaction gas flow paths with the evaluation method of separator by making water droplet, obtains the described water droplet angle that drops and gets final product (claim 10).
Polymer electrolyte fuel cells of the present invention is with in the evaluation method of separator, the described water droplet angle that drops also can be a environment temperature in the scope below 90 ℃ more than 50 ℃, and under the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70%, the water droplet of the water droplet that the above 80 μ L of 50 μ L the are following angle (claim 11) that drops.If make such structure, then need not the strict physical condition that reproduces and just can measure the angle that water droplet drops, so can be easily and estimate the dew discharging performance exactly.
Again, the invention provides a kind of bonding agent that contains conductive carbon and reinforcing conductive carbon, at least on an interarea, form the manufacture method of the polymer electrolyte fuel cells of reaction gas flow paths with separator, under the environment temperature and the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70% in 90 ℃ of following scopes more than 50 ℃, when making the following water droplet drippage of the above 80 μ L of 50 μ L, the surface of reaction gas flow paths forms the water droplet structure (claim 12) of angle below 5 degree above 45 are spent that drop.
Adopt the manufacture method of polymer electrolyte fuel cells of the present invention with separator, can satisfy above-mentioned water droplet and drop the structure of condition of angle except forming, by adopting well-known separator manufacturing technology such as well-known process for treating surface (physical surface treatment, chemical surface treatment etc.) (comprise also that material is selected, the adjusting of the blending ratio of the mixed method of material and material etc.), can be easily and obtain above-mentioned polymer electrolyte fuel cells separator of the present invention reliably.
The invention effect
As mentioned above, adopt the present invention, even the polymer electrolyte fuel cells separator that also has the surface of dew discharging performance excellence under the little condition of the pressure loss of supply gas then can be provided.In addition, if adopt the present invention, even the polymer electrolyte fuel cells of the reliability excellence of the generation that also can fully suppress overflow phenomena under the little condition of the pressure loss of supply gas then can be provided.Also have,, then can provide the polymer electrolyte fuel cells that accurately to estimate the dew discharging performance evaluation method of separator if adopt the present invention.In addition, even can be easily and make the polymer electrolyte fuel cells separator that under the little condition of the pressure loss of supply gas, also has the surface of dew discharging performance excellence reliably.
Industrial applicability
Even the present invention is applicable to the polymer electrolyte fuel cells separator that also has the surface of dew discharging performance excellence under the little condition of the pressure loss of supply gas, even under the little condition of the pressure loss of supply gas, also can fully suppress the polymer electrolyte fuel cells of the reliability excellence of overflow phenomena generation, can accurately estimate the evaluation method of the polymer electrolyte fuel cells of dew discharging performance with separator, even and as the polymer electrolyte fuel cells of making easily and reliably the surface that under the little condition of the pressure loss of supply gas, also has dew discharging performance excellence with the polymer electrolyte fuel cells of separator manufacture method with separator.
Concrete example
At first, the opinion as the inventor of background of the present invention is described.
As mentioned above, the inventor finds following situation, promptly the result who verifies with the dew discharging performance on the gas flow passage surface of separator (hereinafter referred to as " separator ") attached to polymer electrolyte fuel cells is shown, in taking place, operating temperature range produces in the gas flow path in the polymer electrolyte fuel cells of endemism of aqueous water, with its (1) as in the past, the contact angle of the water droplet that is conceived to remain static on the gas flow passage surface (soakage) designs (hydrophily to the structure of gas flow passage surface, hydrophobicity, roughness arithmetic average deviation value (Ra) etc.), when and for example (2) are conceived to form the beginning mobile status attached to the pushing that the water droplet on the gas flow passage surface is subjected to flowing into the reacting gas flow in the stream " water droplet drop angle " of this water droplet, structure to gas flow passage surface designs (more specifically, be designed to " environment temperature in 90 ℃ of following scopes more than 50 ℃; and under the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70%; when making the following water droplet drippage of the above 80 μ L of 50 μ L; the water droplet on the surface of reaction gas flow paths drops angle below 5 degree above 45 are spent "), the latter can be easily and is obtained drainage good in the operate condition { the particularly good drainage under the little condition of the pressure loss of supply gas (for example in the condition below the 10kPa) } reliably, is very effective.
For example, generally speaking, if the surperficial possess hydrophilic property or the hydrophobicity of the gas flow path of separator, then the dew discharging performance of separator trend is good.Yet, under the situation that separator is only made according to above-mentioned (1) design, even even excellent and seldom also have under the situation of limited contact angle in hydrophily, the dew of the gas flow passage surface of separator exists with the state of the water piece that forms limited area.So the formation dewfall if water droplet is superimposed then produces the situation that water droplet stops up stream sometimes.
Again, in the gas flow passage surface of separator under the situation of hydrophobicity excellence, the water of dewfall is still to keep the state of very little water droplet on the gas flow passage surface of separator, the mode that tumbles with the gas flow passage surface from separator is washed away by gas, is not easy to cause the obstruction of separator stream.Yet, separator is under situation about only making according to the design of above-mentioned (1), when the roughness arithmetic average deviation value (Ra) of the gas flow passage surface of separator is big, the roughness arithmetic average deviation value (Ra) of the gas flow passage surface of separator, be trickle concavo-convex, the function that plays the picture anchor, produce the situation that water droplet stops up stream sometimes.
Therefore, for the evaluation of the dew discharging performance in the gas flow passage surface of separator, only hydrophily or the hydrophobicity evaluation according to the design of above-mentioned (1) is inadequate.
The inventor has found following situation, promptly utilize the water droplet angle [alpha] evaluation of dropping, thereby can be with only irrespectively according to the hydrophily of the design of above-mentioned (1) and hydrophobicity, easily and correctly the dew discharging performance of the gas flow passage surface of the separator of the condition of work that is fit to fuel cell is estimated.
Here, among the present invention so-called " contact angle ", be meant the angle (being positioned at the angle of the inside of liquid) that liquid level and solid face form on the position of the Free Surface of inactive liquid (water droplet) contact solid walls (separator) (Japanese " " the physics and chemistry dictionary " of rock ripple the 5th edition " 739 pages described in contact angle), more specifically, be that this measuring object is configured, make the surface level of this measuring object (separator), placing a certain amount of water droplet on this surface and making under its static situation, the angle (being positioned at the angle of the inside of water droplet) of the surface of above-mentioned measuring object and the liquid level of water droplet (face that contacts with extraneous gas that is different from the surface of measuring object) formation.
Again, as mentioned above, so-called " water droplet drop angle " is meant the angle [alpha] of obtaining according to the method for measurement that illustrates with Fig. 1 described later and Fig. 2.
Fig. 1 illustrates the drop schematic diagram of method of measurement of angle of water droplet.The drop method of measurement of angle of water droplet is as follows, flatly the surface of allocating and measuring object 300, be the flow path surfaces of separator.Then, the water droplet 310 of ormal weight is dropped in the surface of measuring object 300.Then, the surface of measuring object 300 is tilted gradually, as shown in Figure 1, the surface tilt degree α that this water droplet 310 is begun the measuring object 300 when mobile from initial position is recorded in photo or the image.Can measure the water droplet angle [alpha] that drops according to this photo or image.
Again, Fig. 2 illustrates the drop schematic diagram of indirect measurement method of angle of water droplet.In general, water droplet drop angle [alpha] according to " R γ (and cos θ r-cos θ a)=mgsin α " calculate (here, R represents that outer perimeter (length of whole week), the γ of the face that water droplet contacts with the surface of measuring object 300 represent that the surface tension of water, θ a represent the advancing contact angle degree, and θ r represents that receding contact angle degree, m represent that quality, the g of water droplet are gravity).Therefore, as shown in Figure 2, water droplet in the time of will be from the inclined plane landing is recorded in photo or the image in advance, according to above-mentioned outer perimeter R, advancing contact angle degree θ a, the receding contact angle degree θ r of photo or image measurement water droplet, thereby can calculate the water droplet angle [alpha] that drops.Also have, for the simplified measurement method, also can utilize the measuring appliance of advancing contact angle degree θ a and receding contact angle degree θ r, the dynamic soakage exerciser WET-6000 that for example RHESCA company makes, advancing contact angle degree θ a and receding contact angle degree θ r are measured, calculate the water droplet angle [alpha] that drops.Moreover, can be approximately in the shape of the face that water droplet contacts with the surface of measuring object 300 under the situation of circle (proper circle), also can calculate above-mentioned outer perimeter R approx with the diameter D of above-mentioned (circle) of the water droplet shown in Fig. 2.
Under the little condition of the pressure loss of supply gas (for example little gas pressure of 10kPa), for the water droplet that forms on the surface that can make gas flow path moves, the value of above-mentioned " cos θ r-cos θ a " should be little, more specifically, as long as water droplet drops angle [alpha] to satisfy condition of the present invention just passable.
Drop the condition of angle except satisfying above-mentioned water droplet, by adopting the well-known separator manufacturing technology of well-known process for treating surface (physical surface treatment, chemical surface treatment etc.) (also comprising the adjusting of material selection, material mixing method and material mixing ratio etc.), can be easily and obtain polymer electrolyte fuel cells separator of the present invention reliably.
Particularly the inventor finds following situation, does not promptly carry out the surface design according to above-mentioned viewpoint (2), and serves as main to carry out surface design with above-mentioned viewpoint (1), is the extremely difficult one of the main reasons that obtains stable and good drainage of existing compression forming separator.
More particularly, be that the mixture that will contain conductive carbon and bonding agent forms existing compression forming separator as constituent material.For example, the part that is made of conductive carbon of gas flow passage surface has in work initial stage hydrophobicity strong, but As time goes on is soaked in water easily gradually and changes hydrophilic characteristic into.On the other hand, the part that is made of the bonding agent (synthetic resin) of gas flow passage surface has comparatively inadequate hydrophobicity.And hydrophily and its physical structure of hydrophobicity (surface roughness etc.) of the part that is made of above-mentioned conductive carbon change sometimes.Existing compression forming separator serves as the main surface design of carrying out with above-mentioned viewpoint (1), and therefore trickle chemical constitution on the surface of gas flow path (chemical composition of decision hydrophily, hydrophobicity etc. etc.) and trickle physical structure (concaveconvex shape of decision roughness arithmetic average deviation value (Ra) etc. etc.) form uneven state easily shown in above-mentioned example.For example, the part that constitutes by above-mentioned conductive carbon and forms uneven state (size inequality, dispersity uneven) easily by the part that bonding agent (synthetic resin) constitutes.So find following situation, promptly be accompanied by this inhomogeneous state, be not only the little part (part that water droplet moves easily) of value of above-mentioned " cos θ r-cos θ a ", and the big part (part that water droplet is difficult to move) of value of " cos θ r-cos θ a " also is present in gas flow passage surface in a large number, and this is as the extremely difficult one of the main reasons that obtains good drainage of whole gas flow path.
So, the inventor finds following situation, even compression forming separator just, trickle chemical constitution by making gas flow passage surface (decision hydrophily, hydrophobic chemical composition etc.) and trickle physical structure (determining the concaveconvex shape of roughness arithmetic average deviation value (Ra) etc.) satisfy above-mentioned water droplet drop angle condition approach full and uniformly, also can obtain good drainage.
Here, the separator flow path surfaces is in high temperature and moisture state during generating.Particularly separator contains under the situation of conductive carbon, and under drying regime and moisture state, the hydrophily of insulation surface is that contact angle is different with hydrophobicity.Infer that thus is because the hydrophily of carbon and hydrophobicity are different under drying regime and moisture state.Therefore, measure water droplet and drop in the process of angle [alpha], preferably under the atmosphere condition that the running status with polymer electrolyte fuel cells (being designated hereinafter simply as PEFC) is equal to, use the water droplet capacity that is equal to the dew that produces to measure.
Yet, be difficult to reproduce exactly the atmosphere condition of PEFC running status sometimes.Particularly the atmosphere condition and the on-fixed of PEFC running status, but because of the running status of PEFC changes, it is just very difficult therefore to produce the atmosphere condition itself of determining the PEFC running status.Here, the inventor waits the following situation of finding by experiment, promptly when the measurement water droplet drops angle [alpha], need not tightly to reproduce physical conditions such as environment temperature, ambient humidity, light and temperature and water droplet capacity.Promptly recognize and to estimate PEFC exactly with the dew discharging performance of separator according to the water droplet of in defined terms, the measuring angle [alpha] that drops.Specifically, be to verify out under environment temperature in 90 ℃ of following scopes more than 50 ℃ and the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70% to place measuring instrument, can estimate the dew discharging performance of PEFC exactly by means of the water droplet of measuring with the water droplet below the 80 μ L more than the 50 μ L angle [alpha] that drops with separator.Therefore, need not to reproduce physical condition closely and measure, just can measure the water droplet angle [alpha] that drops, therefore can be easily and estimate the discharging performance of dew exactly.
Moreover, measure when water droplet drops angle [alpha] and also temperature, relative humidity and water droplet capacity can be grasped as parameter.Therefore, also can wait by experiment and obtain drop dependency relation between angle and temperature, relative humidity and the water droplet capacity of water droplet in advance, the above-mentioned water droplet angle [alpha] that drops is modified to water droplet under the atmosphere condition of the PEFC running status angle [alpha] that drops according to above-mentioned dependency relation.Therefore can estimate the dew discharging performance more accurately.
The present invention finishes according to this opinion.Below with reference to accompanying drawing the concrete example that enforcement the present invention uses is described.
Example 1
Fig. 3 is the stereogram of the PEFC of example 1.Fig. 4 is the exploded perspective view of structure that the PEFC of Fig. 3 is shown.Among Fig. 4, for convenience of description, decompose the part of the stepped construction that shows PEFC (STACK) 200.
PEFC200 is that the cell (cell) 100 that will utilize which generate electricity by electrochemical reaction is in addition stacked and form.Here, 100 cells 100 are in addition stacked, form PEFC200.
The stacked direction end of cell 100 is clamped by end plate 43,43 by collector plate 41,41 and insulation board 42,42, fixes from both sides with fastening bolt (not shown) between the end 43,43.Every here electrode area is with 10kgf/cm 2Fixedly press fit.
External loadings such as electric terminal 41A, the 41A of collector plate 41,41 and electric equipment link, output power.
Make and connect the reducing agent stream 40 that oxidant gas supplies with the oxidant stream 30 of manifold (manifold) 30D and oxidant gas discharge manifold 30E and be connected reducing agent gas supply manifold 40D and reducing agent gas discharge manifolds 40E and be formed on the PEFC200.
Oxidant stream 30 forms the following stated structure, and promptly oxidant gas is supplied with manifold 30D by oxidant gas provides, and is diverted to each cell 100, behind each cell 100, collaborates once more to be discharged into outside the PEFC200 from oxidant gas discharge manifold 30E.Reducing agent stream 40 also forms same structure.Adopt oxygen or air as oxidant gas here.In addition, with hydrogen or hydrogeneous gas as reducing agent gas.
On PEFC200, form cooling agent again and supply with manifold 45D, coolant discharge manifold 45E.
Coolant flow path 45 forms the following stated structure, and promptly cooling agent is supplied with manifold 45D by cooling agent provides, and is diverted between each stacked cell 100, after between each cell 100, collaborates once more to be discharged into outside the PEFC200 from coolant discharge manifold 45E.
Here, cell 100 forms the structure that MEA10 and separator 15,20 is stacked.
20 two kinds of separator use cathode isolation layer 15 and anode separators.The stream difference of surface both.And, as shown in Figure 2, between MEA10 and cathode isolation layer 15, form oxidant stream 30, between MEA10 and anode separator 20, form reducing agent stream 40.
Fig. 5 is the schematic diagram of the basic structure of expression MEA.
MEA10 forms the following stated structure, promptly possesses: the tall dielectric film 1 that is made of the amberplex that hydrogen ion is seen through, the carbon dust to carry platinum metal catalysts that forms the structure of clamping polyelectrolyte membrane 1 are the pair of electrodes catalyst layer (oxidant gas side electrode catalyst layer 2 and reducing agent gas side electrode catalyst layer 3) of main component and a pair of diffusion electrode layer (oxidant gas side diffusion electrode layer 4 and reducing agent gas side diffusion electrode layer 5) that is arranged at the outer surface of this a pair of electrode catalyst layer.This diffusion electrode layer 4,5 forms the structure that has gas permeability and electronic conductivity concurrently.For example has cellular structure.
And oxidant gas side electrode catalyst layer 2, oxidant gas side diffusion electrode layer 4 and cathode isolation layer 15 are formed negative electrode.
Again, reducing agent gas side electrode catalyst layer 3, reducing agent gas side diffusion electrode layer 5 and anode separator 20 constitute anode.
Polyelectrolyte membrane 1 is made of the proton-conducting polyelectrolyte membrane of perfluorocarbon sulfonic acid being made the thick film of 50 μ m (U.S. Dupont corporate system Nafionl12).Here, overall dimension is 20cm * 20cm.
Diffusion electrode layer 4,5 is made of carbon cloth.The overall dimension of carbon cloth (the system TGP-H-090 of Dongli Ltd.) is 12cm * 12cm, thickness is 220 μ m, be connected the mixture of the waterborne suspension (the system D-1 of Daikin Ind Ltd) of coating carbon black powders and polytetrafluoroethylene (PTFE) on the face of a side with electrode catalyst layer 2,3, sintering formed hydrophobic layer in 30 minutes under 400 ℃ condition.
Utilize silk screen print method that catalyst paste is coated in carbon cloth (diffusion electrode layer 4,5) and go up formation electrode catalyst layer 2,3.The platinum particle of about 30  of use average particulate diameter is carried on the catalyst fines of acetylene black powder (conductive carbon black of Deuki Kagaku Kogyo Co., Ltd (DENKA BLACK) FX-35) in the catalyst paste with the ratio of 25 weight %.The suspension (the system Flemion FSS-1 of Asahi Glass Co., Ltd) that perfluorocarbon sulfonic acid is dispersed in the alcohol solvent is mixed in the solution that this catalyst fines is scattered in isopropanol solvent, makes catalyst paste.The platinum amount that is included in the catalyst electrode 2,3 is 0.3mg/cm 2, the amount of perfluorocarbon sulfonic acid is 1.0mg/cm 2
Then, the carbon cloth (diffusion electrode layer 4,5) that forms electrode catalyst layer 2,3 is engaged with the two sides central portion of polyelectrolyte membrane 1, form MEA10 with hot-press method.Pass oxidant gas and supply with the edge part that manifold hole 30A, oxidant gas delivery pipe fork hole 30B, reducing agent gas supply manifold hole 40A, reducing agent gas discharge manifolds hole 40B, cooling agent supply manifold hole 45A and coolant discharge manifold hole 45B arrive polyelectrolyte membrane 1.Posting the air seal member 50 of Viton system O-ring-type on the polyelectrolyte membrane 1 around diffusion electrode layer 4,5 and various manifold hole 30A, 30B, 40A, 40B, 45A, the 45B.
Fig. 6 is the front view of oxidant gas stream pattern that the cathode isolation layer of Fig. 4 is shown.Fig. 7 is the front view of reducing agent gas flow path pattern that the cathode isolation layer of Fig. 4 is shown.Fig. 8 is the back view of coolant flow path pattern that the cathode isolation layer of Fig. 4 is shown.
As shown in Figure 6, on cathode isolation layer 15 and front that MEA10 docks, supply with the mode of manifold hole 30A and oxidant gas discharge manifold hole 30B and form oxidant gas stream groove (reaction gas flow paths) 30C that constitutes by groove to connect oxidant gas.Make oxidant gas stream groove 30C be formed on logical structure in the cell 100 all over the part of docking with oxidant gas side diffusion electrode layer 4.On the other hand, as shown in Figure 8, form cooling water stream groove (cooling water stream) 45C that constitutes by groove in the mode that connects cooling agent supply manifold hole 45A and coolant discharge manifold hole 45B at the back side of cathode isolation layer 15.
And for example shown in Figure 7, the front that contacts with MEA10 of anode separator 20 forms reducing agent gas flow path groove (reaction gas flow paths) 40C that is made of groove in the mode of reducing agent gas being supplied with manifold hole 40A and reducing agent gas discharge manifolds hole 40B and being linked.Make reducing agent gas flow path groove 40C be formed on logical structure in the cell 100 all over the part of docking with reducing agent gas side diffusion electrode layer 5.In addition, identical with cathode isolation layer 15, form the cooling water stream groove 45C that constitutes by groove at the back side of anode separator 20 in the mode that connects cooling agent supply manifold hole 45A and coolant discharge manifold hole 45B.
Make the coolant flow path groove 45C of cathode isolation layer 15 and anode separator 20 be formed on the structure that the back side of oxidant gas stream groove 30C and reducing agent gas flow path groove 40C is cooled off in the cell 100 everywhere here.And in the lamination of cell 100, the coolant flow path groove 45C of the coolant flow path groove 45C of cathode isolation layer 15 and anode separator 20 unification forms coolant flow path 45.
Here, the size of cathode isolation layer 15 and anode separator 20 is similarly 20cm * 20cm, thickness is similarly 3mm, and making oxidant gas stream groove 30C and its width of reducing agent gas flow path groove 40C is that 1.2mm, the degree of depth are that the recess of 0.7mm forms the many parallel structures in interval with 1.0mm as shown in Figure 6 and Figure 7.On the whole back side of whole oxidant gas stream groove 30C, be the coolant flow path groove 45C of cathode isolation layer 15 wide as shown in Figure 8.Make the tabular surface at cathode isolation layer 15 back side stay the central portion of the big slot part of this width with the form that is dispersed on several points.Therefore can in the process of stacked and binding cell 100, disperse binding strength.
Pass oxidant gas again and supply with manifold hole 30A, oxidant gas discharge manifold hole 30B, reducing agent gas supply manifold hole 40A, reducing agent gas discharge manifolds hole 40B, cooling agent supply manifold hole 45A and coolant discharge manifold hole 45B, arrive the edge part of cathode isolation layer 15 and anode separator 20, corresponding with MEA10.Also have, assembling is during cell 100 and during battery stack, link oxidant gas and supply with manifold hole 30A, form oxidant gas and supply with manifold 30D, link oxidant gas discharge manifold hole 30B and form oxidant gas discharge manifold 30E, link reducing agent gas and supply with manifold hole 40A, form reducing agent gas and supply with manifold 40D, link reducing agent gas discharge manifolds hole 40B, form reducing agent gas discharge manifolds 40E, link cooling agent and supply with manifold hole 45A, form cooling agent and supply with manifold 45D, and binding coolant discharge manifold hole 45B forms coolant discharge manifold 45E.
Here, to describing as the cathode isolation layer 15 of feature of the present invention and the raw material and the surface of anode separator 20.
The bonding agent of conductive carbon and reinforcing conductive carbon is mixed formation separator 15,20.Bonding agent can adopt rubber, resin etc.Can use the high temperature resin how wet separator environment for use has tolerance as resin.For example, epoxy resin, phenolic resins, PPS, polypropylene, liquid crystal polymer and PTER etc.Here use the mixture that electrographite powder 80wt%, the carbon black 5wt% of average particulate diameter 100 μ m and the phenolic resins 15wt% before the thermmohardening is mixed and obtain.This mixture input is duplicated the mould of the shape of separator 15,20, make phenolic resin curing, form separator 15,20 by about 180 ℃ hot pressing.
Separator flow passage groove 30C, the 40C surface that forms like this keep non-processor former state, be that former state keeps the epidermal area that is rich in phenolic resins.
Here, the evaluation method of separator of the present invention is by measuring the above-mentioned water droplet angle [alpha] that drops, and the discharging performance of the dew of this separator is estimated.Promptly according in environment temperature below 90 ℃ and relative humidity more than 50 ℃ under the ambient humidity, light and temperature condition of 100% following scope more than 70%, be dropped in the water droplet drippage angle of the following water droplet of the above 80 μ L of 50 μ L of the oxidant gas stream groove 30C of separator 15,20 or reducing agent gas flow path groove 40C, the discharging performance of the dew of separator 15,20 is estimated.In this example, calculate water droplet under the moisture state of the 70 ℃ of temperature angle [alpha] that drops and be about 45 degree.
Here, water droplet drops in the measuring process of angle [alpha], and preferably lower surface and the side of oxidant gas stream groove 30C or reducing agent gas flow path groove 40C are smooth on water droplet drops direction.Can prevent more reliably that like this water droplet angle [alpha] that drops from changing because of shape effects such as ladder difference and zigzag parts.In addition, also be difficult to sometimes under the moisture state water droplet is judged, thereby be difficult to directly measure the correct water droplet angle [alpha] that drops.Therefore, the dynamic soakage exerciser WET-6000 by using RHESCA company to make measures advancing contact angle degree θ a and receding contact angle degree θ r, according to the above-mentioned relation formula, also can calculate the water droplet angle [alpha] that drops.
Moreover, the surface roughness of separator flow passage groove 30C, 40C its roughness arithmetic average deviation value Ra (center line average height)=0.7.Contact angle θ d under the drying regime is about 80 degree, and the contact angle θ w under the moisture state of 70 ℃ temperature is about 60 degree.Here use contact pin type surface roughness measuring instrument (TaylorHobson corporate system Form Talysurf-120),, measure roughness arithmetic average deviation value Ra according to the method for measurement of JIS B0651.
Action to the PEFC200 that constitutes as mentioned above describes below.Oxidant gas is supplied with manifold 30D shunting through oxidant gas and is supplied with each cell 100.In each cell 100, oxidant gas is supplied with negative electrode.Be exposed to oxidant gas side diffusion electrode layer 4 here.In addition, hydrogen or hydrogeneous reducing agent gas offer anode too.Be exposed to reducing agent gas side diffusion electrode layer 5 here.
Then, oxidant gas sees through oxidant gas side diffusion electrode layer 4, arrives oxidant gas side electrode catalyst layer 2.Equally, reducing agent gas also sees through reducing agent gas side diffusion electrode layer 5 and arrives reducing agent gas side electrode catalyst layer 3.
If through cathode isolation layer 15, anode separator 20, collector plate 41,41 (with reference to figure 1) and outside electric circuit (not shown), constitute the electrical connection circuit of oxidant gas side electrode catalyst layer 2 and reducing agent gas side electrode catalyst layer 3, then in oxidant gas side electrode catalyst layer 2, according to the difference of the ionization tendency of reducing agent gas, make oxygen ionization.Equally, in reducing agent gas side electrode catalyst layer 3, make the hydrogen ionization.
Hydrogen ion combines with oxonium ion at oxidant gas side electrode catalyst layer 2 by polyelectrolyte membrane 1 and produces water.In addition, along with the ionization of hydrogen, the electronics that produces in reducing agent gas side electrode catalyst layer 3 is through reducing agent gas side diffusion electrode layer 5 and the anode separator 20 that contains conductive carbon, flow into the cell 100 or the outside electric circuit (not shown) of adjacency, produce electricity output.
Embodiment 1
Embodiment 1 adopts the PEFC200 of example 1, is that benchmark carries out operation test with general fuel availability and the oxygen utilization rate of PEFC.PEFC200 remains on 70 ℃.Reducing agent gas uses the gas of 80wt% hydrogen and 20wt% carbon dioxide composition.
Reducing agent gas by humidification, heat with the dew point that reaches 70 ℃, and supply with manifold 40D by reducing agent gas and provide.Air is used as oxidant gas.Oxidant gas by humidification, heat with the dew point that reaches 70 ℃, and supply with manifold 30D by oxidant gas and provide.
Then, at fuel availability 75%, the oxygen utilization rate 50% of oxidant gas, the current density 0.3A/cm of reducing agent gas 2Output condition under continue the full load generating.At this moment, the pressure loss (hereinafter referred to as the reducing agent gas side pressure loss) that reducing agent gas is supplied with between manifold 40D and the reducing agent gas discharge manifolds 40E is about 7kPa, the pressure loss (hereinafter referred to as the oxidant gas side pressure loss) that reducing agent gas is supplied with between manifold 30D and the oxidant gas discharge manifold 30E is about 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72V-43.2A).Here, the generating of so-called full load is meant that PEFC is stably can be the most effectively and generating during the load to greatest extent of stably generating electricity.
During operation test,, implement former state and keep the fuel utilization ratio when being equal to the full load generating and the low output operation of oxygen utilization efficient incipient moment and per 500 hours again.Be that former state remains on fuel availability 75%, oxygen utilization rate 50%, make current density narrow down to 0.06A/cm 2Power generation continuous 24 hours of fractional load.At this moment, do not find voltage fluctuation, battery output is stable to be carried out.Current density is narrowed down to 0.06A/cm here, 2It is the minimum output state of imagining in the PEFC200 practicality.
Then, on one side current density is maintained 0.06A/cm 2Yi Bian, confirm the limit of fuel utilization ratio and oxygen utilization efficient.Promptly, perhaps oxygen utilization rate is brought up to 50%, reduce the low output limit test of the reducing agent gas side pressure loss or the oxidant gas side pressure loss for fuel availability is brought up to 75%.Consequently, if the fuel availability of reducing agent gas is higher than 75%, then find voltage fluctuation as can be seen.In addition, if the oxygen utilization rate of oxidant gas is higher than 50%, then find voltage fluctuation as can be seen.Fuel availability is higher than 75%, oxygen utilization rate is higher than 50%, current density is 0.06A/cm 2Reducing agent gas side limit low pressure loss Pa under the condition is 2.5kPa, and oxidant gas side limit low pressure loss Pc is 2.3kPa.
Comparative example 1
Comparative example 1 uses with the PEFC200 of example 1 same model and carries out the operation test identical with embodiment 1.
But sandblast processing is carried out on separator flow passage groove 30C, 40C surface after the moulding, and the epidermal area of removal phenolic resins reaches the degree of depth about several μ m.At this moment the surface roughness of separator flow passage groove 30C, 40C (roughness arithmetic average deviation value) Ra=1.5.In addition, the contact angle θ d under the drying regime is about 80 degree, and contact angle θ w is about 30 degree under the moisture state of 70 ℃ of temperature.In addition, adopt separator evaluation method of the present invention, then the water droplet under the moisture state of 70 ℃ of temperature drop angle [alpha] be about 50 the degree.
Consequently, carry out fuel availability 75%, oxygen utilization rate 50%, the current density 0.3A/cm identical with embodiment 1 2Full load when generating, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.5V-43.2A).
Carry out fuel availability 75%, oxygen utilization rate 50%, the current density 0.06A/cm identical again with embodiment 1 2Fractional load when generating, in the partial monosomy battery, from every a few minutes～dozens of minutes finds voltage fluctuation.The voltage fluctuation amplitude is about 100mV.Therefore, in order to reduce fuel utilization ratio and oxygen utilization efficient, improve the reducing agent gas side pressure loss or the oxidant gas side pressure loss, to eliminating maximum conditions that voltage fluctuation finds, being that the result that limit low pressure loss is tested shows, reducing agent gas side limit low pressure loss Pa is 2.8kPa.In addition, oxidant gas side limit low pressure loss Pc is 2.6kPa.
Example 2
The PEFC200 of the invention process form 2 is except the surface treatment difference of cathode isolation layer 15 and anode separator 20, and other are identical with example 1.
Promptly with the example 1 the same separator 15,20 that forms.Then, stage sandblast processing is carried out on separator flow passage groove 30C, 40C surface.Here, so-called stage sandblast processing is meant with the processing of sandblasting earlier and compares, after its little repeatedly sandblast processing of particle diameter of sandblasting and adding the particle that uses man-hour of processing of sandblasting.Utilize bigger alumina particle to carry out wet shot for example, at first, then, utilize the alumina particle that reduces particle diameter to carry out the processing of several wet shot successively.In addition, then improper when using tiny alumina particle to carry out sandblast if utilize with the blasting method of gas as carrier, therefore, adopt the wet shot method of liquid state as carrier.Here use wet shot cleaning device (MACOHO Co., Ltd. system).
By increase and decrease should be stage sandblast processing, the separator water droplet on adjustment separator flow passage groove 30C, the 40C surface angle [alpha] that drops.Here, formula sandblast processing implementation phase of with surface roughness (the roughness arithmetic average deviation value) Ra of separator flow passage groove 30C, 40C requiring in the scope of Ra=3～7, angle [alpha] is adjusted into below 45 degree thereby the water droplet that will obtain according to the evaluation method of separator of the present invention drops.Get across though the reason of such effect will not occur,,,, form on concavo-convex trickleer concavo-convexly, promptly form multistage concaveconvex structure trickle on separator flow passage groove 30C, 40C surface by stage sandblast processing according to the inventor's supposition.Can infer to utilize this multistage concaveconvex structure to form bigger specific area, the increase of this specific area and water droplet drop the reducing of angle [alpha], be that the drop improvement of angle [alpha] of water droplet is associated.
Moreover angle [alpha] has such dependency relation though surface roughness (roughness arithmetic average deviation value) Ra and water droplet drop, and the concrete dependency relation material because of separator at least is different.
Embodiment 2
Embodiment 2 uses the PEFC200 of examples 2 to carry out the operation test identical with embodiment 1.Carry out stage sandblast processing, make separator 15,20 its separator flow passage groove 30C, 40C surface roughness (roughness arithmetic average deviation value) reach (embodiment 2～3 that is equivalent to Fig. 9) till the Ra=3.7.The water droplet that the evaluation method of separator of the present invention obtains drop angle [alpha] be 25 the degree.
Carry out fuel availability 75%, oxygen utilization rate 50%, current density 0.3A/cm 2Full load when generating, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.3V-43.2A).
Again, carrying out fuel availability 75%, oxygen utilization rate 50%, the current density identical with embodiment 1 is 0.06A/cm 2Fractional load when generating, voltage fluctuation does not take place, voltage output is stable to be carried out.
Then, the same with embodiment 1, Yi Bian current density is maintained 0.06A/cm 2Yi Bian, carry out the low output test of the limit.Consequently, if the fuel availability of reducing agent gas is higher than 80%, then find voltage fluctuation as can be seen.In addition, if be higher than 55%, then find voltage fluctuation as can be seen at the oxygen utilization rate of oxidant gas.Be 80% at fuel availability, oxygen utilization rate is 55%, current density is 0.06A/cm 2Reducing agent gas side limit low pressure loss Pa under the condition is 2.4kPa, and oxidant gas side limit low pressure loss Pc is 2.3kPa.
Again, separator flow passage groove 30C, the different separator 15,20 of 40C surface roughness (roughness arithmetic average deviation value) Ra are adopted in the increase and decrease of adjusting stage formula sandblast processing, implement same operation test.
Fig. 9 illustrates surface roughness (roughness arithmetic average deviation value) Ra the characteristic of the separator and the PEFC of example 2 as parameter.
As shown in the figure, under the situation of separator flow passage groove 30C, 40C surface roughness (roughness arithmetic average deviation value) Ra=2.5 and 8 (embodiment 2-1 and 2-7), the water droplet that the evaluation method of separator of the present invention obtains drop angle [alpha] all be approximately 50 the degree, Pa is 3kPa and 3.5kPa, Pc is 2.9kPa and 3kPa, during the fractional load generating, if fuel utilization ratio and oxygen utilization efficient are reduced, then battery output is unstable.
Example 3
The difference, other are identical with example 2 in the surface treatment of cathode isolation layer 15 and anode separator 20 for the PEFC200 of the invention process form 3.Promptly with the example 1 the same separator 15,20 that forms, the same with example 2 stage sandblast processing is carried out on separator flow passage groove 30C, 40C surface.
Then, after stage sandblast machines, utilize plasma cleaning device (the system PC-1000 of SAMCO society of Co., Ltd.) to carry out oxygen plasma treatment.Even by oxygen plasma treatment, separator flow passage groove 30C, 40C surface roughness (roughness arithmetic average deviation value) and example 2 are roughly the same, Ra=3.7.Yet the contact angle θ d under the drying regime is about 10 degree, and the contact angle θ w under the moisture state of 70 ℃ of temperature is about 0 degree, promptly can not measure.In addition, if adopt the evaluation method of separator of the present invention, then the angle [alpha] that drops of the water droplet the moisture state of 70 ℃ of temperature under is about 5 and spends.In a word, by oxygen plasma treatment, the water droplet that can improve separator flow passage groove 30C, the 40C surface of the embodiment 2-3 of Fig. 9 angle [alpha] that drops.
The reason that such effect occurs is not made clear.Therefore, it is that being awarded followingization 1 and changing the oxide functional group shown in 2 on carbon surface is the hydrophilic functional group that the inventor analyzes the result who obtains with XPS (x-ray photoelectron spectrophotometric spectra) to separator flow passage groove 30C, 40C surface.
(changing 1)
-C＝O
(changing 2)
-C-OH
Promptly according to the inventor's supposition, infer that the polarity that separator flow passage groove 30C, 40C surface becomes greatly because of the hydrophilic functional group, separator flow passage groove 30C, 40C surface forms hydrophily, and the drop improvement of angle [alpha] has Tribute to offer to water droplet for this.Therefore, if infer the method that to make hydrophily or hydrophobic functional group to combine easily with separator flow passage groove 30C, 40C surface chemistry, the water droplet that then can improve separator flow passage groove 30C, the 40C surface angle [alpha] that drops.Even the UV ozone treatment of irradiation ultraviolet radiation also can increase the polarity on separator flow passage groove 30C, 40C surface under ozone atmosphere for example, therefore can improve the water droplet angle [alpha] that drops equally.In addition, utilize fluoro plasma to handle, also can make the graphite chemical bond on fluoride functional group and separator flow passage groove 30C, 40C surface, therefore can increase the hydrophobicity on separator flow passage groove 30C, 40C surface.In a word, can improve the water droplet angle [alpha] that drops.
Moreover these plasma treatment also can be the methods of not carrying out reduced pressure treatment ground irradiation plasma under the atmospheric pressure atmosphere.In addition, plasma processing apparatus also can be the parallel plate-type or the cylinder type plasma processing apparatus of electrode deployment on the side of barrel process chamber of electrode parallel opposed.
In addition, the following opposed face store method that is rich in hydrophilic functional group's separator 15,20 describes.In order to prevent or to suppress hydrophobic airborne organic substance etc., preferably carry out vacuum and preserve attached on the hydrophilic functional group.Yet, know that the hydrophily on separator flow passage groove 30C, 40C surface can change because of the difference of the packing method of separator 15,20.
Figure 11 illustrates the comparison of the contact angle θ d under the drying regime on different separator flow passage groove surfaces of packing method of separator of this example.As shown in the figure, pack separator 15,20 respectively, carry out vacuum and preserve with Polythene Bag of selling on the market and aluminium foil.Then, after preserving through 1 hour vacuum, take out separator 15,20 both, the contact angle θ d on separator flow passage groove 30C, 40C surface is carried out 3 times measures.Under the situation of packing with Polythene Bag, contact angle θ d increases as can be known, the hydrophily decline.On the other hand, with under the situation of In Aluminium Foil Packing, carry out 3 times measurement, contact angle θ d all keeps below 10 degree.The reason that such effect occurs is not made clear.But, can think that therefore if make as contacts with it such as same organic Polythene Bags, then Biao Mian hydrophilic functional group will reduce because the carbon formed body on formation separator flow passage groove 30C, 40C surface is an organic substance according to the inventor's supposition.On the other hand, its chemical composition of aluminium foil that is made of inorganic matter is with different as organic carbon formed body, even can think therefore that aluminium foil and separator flow passage groove 30C, 40C are surperficial contacts, the hydrophilic functional group can not reduce yet.Therefore, can think that separator that separator flow passage groove 30C, 40C surface are rich in the hydrophilic functional group is suitable for packing and carrying out the method that vacuum is preserved with inorganic material.
In addition, below the stage processing of sandblasting is described with the complementary effect of oxygen plasma treatment.
Figure 12 illustrate do not carry out stage sandblast processing and implement under the drying regime on separator flow passage groove surface of separator of oxygen plasma treatment contact angle θ d over time.As shown in the figure, it is 40 degree that the contact angle θ d that oxygen plasma treatment was handled just now handled just now in processing, does not obtain enough hydrophilies.In addition, rise more than 10 degree at contact angle θ d after 5 days, final contact angle θ d rises to about 80.
Figure 13 illustrate under the drying regime on separator flow passage groove surface of the separator that carries out stage sandblast processing and oxygen plasma treatment contact angle θ d over time.As shown in the figure, the contact angle θ d that oxygen plasma treatment was handled just now is below 10 degree, even and through 30 days, this effect was also keeping.The reason that such effect occurs does not obtain explaining.According to the inventor's supposition, the etch effect of utilizing oxygen plasma treatment to produce also forms trickleer concavo-convexly in the multistage concaveconvex structure that the stage processing of sandblasting produces, and therefore the specific area on separator flow passage groove 30C, 40C surface increases.Then, oxygen plasma treatment is carried out on separator flow passage groove 30C, 40C surface that the contrast table area is big, therefore forms more hydrophilic functional group on separator flow passage groove 30C, 40C surface.Can think that what of this hydrophilic functional group have contribution to the hydrophily with durability.
Embodiment 3
Embodiment 3 uses the PEFC200 of examples 3 to carry out the operation test identical with embodiment 1.
Consequently, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.3A/cm 2Full load when generating, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.6V-43.2A).
In addition, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.06A/cm 2Fractional load when generating, voltage fluctuation does not take place, battery output is stable to be carried out.
Then, the same with embodiment 1, Yi Bian current density is maintained 0.06A/cm 2Yi Bian, carry out the low output test of the limit.Consequently, if the fuel availability of reducing agent gas is higher than 90%, then find voltage fluctuation as can be seen.In addition, if the oxygen utilization rate of oxidant gas is higher than 65%, then find voltage fluctuation as can be seen.Be 90% at fuel availability, oxygen utilization rate is 65%, current density is 0.06A/cm 2Reducing agent gas side limit low pressure loss Pa under the condition is 2.1kPa, and oxidant gas side limit low pressure loss Pc is 2.0kPa.
Example 4
The difference, other are identical with example 1 in the material of cathode isolation layer 15 and anode separator 20 and surface treatment for the PEFC200 of the invention process form 4.
Be that separator 15,20 adopts average particulate diameter be that Delanium powder 79wt%, carbon black 5wt%, the average particulate diameter of 100 μ m is that the high-purity mangesium oxide alumina particles 2wt% of 0.5 μ m and the phenolic resins 14wt% before the hot curing are mixed the mixture that obtains.This mixture input is duplicated the mould of separator 15,20 shapes, make phenolic resin curing, form separator 15,20 by about 180 ℃ hot pressing.
Then, similarly stage sandblast processing is carried out on separator flow passage groove 30C, 40C surface with example 2.The surface roughness of separator flow passage groove 30C, 40C (roughness arithmetic average deviation value) is Ra=6.5.
Consequently, the contact angle θ d under the drying regime is about 20 degree, and the contact angle θ w under the moisture state of 70 ℃ temperature is about 0 degree, promptly can survey.According to the evaluation method of separator of the present invention, the water droplet drippage angle [alpha] under the moisture state of 70 ℃ of temperature is about 10 degree.
Embodiment 4
Embodiment 4 uses the PEFC200 of examples 4 to carry out the operation test identical with embodiment 1.
Consequently, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.3A/cm 2Full load when generating, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.3V-43.2A).
In addition, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.06/cm 2Fractional load when generating, voltage fluctuation does not take place, battery output is stable to be carried out.
Then, the current density former state is maintained 0.06A/cm 2, fuel availability brought up to more than 75% or with oxygen utilization rate bring up to more than 50%, carry out the fractional load generating.Consequently, if the fuel availability of reducing agent gas is higher than 85%, then find voltage fluctuation as can be seen.In addition, if the oxygen utilization rate of oxidant gas is higher than 60%, then find voltage fluctuation as can be seen.
Be 85% at fuel availability, oxygen utilization rate is 60%, current density is 0.06A/cm 2Reducing agent gas side limit low pressure loss Pa under the condition is 2.2kPa, and oxidant gas side limit low pressure loss Pc is 2.1kPa.
Example 5
The PEFC200 of example 5 of the present invention is except the material and surface treatment difference of cathode isolation layer 15 and anode separator 20, and other are identical with example 1.
Be that separator 15,20 employings are that Delanium powder 79wt%, the carbon black 5wt% of 100 μ m, high-purity titanium (titan) particle 2wt% and the preceding phenolic resins 14wt% of hot curing that average particulate diameter is 0.5 μ m are mixed the mixture that obtains with average particulate diameter.This mixture input is duplicated the mould of separator 15,20 shapes, make phenolic resin curing, form separator 15,20 by about 180 ℃ hot pressing.
Then, the same with example 2 stage sandblast processing is carried out on separator flow passage groove 30C, 40C surface.The surface roughness of separator flow passage groove 30C, 40C (roughness arithmetic average deviation value) is Ra=6.5.
Consequently, the contact angle θ d under the drying regime is about 20 degree, and the contact angle θ w under the moisture state of 70 ℃ temperature is about 0 degree, promptly can survey.If adopt the evaluation method of separator of the present invention, then the drippage of the water droplet under the moisture state under 70 ℃ temperature angle [alpha] is about 10 degree.
Embodiment 5
Embodiment 5 uses the PEFC200 of examples 5 to carry out the operation test identical with embodiment 1.
Consequently, be 75% at fuel availability, oxygen utilization rate is 50%, current density is 0.3A/cm 2Condition under, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.3V-43.2A).
In addition, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.06A/cm 2Fractional load when generating, voltage fluctuation does not take place, battery output is stable to be carried out.
Then, the same with embodiment 1, Yi Bian current density is maintained 0.06A/cm 2Yi Bian, carry out the low output test of the limit.Consequently, if the fuel availability of reducing agent gas is higher than 85%, then find voltage fluctuation as can be seen.In addition, if the oxygen utilization rate of oxidant gas is higher than 60%, then find voltage fluctuation as can be seen.Be 85% at fuel availability, oxygen utilization rate is 60%, current density is 0.06A/cm 2Reducing agent gas side limit low pressure loss Pa under the condition is 2.2kPa, and oxidant gas side limit low pressure loss Pc is 2.1kPa.
Example 6
The PEFC200 of the invention process form 6 is except difference on the material of cathode isolation layer 15 and anode separator 20, and other are identical with example 1.
Be that separator 15,20 adopts average particulate diameter be that epoxy resin 14wt% before Delanium powder 79wt%, carbon black 5wt%, PEFE powder 2wt% and the hot curing of 100 μ m is mixed the mixture that obtains.This mixture input is duplicated the mould of separator 15,20 shapes, make epoxy resin cure, form separator 15,20 by about 180 ℃ hot pressing.
Separator flow passage groove 30C, the 40C surface that forms like this keeps the state that is untreated, is the epidermal area that former state keeps epoxy resin.(roughness arithmetic average deviation value is Ra=0.8 to the roughness on separator flow passage groove 30C, 40C surface.In addition, the contact angle θ d under the drying regime is about 110 degree, and the contact angle θ w under the moisture state under 70 ℃ the temperature is about 100 degree.When adopting the evaluation method of separator of the present invention, the angle [alpha] that drops of the water droplet under 70 ℃ of temperature moisture states is about 20 degree.
Embodiment 6
Embodiment 6 uses the PEFC200 of examples 6 to carry out the operation test identical with embodiment 1.
Consequently, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.3A/cm 2Full load when generating, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.3V-43.2A).
In addition, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.06/cm 2Fractional load when generating, voltage fluctuation does not take place, battery output is stable to be carried out.
Then, the same with embodiment 1, Yi Bian current density is maintained 0.06A/cm 2Yi Bian, carry out the low output test of the limit.Consequently, if the fuel availability of reducing agent gas is higher than 80%, then find voltage fluctuation as can be seen.In addition, if the oxygen utilization rate of oxidant gas is higher than 55%, then find voltage fluctuation as can be seen.Be 80% at fuel availability, oxygen utilization rate is 55%, current density is 0.06A/cm 2Reducing agent gas side limit low pressure loss Pa under the condition is 2.3kPa, and oxidant gas side limit low pressure loss Pc is 2.2kPa.
Comparative example 2
Comparative example 2 uses with the PEFC200 of example 6 same models and carries out the operation test identical with embodiment 1.
But similarly stage sandblast processing is carried out on separator flow passage groove 30C, 40C surface after the moulding with example 2.The roughness of separator flow passage groove 30C, 40C (roughness arithmetic average deviation value Ra) is Ra=6.3.In addition, the contact angle θ d under the drying regime is about 110 degree, and 70 ℃ of temperature moisture states contact angle θ w down is about 100 and spends.If adopt the evaluation method of separator of the present invention, then 70 ℃ of temperature, moisture state water droplets down angle [alpha] that drops is about 50 and spends.
Consequently, carry out that fuel availability is 75%, oxygen utilization rate is 50%, current density is 0.3A/cm 2Full load when generating, the reducing agent gas side pressure loss is about 7kPa, the oxidant gas side pressure loss is 6kPa, continues to keep more than 8000 hours the battery output of 3.1kW above (72.3V-43.2A).
In addition, carry out fuel availability and be 75%, oxygen utilization rate is 50%, when current density is the fractional load generating of 0.06A/cm2, in the partial monosomy battery, every a few minutes～dozens of minutes finds voltage fluctuation.The voltage fluctuation amplitude is about 70mV.Therefore, in order to reduce fuel utilization ratio and oxygen utilization efficient, improve the reducing agent gas side pressure loss or the oxidant gas side pressure loss, to eliminating maximum conditions that voltage fluctuation finds is limit low pressure loss when verifying, reducing agent gas side limit low pressure loss Pa is 2.7kPa.In addition, oxidant gas side limit low pressure loss Pc is 2.5kPa.
Here, the result to above embodiment and comparative example gathers explanation.
Figure 10 illustrates separator in embodiment 1～6 and the comparative example 1,2 and the characteristic of PEFC.When carrying out the fractional load generating, fuel utilization ratio and oxygen utilization efficient when being equal to full load and generating electricity specified output in order to keep, need make reducing agent gas side limit low pressure loss Pa below 2.5kPa, oxidant gas side limit low pressure loss Pc is below 2.3kPa.As shown in the figure, the water droplet that utilizes the evaluation method of separator of the present invention the to obtain angle [alpha] that drops can satisfy such condition when 5 degree～45 degree scopes.
On the other hand, confirm separator 15,20, promptly comprised conductive carbon and reinforcing in the separator of material of bonding agent of conductive carbon, irrelevant with the shape of separator flow passage groove 30C, 40C, Ra is under the situation of Ra=4.0 μ m in surface roughness (roughness arithmetic average deviation value), can fully reduce the size of gas flow path of actual manufacturing and the skew of design load.
In addition, in implementing form 3 explanation like that, the drop improvement means of angle [alpha] of the water droplet of separator of material that oxygen plasma treatment as separator 15,20, promptly comprises the bonding agent of conductive carbon and reinforcing conductive carbon are effective.Here, under the situation on the surface more than the Ra=1.5, oxygen plasma treatment can be had a mind to the free burial ground for the destitute more fully and be improved the water droplet angle [alpha] that drops.By inference, its main cause is, if more than the Ra=1.5 μ m, then can fully form surface roughness, be trickle concavo-convex, therefore can fully form functional group by oxygen plasma treatment.Therefore, preferably separator flow passage groove 30C, 40C surface is more than the Ra=1.5 μ m.
In sum, if separator flow passage groove 30C, 40C surface its roughness arithmetic average deviation value Ra is below 4.0 μ m more than 1.5, then easily separator 15,20 compactnesses are turned to the size of practicability level, thereby can fully reduce the size of gas flow path of actual manufacturing and the deviation of design load, and can fully seek to improve the water droplet angle [alpha] that drops by oxygen plasma treatment.Therefore, even under the low condition of the pressure loss of supply gas, also be fit to separator as the PEFC of the discharging performance excellence of dew.
In addition, if the spacing of making between trickle protuberance is roughly the following surface of 5 μ m, then the water at separator flow passage groove 30C, 40C surface sweating will be tangled because of the anchor effect, and the pressure loss is big, thereby can prevent oscillation phenomenon more fully.Therefore, if the spacing between its trickle protuberance of separator flow passage groove 30C, 40C surface is roughly below the 5 μ m, even then under the low condition of the reaction gas pressure loss of supplying with, therefore the vibration of supply pressure loss that also can inhibitory reaction gas can suppress the vibration of the generating output of PEFC100.
More than example of the present invention is illustrated, but the present invention is not limited to above-mentioned example, the those of ordinary skill of the industry can use various improved means and alternative means within the scope of the invention.
Description of drawings
Fig. 1 is the drop schematic diagram of method of measurement of angle of water droplet.
Fig. 2 is the drop schematic diagram of indirect measurement method of angle of water droplet.
Fig. 3 is the stereogram of the PEFC of example 1.
Fig. 4 is the exploded perspective view of structure of the PEFC of Fig. 3.
Fig. 5 is the schematic diagram of the basic structure of MEA.
Fig. 6 is the front view of oxidant gas stream pattern of the cathode isolation layer of Fig. 4.
Fig. 7 is the front view of reducing agent gas flow path pattern of the anode separator of Fig. 4.
Fig. 8 is the back view of coolant flow path pattern of the cathode isolation layer of Fig. 4.
Fig. 9 is with the characteristic of surface roughness (roughness arithmetic average deviation value) Ra as the separator and the PEFC of parametric representation example 2.
Figure 10 represents separator in embodiment 1～6 and the comparative example 1,2 and the characteristic of PEFC.
Figure 11 is the comparison diagram of the contact angle θ d of separator flow passage groove surface under drying regime that cause because of the difference of packing method of the separator of this example.
Figure 12 illustrate the separator flow passage groove surface of not carrying out stage sandblast processing and implementing the separator of oxygen plasma treatment be under the dry state contact angle θ d over time.
The contact angle θ d of separator flow passage groove surface under drying regime that Figure 13 illustrates the separator that carries out stage sandblast processing and oxygen plasma treatment over time.
Symbol description
1 polyelectrolyte membrane
2 oxidant gas side electrode catalyst layers
3 reducing agent gas side electrode catalyst layers
4 oxidant gas side diffusion electrode layers
5 reducing agent gas side diffusion electrode layers
10 MEA
15 cathode isolation layers
20 anode separators
30 oxidant gas streams
The 30A oxidant gas is supplied with manifold hole
30B oxidant gas discharge manifold hole
30C oxidant gas stream groove (separator flow passage groove)
The 30D oxidant gas is supplied with manifold
30E oxidant gas discharge manifold
40 reducing agent streams
Former dose of gas of 40A is supplied with manifold hole
40B reducing agent gas discharge manifolds hole
40C reducing agent gas flow path groove (separator flow passage groove)
40D reducing agent gas is supplied with manifold
40E reducing agent gas discharge manifolds
41 collector plates
The 41A electric terminal
42 insulation boards
43 end plates
45 coolant flow path
The 45A cooling agent is supplied with manifold hole
45B coolant discharge manifold hole
45C coolant flow path groove
The 45D cooling agent is supplied with manifold
The 45E coolant discharge manifold
50 air seal members
100 cells
200 polymer electrolyte fuel cells (PEFC)
300 measuring objects
310 water droplets
Contact angle under the θ d drying regime
Contact angle under the moisture state under the temperature that θ w is 70 ℃
θ a advancing contact angle degree
θ r receding contact angle degree
The α water droplet angle that drops
Pa reducing agent gas side limit low pressure loss
Pc oxidant gas side limit low pressure loss

Claims (12)

1. a polymer electrolyte fuel cells separator is characterized in that,
This separator comprises conductive carbon and reinforces the bonding agent of conductive carbon, forms reaction gas flow paths at least on an interarea,
Under the environment temperature and the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70% in 90 ℃ of following scopes more than 50 ℃, make under the situation of the following water droplet drippage of the above 80 μ L of 50 μ L, the water droplet drippage angle on the surface of described reaction gas flow paths is below 45 degree more than 5 degree.
2. polymer electrolyte fuel cells separator according to claim 1 is characterized in that, the roughness arithmetic average deviation value Ra on the surface of described reaction gas flow paths is below the above 4.0 μ m of 1.5 μ m.
3. polymer electrolyte fuel cells separator according to claim 1 is characterized in that, among the roughness arithmetic average deviation value Ra of described reaction gas flow paths, the spacing between trickle protuberance is below about 5 μ m.
4. polymer electrolyte fuel cells separator according to claim 1 is characterized in that, the surface of described reaction gas flow paths forms by the processing of sandblasting, laser processing or processing and forming.
5. polymer electrolyte fuel cells separator according to claim 1 is characterized in that, the staged processing of sandblasting has been carried out on the surface of described reaction gas flow paths.
6. polymer electrolyte fuel cells separator according to claim 1 is characterized in that, oxygen plasma treatment has been carried out on the surface of described reaction gas flow paths.
7. polymer electrolyte fuel cells separator according to claim 1 is characterized in that, utilizes the method for the mixture compression forming that contains described conductive carbon and described bonding agent to form.
8. a polymer electrolyte fuel cells is characterized in that, possesses the described polymer electrolyte fuel cells separator of claim 1.
9. a polymer electrolyte fuel cells is with the evaluation method of separator, it is characterized in that,, with the water droplet on the surface of the reaction gas flow paths that forms in the separator angle that drops the dew discharging performance of this reaction gas flow paths is estimated according to polymer electrolyte fuel cells.
10. polymer electrolyte fuel cells according to claim 9 is characterized in that with the evaluation method of separator, is dropped in the surface of described reaction gas flow paths by making water droplet, obtains the described water droplet angle that drops.
11. the polymer electrolyte fuel cells according to claim 9 evaluation method of separator, it is characterized in that, the described water droplet angle that drops is a environment temperature in the scope below 90 ℃ more than 50 ℃, and under the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70%, the water droplet of the water droplet that the above 80 μ L of 50 μ L the are following angle that drops.
12. the polymer electrolyte fuel cells manufacture method of separator, it is the bonding agent that contains conductive carbon and reinforce conductive carbon, at least on an interarea, form the manufacture method of the polymer electrolyte fuel cells of reaction gas flow paths, it is characterized in that with separator
Under the environment temperature and the ambient humidity, light and temperature condition of relative humidity in 100% following scope more than 70% in 90 ℃ of following scopes more than 50 ℃, when making the following water droplet drippage of the above 80 μ L of 50 μ L, the surface of reaction gas flow paths forms the water droplet structure of angle below 5 degree above 45 are spent that drop.
CNB2005800008657A 2004-05-31 2005-05-30 Polyelectrolyte fuel cell-use separator, polyelectrolyte fuel cell, method of evaluating polyelectrolyte fuel cell-use separator, and production method of polyelectrolyte fuel cell-use separator Active CN100505401C (en)

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JP2004161913 2004-05-31
JP162890/2004 2004-06-01
PCT/JP2005/009875 WO2005117180A1 (en) 2004-05-31 2005-05-30 Polyelectrolyte fuel cell-use separator, polyelectrolyte fuel cell, method of evaluating polyelectrolyte fuel cell-use separator, and production method of polyelectrolyte fuel cell-use separator

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN101971399A (en) * 2008-03-14 2011-02-09 昭和电工株式会社 Fuel cell separator and method of manufacturing the same
CN101622747B (en) * 2007-12-28 2012-07-25 松下电器产业株式会社 Fuel cell
CN111540925A (en) * 2020-05-07 2020-08-14 擎能动力科技(苏州)有限公司 Single fuel cell, fuel cell stack and working mode

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DK179150B1 (en) * 2016-10-19 2017-12-11 Serenergy As A fuel cell stack and its method of production, a separator plate in particular a bipolar plate, for a fuel cell and its production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101622747B (en) * 2007-12-28 2012-07-25 松下电器产业株式会社 Fuel cell
CN101971399A (en) * 2008-03-14 2011-02-09 昭和电工株式会社 Fuel cell separator and method of manufacturing the same
CN111540925A (en) * 2020-05-07 2020-08-14 擎能动力科技(苏州)有限公司 Single fuel cell, fuel cell stack and working mode
CN111540925B (en) * 2020-05-07 2020-11-20 擎能动力科技(苏州)有限公司 Single fuel cell, fuel cell stack and working mode

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