CN100418259C - Solid polyelectrolyte fuel cell - Google Patents
Solid polyelectrolyte fuel cell Download PDFInfo
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- CN100418259C CN100418259C CNB2006100086296A CN200610008629A CN100418259C CN 100418259 C CN100418259 C CN 100418259C CN B2006100086296 A CNB2006100086296 A CN B2006100086296A CN 200610008629 A CN200610008629 A CN 200610008629A CN 100418259 C CN100418259 C CN 100418259C
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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
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Abstract
Provided is a solid polyelectrolyte fuel cell capable of suppressing a gas leak between a fuel electrode film side and an oxide electrode film side by suppressing deterioration of a solid polyelectrolyte film on its peripheral side. A solid polyelectrolyte fuel cell (10) includes: a cell in which electrode films (12, 13) are provided on one side and the other side of a solid polyelectrolyte film, respectively; a first gas diffusion layer (14) provided so as to cover the electrode film (12) on one side of the cell; a second gas diffusion layer (15) provided so as to cover the electrode film (13) on the other side of the cell; and separators (16) provided on the one side and the other side of the cell, respectively, with the gas diffusion layers (14, 15) interposed therebetween. The solid polyelectrolyte fuel cell includes: first insulating layers (18) which are provided between the solid polyelectrolyte film (11) of the cell and the gas diffusion layers (14, 15) and have electrical insulating properties; and second insulating layers (19) which are provided on peripheral edges of the gas diffusion layers (14, 15) and have electrical insulating properties.
Description
Technical field
The present invention relates to solid macromolecular electrolyte type fuel cell.
Background technology
The summary that Figure 10 illustrates the pith of polymer electrolyte fuel cell in the past constitutes.
As shown in figure 10, has proton (H
+) side bonds of conductive solid polyelectrolyte membrane 111 contains catalyst metals such as Pt-Ru class and have conductivity and the fuel electrodes film 112 of gas-premeable.At catalyst metals such as the bonding Pt of the containing classes of the opposite side of solid polyelectrolyte membrane 111 and have conductivity and the oxidation utmost point film 113 of gas-premeable.
In fuel electrodes film 112 sides of electrode film as a side of the solid polyelectrolyte membrane assembly of electrode (battery) that contains above-mentioned solid polyelectrolyte membrane 111, fuel electrodes film 112, oxidation utmost point film 113 etc., have diffusible first gas diffusion layers 114 of conductivity and gas and surround and bonding in the mode that coats this fuel electrodes film 112, it is bonding promptly directly to contact solid polyelectrolyte membrane 111 ground than the fuel electrodes film 112 first big gas diffusion layers 114 with this fuel electrodes film 112.Surrounding as oxidation utmost point film 113 sides of the electrode film of battery opposite side and bondingly having conductivity and diffusible second gas diffusion layers 115 of gas and make it to coat this oxidation utmost point film 113, be bonding second gas diffusion layers 115 bigger, and make its directly this oxidation utmost point film 113 and solid polyelectrolyte membrane 111 of contact than oxidation utmost point film 113.
At a side and the opposite side of the above-mentioned battery of bonding above-mentioned gas diffusion layer 114,115, form fuel gas runner such as hydrogen on the one hand, when forming oxidizing gas runner such as air or oxygen on the other hand, the dividing plate 116 with conductivity be set respectively.
The periphery of the above-mentioned solid polyelectrolyte membrane 111 that exposes from the periphery of above-mentioned electrode film 112,113 and above-mentioned gas diffusion layer 114,115 by encapsulant 117 by aforementioned barriers 116 clampings.
In addition, in Fig. 9, put down in writing, very close to each other and driving fit is at the end face of this electrode film 112,113 between the end face of above-mentioned gas diffusion layer 114,115 and above-mentioned electrode film 112,113, but in fact, also have and the end face of above-mentioned electrode film 112,113 between gapped and be in direct contact with and carry out bonding situation on the above-mentioned solid polyelectrolyte membrane 111.
In this solid macromolecular electrolyte type fuel cell 110 in the past, in fueling gas in the above-mentioned fuel gas runner of aforementioned barriers 116, when the above-mentioned oxidizing gas runner of aforementioned barriers 116 is supplied with oxidizing gas, fuel gas supplies in the fuel electrodes film 112 while spreading in first gas diffusion layers 114, simultaneously, oxidizing gas supplies to oxidation utmost point film 113 while spreading in second gas diffusion layers 115, electrochemical reaction takes place in fuel gas and oxidizing gas in above-mentioned battery thus, at the proton (H of fuel electrode 112 sides by the hydrogen generation
+) interior to oxidation utmost point film 113 side shiftings through solid polyelectrolyte membrane 111, simultaneously, at the electronics (e of fuel electrodes film 112 sides by the hydrogen generation
-) from first gas diffusion layers 114 and aforementioned barriers 116 via external circuit by above-mentioned dividing plate 116 and second gas diffusion layers 115 to oxidation utmost point film 113 side flow.Thus, make oxygen and above-mentioned proton and above-mentioned electron reaction generate water, can generate electricity simultaneously in oxidation utmost point film 113 sides.
No. 3271410 communique of [patent documentation 1] special permission
No. 3345240 communique of [patent documentation 2] special permission
[patent documentation 3] spy opens the 2003-123777 communique
Summary of the invention
Invent problem to be solved
But, in above-mentioned solid macromolecular electrolyte type fuel cell in the past, when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., generate hydrogen peroxide (H
2O
2) wait the side reaction product, and when generating hydroxy radical free radicals such as (OH) by this hydrogen peroxide, this free radical makes solid polyelectrolyte membrane 111 deteriorations, might between fuel electrodes film 112 sides and oxidation utmost point film 113 sides gas leakage take place.
When present inventors have confirmed the deterioration of the solid polyelectrolyte membrane 111 that caused by this free radical, learn that its major part all occurs in the perimeter sides of solid polyelectrolyte membrane 111.
Therefore, the objective of the invention is to, by the clear and definite degradation mechanism of solid polyelectrolyte membrane, and based on this deterioration countermeasure of implementing solid polyelectrolyte membrane, the deterioration of the perimeter sides that can suppress solid polyelectrolyte membrane is provided and suppress fuel electrodes film side and oxidation utmost point film side between the solid macromolecular electrolyte type fuel cell of gas leakage.
The method of dealing with problems
For addressing the above problem, the solid macromolecular electrolyte type fuel cell that first invention relates to is to possess: the solid polyelectrolyte membrane assembly of electrode that is provided with electrode film at the one side and the another side of solid polyelectrolyte membrane, with first gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the side that is coated on above-mentioned solid polyelectrolyte membrane assembly of electrode, with second gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the opposite side that is coated on above-mentioned solid polyelectrolyte membrane assembly of electrode, solid macromolecular electrolyte type fuel cell with the dividing plate that is provided with at a side of above-mentioned solid polyelectrolyte membrane assembly of electrode and opposite side respectively by the above-mentioned gas diffusion layer, it is characterized in that, for the above-mentioned solid polyelectrolyte membrane that prevents above-mentioned solid polyelectrolyte membrane assembly of electrode and above-mentioned first gas diffusion layers contact with the direct of at least one in above-mentioned second gas diffusion layers, possess between at least one that is arranged in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers and be suppressed at the first degradation inhibiting material that produces free radical between in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers at least one.
The solid macromolecular electrolyte type fuel cell that second invention relates to is to have: the solid polyelectrolyte membrane assembly of electrode that electrode film is set on the one side of solid polyelectrolyte membrane and another side, with first gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the side that covers above-mentioned solid polyelectrolyte membrane assembly of electrode, with second gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the opposite side that covers above-mentioned solid polyelectrolyte membrane assembly of electrode, and the solid macromolecular electrolyte type fuel cell that is separately positioned on the dividing plate of side of above-mentioned solid polyelectrolyte membrane assembly of electrode and opposite side by the above-mentioned gas diffusion layer, it is characterized in that at least one in above-mentioned first gas diffusion layers and above-mentioned second gas diffusion layers do not contact and only be arranged on the above-mentioned electrode film with the above-mentioned solid polyelectrolyte membrane of above-mentioned solid polyelectrolyte membrane assembly of electrode.
The 3rd solid macromolecular electrolyte type fuel cell that invention relates to is to have: the solid polyelectrolyte membrane assembly of electrode that electrode film is set on the one side of solid polyelectrolyte membrane and another side, with first gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the side that covers above-mentioned solid polyelectrolyte membrane assembly of electrode, with second gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the opposite side that covers above-mentioned solid polyelectrolyte membrane assembly of electrode, and the solid macromolecular electrolyte type fuel cell that is separately positioned on the dividing plate of side of above-mentioned solid polyelectrolyte membrane assembly of electrode and opposite side by the above-mentioned gas diffusion layer, it is characterized in that the perimeter sides of the above-mentioned solid polyelectrolyte membrane that exposes from the above-mentioned electrode film of above-mentioned solid polyelectrolyte membrane assembly of electrode contains and suppresses hydrogen peroxide decomposes is the degradation inhibiting material that water and oxygen produce free radical.
The 4th solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, in the solid macromolecular electrolyte type fuel cell of in first or second invention, putting down in writing, for in the above-mentioned solid polyelectrolyte membrane that prevents above-mentioned solid polyelectrolyte membrane assembly of electrode and above-mentioned first gas diffusion layers and above-mentioned second gas diffusion layers at least one directly contacts, have at least one the periphery end that is arranged in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers, and suppress the second degradation inhibiting material of generation free radical between in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers at least one.
The 5th solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, any one, in the solid macromolecular electrolyte type fuel cell of record, between the above-mentioned solid polyelectrolyte membrane of above-mentioned solid polyelectrolyte membrane assembly of electrode and aforementioned barriers, be provided with the space from first to the 3rd invention.
The 6th solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, in the solid macromolecular electrolyte type fuel cell of the record in the 5th invention, for above-mentioned solid polyelectrolyte membrane and the direct of aforementioned barriers that prevents above-mentioned solid polyelectrolyte membrane assembly of electrode contacts, then has the 3rd degradation inhibiting material that is arranged on above-mentioned space and suppress to produce between this solid polyelectrolyte membrane and this dividing plate free radical.
The 7th solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, in the solid macromolecular electrolyte type fuel cell of record, above-mentioned degradation inhibiting material is the material with electrical insulating property in each invention of first, the 4th, the 6th.
The 8th solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, in the solid macromolecular electrolyte type fuel cell of record, above-mentioned degradation inhibiting material is to be the material of water and oxygen with hydrogen peroxide decomposes in each invention of first, the 4th, the 6th.
The 9th solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, in each invention of first, the 4th, the 6th in the solid macromolecular electrolyte type fuel cell of record, above-mentioned degradation inhibiting material is the periphery of the above-mentioned electrode film that prolong to be provided with of at least one the periphery from above-mentioned first gas diffusion layers and above-mentioned second gas diffusion layers.
The tenth solid macromolecular electrolyte type fuel cell that invention relates to, it is characterized in that, in the solid macromolecular electrolyte type fuel cell of the 6th invention record, above-mentioned the 3rd degradation inhibiting material is the encapsulant with the space sealing of the periphery of the aforementioned barriers of adjacency.
The effect of invention
As mentioned above, in solid macromolecular electrolyte type fuel cell, when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., when generating hydrogen peroxide (H
2O
2) when waiting side reaction to generate material, in the past, can generate material by side reactions such as this hydrogen peroxide and generate hydroxyl radical free radical free radicals such as (OH), this free radical might make the solid polyelectrolyte membrane deterioration, and between fuel electrodes film side and the oxidation utmost point film side gas leakage takes place.
Therefore, present inventors carry out found that of deterioration test of the solid polyelectrolyte membrane that caused by such free radical, compare the deterioration that a side of the perimeter sides of solid polyelectrolyte membrane (place that contacts with the above-mentioned gas diffusion layer) is very many with the center side (place that contacts with above-mentioned electrode film) of solid polyelectrolyte membrane.
Present inventors carry out further Investigational results presumption to its reason, and the deterioration of above-mentioned solid polyelectrolyte membrane is based on following phenomenon and takes place.
That is hydrogen peroxide (the H that generates when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc.,
2O
2) wait side reaction generation material between solid polyelectrolyte membrane and oxidation utmost point film, before producing hydroxyl radical free radical free radicals such as (OH), just to be decomposed into water and oxygen by the above-mentioned catalyst metals in this oxidation utmost point film, the deterioration (with reference to following formula (1)) that therefore, can suppress solid polyelectrolyte membrane.But, above-mentioned hydrogen peroxide (H
2O
2) wait side reaction generate material between solid polyelectrolyte membrane and above-mentioned gas diffusion layer with proton (H
+) and electronics (e
-) reaction at once, generate hydroxyl radical free radical free radicals such as (OH), make solid polyelectrolyte membrane deterioration (with reference to following formula (2)).
H
2O
2→H
2O+1/2O
2 (1)
H
2O
2+H
++e
-→·OH+H
2O (2)
Therefore, in the solid macromolecular electrolyte type fuel cell that the present invention relates to, by making above-mentioned formation, can seek following effect: in the solid polyelectrolyte membrane perimeter sides, prevent from this gas diffusion layers side supply electronics at the interface of solid polyelectrolyte membrane and above-mentioned gas diffusion layer, be suppressed at the reaction of the above-mentioned formula (2) on this gas diffusion layers, prevent between solid polyelectrolyte membrane and this gas diffusion layers by hydrogen peroxide (H
2O
2) wait side reaction to generate material generation hydroxyl radical free radical free radicals such as (OH), or by the hydrogen peroxide (H that between solid polyelectrolyte membrane and this gas diffusion layers, generates
2O
2) wait side reaction to generate material generation hydroxyl radical free radical free radicals such as (OH) before with this hydrogen peroxide (H
2O
2) wait side reaction generation material to be decomposed into water and oxygen, the reaction of the above-mentioned formula (1) of promotion between solid polyelectrolyte membrane and this gas diffusion layers, promptly suppress the reaction of above-mentioned formula (2), prevent by the hydrogen peroxide (H between solid polyelectrolyte membrane and this gas diffusion layers
2O
2) wait side reaction to generate material generation hydroxyl radical free radical free radicals such as (OH).
Therefore, according to the solid macromolecular electrolyte type fuel cell that the present invention relates to, because the hydrogen peroxide (H that can suppress when supplying to fuel gas and oxidizing gas in the battery significantly or generate when carrying out above-mentioned reaction etc.
2O
2) wait side reaction to generate the generation of the hydroxyl radical free radical free radicals such as (OH) of material generation, therefore, can reduce the deterioration of the edge side of the solid polyelectrolyte membrane that causes by this free radical significantly, and prevent the gas leakage between fuel electrodes film side and oxidation utmost point film side.
Description of drawings
[Fig. 1] is the summary pie graph of major part of first embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 2] is the summary pie graph of major part of second embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 3] is the summary pie graph of major part of the 3rd embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 4] is the summary pie graph of major part of the 4th embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 5] is the summary pie graph of major part of the 5th embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 6] is the summary pie graph of major part of the 6th embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 7] is the summary pie graph of major part of the 7th embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 8] is the summary pie graph of major part of other embodiments of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Fig. 9] is the summary pie graph of major part of other embodiments of the solid macromolecular electrolyte type fuel cell that the present invention relates to.
[Figure 10] is the summary pie graph of major part of an example of solid macromolecular electrolyte type fuel cell in the past.
Symbol description
10 solid macromolecular electrolyte type fuel cells
The 10a cushion space
11 solid polyelectrolyte membranes
12 fuel electrodes films
13 oxidation utmost point films
14 first gas diffusion layers
15 second gas diffusion layers
16 dividing plates
17 encapsulants
18 first insulating barriers
19 second insulating barriers
20 solid macromolecular electrolyte type fuel cells
28a, the 28b first hydrogen peroxide decomposes layer
29a, the 29b second hydrogen peroxide decomposes layer
30 solid macromolecular electrolyte type fuel cells
34 first gas diffusion layers
35 second gas diffusion layers
39 spacers
40 solid macromolecular electrolyte type fuel cells
42 fuel electrodes films
43 oxidation utmost point films
44 first gas diffusion layers
45 second gas diffusion layers
50 solid macromolecular electrolyte type fuel cells
59 spacers
60 solid macromolecular electrolyte type fuel cells
69 the 3rd insulating barriers
70 solid macromolecular electrolyte type fuel cells
79 the 3rd insulating barriers
80 solid macromolecular electrolyte type fuel cells
87a, 87b encapsulant
90 solid macromolecular electrolyte type fuel cells
91 solid polyelectrolyte membranes
The 91a edge part
The preferred plan that carries out an invention
Below, the embodiment of the solid macromolecular electrolyte type fuel cell that the present invention relates to based on description of drawings, but the present invention is not subjected to the restriction of following embodiment.
[first embodiment]
First embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 1.Fig. 1 is the summary pie graph of the major part of solid macromolecular electrolyte type fuel cell.
As shown in Figure 1, has proton (H
+) side bonds of conductive solid polyelectrolyte membrane 11 contains catalyst metals such as Pt-Ru class and have conductivity and the fuel electrodes film 12 of gas-premeable.Catalyst metals such as the bonding Pt of the containing class of the opposite side of solid polyelectrolyte membrane 11 and have conductivity and the oxidation utmost point film 13 of gas-premeable.
In fuel electrodes film 12 sides of electrode film as a side of the solid polyelectrolyte membrane assembly of electrode (battery) that comprises above-mentioned solid polyelectrolyte membrane 11, fuel electrodes film 12, oxidation utmost point film 13 etc., having diffusible first gas diffusion layers 14 of conductivity and gas surrounds also bonding with the form that covers this fuel electrodes film 12, that is, than big first gas diffusion layers 14 of fuel electrodes film 12 to be positioned on this fuel electrodes film 12 and the mode on the solid polyelectrolyte membrane 11 is bonded on this fuel electrodes film 12.And be bonded on the above-mentioned solid polyelectrolyte membrane 11 in the mode of direct contact.Second gas diffusion layers 15 with conductivity and gas diffusibility surrounds and is bonded in oxide-film 13 sides as the electrode film of the opposite side of battery in the mode that covers this oxidation utmost point film 13, that is, than big second gas diffusion layers 15 of oxidation utmost point film 12 to be positioned on this oxidation utmost point film 13 and the mode on the solid polyelectrolyte membrane 11 is bonded on this oxidation utmost point film 13.
At a side and the opposite side of the above-mentioned battery of bonding above-mentioned gas diffusion layer 14,15, one side forms fuel gas runners such as hydrogen, and another side forms the runner of oxidizing gases such as air or oxygen, and the dividing plate 16 with conductivity is set respectively simultaneously.
The periphery of the above-mentioned solid polyelectrolyte membrane 11 that exposes from the periphery end of above-mentioned electrode film 12,13 and above-mentioned gas diffusion layer 14,15 is clamped between the aforementioned barriers 16 by paired encapsulant 17.
Be provided as first insulating barrier 18 of the first degradation inhibiting material with electrical insulating property at above-mentioned solid polyelectrolyte membrane 11 with between the above-mentioned gas diffusion layer on the above-mentioned solid polyelectrolyte membrane 11 14,15.In addition, be provided as second insulating barrier 19 of the second degradation inhibiting material with electrical insulating property at the periphery end of above-mentioned gas diffusion layer 14,15.Between above-mentioned solid polyelectrolyte membrane 11 between above-mentioned encapsulant 17 and above-mentioned second insulating barrier 19 and aforementioned barriers 16, cushion space 10a is set.
In addition, as the record in Fig. 1, do not leave the end face of driving fit with gap between the end face of above-mentioned gas diffusion layer 14,15 and above-mentioned electrode film 12,13 at this electrode film 12,13, but in fact, sometimes and the end face of above-mentioned electrode film 12,13 between leave the gap, and be bonded on this solid polyelectrolyte membrane 11 by above-mentioned insulating barrier 18,19 in the mode that is positioned on the above-mentioned solid polyelectrolyte membrane 11.
In addition, as above-mentioned insulating barrier 18,19 material, can enumerate, tetrafluoroethylene resin (PTFE), fluorinated vinyl resin (PVF), pvdf resin (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resins (PFA), ethylene-tetrafluoroethylene copolymer (FTFE), tetrafluoroethene-hexafluoroethylene (four Off ッization ェ チ レ Application-six Off ッization ェ チ レ Application) copolymer (FEP), tetrafluoraoethylene-hexafluoropropylene copolymer resin (PFEP), trifluorochlorethylene resin (PCTFE), chlorine trifluoride ethylene-vinyl copolymer (ECTFE), tetrafluoroethene-luxuriant the copolymer of full Fu Er Evil fluorine type resins such as (TFE/PDD), or PETG (PET), polyethers nitrile (PEN), polyphenylene sulfide (PPS), polyimides (PI), ethylene-vinyl acetate copolymer (EVA), polyethylene (PE), polypropylene (PP), Vingon (PVDC), ethylene-vinyl alcohol copolymer (EVOH), thermoplastic polyurethane (TPU), cellulose triacetate (CTA), polyvinyl alcohol (PVA), polyacrylonitrile (PAN) class, Merlon (PC), poly-methyl starch (PMP), polyphenylene oxide (PPE) class, polyether sulfone (PES), polysulfones resins such as (PS) or polysiloxane-based material etc., but be not limited to these.
In the solid macromolecular electrolyte type fuel cell 10 that such the present embodiment relates to, in fueling gas in the above-mentioned fuel gas runner of aforementioned barriers 16, when the above-mentioned oxidizing gas runner of aforementioned barriers 16 is supplied with oxidizing gas, and, the fuel gas limit is at first gas diffusion layers, 14 diffusion limit fueling utmost point films 12, oxidation utmost point film 13 is supplied with on second gas diffusion layers, 15 diffusion limits in the oxidizing gas limit, thus, fuel gas and oxidizing gas carry out electrochemical reaction in above-mentioned battery, in fuel electrodes film 12 sides, by the proton (H of hydrogen generation
+) in solid polyelectrolyte membrane 11 in oxidation utmost point film 13 side shiftings, in fuel electrodes film 12 sides, the electronics (e that generates by hydrogen
-) from first gas diffusion layers 14 and aforementioned barriers 16 via external circuit, by aforementioned barriers 16 and second gas diffusion layers 15 to oxidation utmost point film 13 side flow.Thus, in oxidation utmost point film 13 sides, oxygen and above-mentioned proton and above-mentioned electron reaction generate water and generate electricity simultaneously.
Here, when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., even generate hydrogen peroxide (H
2O
2) wait side reaction to generate material, because above-mentioned insulating barrier 18 is set at above-mentioned solid polyelectrolyte membrane 11 with between the above-mentioned gas diffusion layer on this solid polyelectrolyte membrane 11 14,15, therefore can suppress to generate material significantly and produce hydroxyl radical free radical free radicals such as (OH) by side reactions such as this hydrogen peroxide, and can reduce the deterioration of the perimeter sides of the solid polyelectrolyte membrane 11 that causes by this free radical significantly, prevent the gas leakage between fuel electrodes film 12 sides and oxidation utmost point film 13 sides.Its cause description is as follows.
As mentioned above, when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., generate hydrogen peroxide (H
2O
2) when waiting side reaction to generate material, in solid macromolecular electrolyte type fuel cell 110 in the past, generate material by side reactions such as this hydrogen peroxide and generate hydroxyl radical free radical free radicals such as (OH), this free radical can make solid polyelectrolyte membrane 111 deteriorations, and the danger of gas leakage might take place between fuel electrodes film 112 sides and oxidation utmost point film 113 sides.
Therefore, the result that present inventors carry out the deterioration test of the solid polyelectrolyte membrane 111 that caused by such free radical judges, compare with the center side (place that contacts with above-mentioned electrode film 112,113) of solid polyelectrolyte membrane 111, the deterioration of the perimeter sides of solid polyelectrolyte membrane 111 (place that contacts with above-mentioned gas diffusion layer 114,115) is very many.
Present inventors carry out further Investigational results presumption to its reason, and the deterioration of above-mentioned solid polyelectrolyte membrane 111 is based on following phenomenon and takes place.
That is hydrogen peroxide (the H that generates when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc.,
2O
2) wait side reaction generation material between solid polyelectrolyte membrane 111 and oxidation utmost point film 113, before producing hydroxyl radical free radical free radicals such as (OH), just to be decomposed into water and oxygen by the above-mentioned catalyst metals in this oxidation utmost point film 113, the deterioration (with reference to following formula (1)) that therefore, can suppress solid polyelectrolyte membrane 111.But, above-mentioned hydrogen peroxide (H
2O
2) wait side reaction generate material between solid polyelectrolyte membrane 111 and above-mentioned gas diffusion layer 114,115 with proton (H
+) and electronics (e
-) reaction at once, generate hydroxyl radical free radical free radicals such as (OH), make solid polyelectrolyte membrane 111 deteriorations (with reference to following formula (2)).
H
2O
2→H
2O+1/2O
2 (1)
H
2O
2+H
++e
-→·OH+H
2O(2)
Therefore, in the present embodiment, for preventing solid polyelectrolyte membrane 11 and above-mentioned gas diffusion layer 14,15 direct contact, by at solid polyelectrolyte membrane 11 be positioned at above-mentioned gas diffusion layer 14 on this solid polyelectrolyte membrane 11, above-mentioned insulating barrier 18 is set between 15 to be prevented from solid polyelectrolyte membrane 11 and this gas diffusion layers 14, this gas diffusion layers 14 on the contact-making surface between 15 (interface), the supply of the electronics of 15 sides, suppress this gas diffusion layers 14, the reaction of the above-mentioned formula (2) on 15 prevents at solid polyelectrolyte membrane 11 and this gas diffusion layers 14, between 15 by hydrogen peroxide (H
2O
2) wait side reaction to generate material generation hydroxyl radical free radical free radicals such as (OH).
Therefore, according to the present embodiment, can suppress the deterioration of perimeter sides of solid polyelectrolyte membrane 11 and the gas leakage between inhibition and fuel electrodes film 12 sides and oxidation utmost point film 13 sides.
In addition, owing between above-mentioned solid polyelectrolyte membrane 11 between above-mentioned encapsulant 17 and above-mentioned second insulating barrier 19 and aforementioned barriers 16, be provided with cushion space 10a, therefore, even solid polyelectrolyte membrane 11 swelling owing to water, make the perimeter sides of solid polyelectrolyte membrane 11 lax, this solid polyelectrolyte membrane 11 that also can be suppressed between solid polyelectrolyte membrane 11 and the above-mentioned electrode film 12,13 produces fold, suppresses generating efficiency and reduces.
And, even solid polyelectrolyte membrane 11 swelling owing to moisture, make the perimeter sides of solid polyelectrolyte membrane 11 lax, above-mentioned gas diffusion layer 14, the perimeter sides of 15 perimeter sides and solid polyelectrolyte membrane 11 becomes state of contact, but pass through at this gas diffusion layers 14,15 periphery end also is provided with above-mentioned insulating barrier 19, therefore can prevent perimeter sides and this gas diffusion layers 14 from solid polyelectrolyte membrane 11, this gas diffusion layers 14 at (interface) between 15 the periphery end, the supply of the electronics of 15 sides, can also suppress this gas diffusion layers 14, the reaction of the above-mentioned formula (2) on 15 the periphery end can also prevent perimeter sides and this gas diffusion layers 14 at solid polyelectrolyte membrane 11, produce from hydrogen peroxide (H between 15 the periphery end
2O
2) wait side reaction to generate the hydroxyl radical free radical free radicals such as (OH) of material.
[second embodiment]
Second embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 2.Fig. 2 is the summary pie graph of the pith of solid macromolecular electrolyte type fuel cell.In addition, for first above-mentioned part that embodiment is same since use with the symbol that in the explanation of above-mentioned first embodiment, uses be same symbol, the explanation of the item repetition that illustrates in Therefore, omited and above-mentioned first embodiment.
The first hydrogen peroxide decomposes layer 28a of the conduct first degradation inhibiting material contain catalyst metals such as Rt-Ru class is set at solid polyelectrolyte membrane 11 with between first gas diffusion layers 14 on this solid polyelectrolyte membrane 11 as shown in Figure 2.The second hydrogen peroxide decomposes layer 29a that contains the conduct second degradation inhibiting material of catalyst metals such as Rt-Ru class in the periphery end setting of first gas diffusion layers 14.
The first hydrogen peroxide decomposes layer 28b of the conduct first degradation inhibiting material contain catalyst metals such as Rt class is set at solid polyelectrolyte membrane 11 with between second gas diffusion layers 15 on this solid polyelectrolyte membrane 11 in addition.The second hydrogen peroxide decomposes layer 29b that contains the conduct second degradation inhibiting material of catalyst metals such as Rt class in the periphery end setting of second gas diffusion layers 15.
Promptly, above-mentioned first embodiment is, for preventing solid polyelectrolyte membrane 11 and above-mentioned above-mentioned gas diffusion layer 14,15 directly contacts, at above-mentioned solid polyelectrolyte membrane 11 and the above-mentioned gas diffusion layer 14 that is positioned on this solid polyelectrolyte membrane 11, between 15 and this gas diffusion layers 14,15 periphery end, setting has the above-mentioned insulating barrier 18 of electrical insulating property, 19, but the present embodiment is in order to prevent solid polyelectrolyte membrane 11 and above-mentioned gas diffusion layer 14,15 directly contacts, at above-mentioned solid polyelectrolyte membrane 11 and the above-mentioned gas diffusion layer 14 that is positioned on this solid polyelectrolyte membrane 11, between 15 and this gas diffusion layers 14,15 periphery end, being provided with hydrogen peroxide decomposes is the above-mentioned hydrogen peroxide decomposes layer 28a of water and oxygen, 28b, 29a, 29b.
In the solid macromolecular electrolyte type fuel cell 20 that such the present embodiment relates to, can obtain electric power by similarly turning round with above-mentioned first embodiment.
Here, when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., even generate hydrogen peroxide (H
2O
2) wait side reaction to generate material, because above-mentioned hydrogen peroxide decomposes layer 28a, 28b are set at above-mentioned solid polyelectrolyte membrane 11 with between the above-mentioned gas diffusion layer on this solid polyelectrolyte membrane 11 14,15, therefore can suppress to generate material significantly and produce hydroxyl radical free radical free radicals such as (OH) by side reactions such as this hydrogen peroxide, and can reduce the deterioration of the perimeter sides of the solid polyelectrolyte membrane 11 that causes by this free radical significantly, can prevent and fuel electrodes film 12 sides and oxidation utmost point film 13 sides between gas leakage.Its cause description is as follows.
As illustrating in above-mentioned first embodiment, the deterioration of the solid polyelectrolyte membrane that causes by free radical, compare with the perimeter sides (place that contacts with the above-mentioned gas diffusion layer) of solid polyelectrolyte membrane, the center side of solid polyelectrolyte membrane (place that contacts with above-mentioned electrode film) is considerably less.This be because, as in above-mentioned first embodiment hydrogen peroxide (H being described
2O
2) wait side reaction generation material between solid polyelectrolyte membrane and electrode film, before producing hydroxyl radical free radical free radicals such as (OH), just to be decomposed into water and oxygen (with reference to above-mentioned formula (1)) by the above-mentioned catalyst metals in this electrode film.
Therefore, in the present embodiment, by above-mentioned hydrogen peroxide decomposes layer 28a, 28b are set at solid polyelectrolyte membrane 11 with between the above-mentioned gas diffusion layer on this solid polyelectrolyte membrane 11 14,15, the hydrogen peroxide (H that generates between by solid polyelectrolyte membrane 11 and this gas diffusion layers 14,15
2O
2) wait side reaction to generate material generation hydroxyl radical free radical free radicals such as (OH) before just with hydrogen peroxide (H
2O
2) wait side reaction generation material to be decomposed into water and oxygen, promote the reaction of the above-mentioned formula (1) between solid polyelectrolyte membrane 11 and this gas diffusion layers 14,15, promptly, suppress the reaction of above-mentioned formula (2), prevent by the hydrogen peroxide (H between solid polyelectrolyte membrane 11 and this gas diffusion layers 14,15
2O
2) wait side reaction to generate material generation hydroxyl radical free radical free radicals such as (OH).
Therefore, same according to the present embodiment with first above-mentioned embodiment, can suppress the deterioration of perimeter sides of solid polyelectrolyte membrane 11 and the gas leakage between inhibition and fuel electrodes film 12 sides and oxidation utmost point film 13 sides.
In addition, even because solid polyelectrolyte membrane 11 is because of the moisture swelling, make the perimeter sides of solid polyelectrolyte membrane 11 lax, the periphery end of above-mentioned gas diffusion layer 14,15 and the perimeter sides of solid polyelectrolyte membrane 11 become state of contact, but owing to also be provided with above-mentioned hydrogen peroxide decomposes layer 29a, 29b at the periphery end of this gas diffusion layers 14,15, the therefore hydrogen peroxide (H that can between periphery end, generate by the perimeter sides of solid polyelectrolyte membrane 11 and this gas diffusion layers 14,15
2O
2) wait side reaction to generate before the material generation hydroxyl radical free radical free radicals such as (OH), just with this hydrogen peroxide (H
2O
2) wait side reaction generation material to be decomposed into water and oxygen, can suppress the reaction of the above-mentioned formula (2) between the periphery end of the perimeter sides of solid polyelectrolyte membrane 11 and this gas diffusion layers 14,15, and can prevent from the hydrogen peroxide (H between the periphery end of the perimeter sides of solid polyelectrolyte membrane 11 and this gas diffusion layers 14,15
2O
2) wait side reaction to generate the generation of the hydroxyl radical free radical free radicals such as (OH) of material.
In addition, as hydrogen peroxide decomposes layer 28a, 28b, 29a, 29b, can promote catalyst metals that hydrogen peroxide decomposes to water and oxygen or active carbon etc., for example, can be the material that contains tungstates at least a among at least a oxide, carbonate or phosphate among Ce, Tl, Mn, Ag, Yb, the W or Ce, Tl, Mn, the Ag etc., not need conductivity or gas-premeable especially.But for example, if contain hydrogen peroxide decomposes layer 28a, 28b, 29a, 29b with the same material of above-mentioned electrode film 12,13, therefore the simplification that can seek to make is preferred.
[the 3rd embodiment]
The 3rd embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 3.Fig. 3 is the summary pie graph of the pith of solid macromolecular electrolyte type fuel cell.In addition, for the part same with first, second above-mentioned embodiment, since use with first, second the explanation of embodiment in the identical symbol of symbol that uses, the identical explanation of item that illustrates in Therefore, omited and above-mentioned first, second embodiment.
As shown in Figure 3, in fuel electrodes film 12 sides of battery, it is bonding in the mode of the opposite face of the contact-making surface with solid polyelectrolyte membrane 11 that only covers this fuel electrodes film 12 to have diffusible first gas diffusion layers 34 of conductivity and gas.In oxidation utmost point film 13 sides of battery, has conductivity and diffusible second gas diffusion layers 35 is bonding in the mode that only covers this oxidation utmost point film 13 face opposite with the contact-making surface of solid polyelectrolyte membrane 11.
At the periphery end of above-mentioned gas diffusion layer 34,35, has the spacer 39 as the second degradation inhibiting material of electrical insulating property with the mode setting of the above-mentioned solid polyelectrolyte membrane 11 of clamping between above-mentioned electrode film 12,13 and above-mentioned encapsulant 17.
As the material of above-mentioned spacer 39, can enumerate fluororesin or other resin or the polysiloxane-based material etc. same, but be not limited to these with the occasion of above-mentioned insulating barrier 18,19.
Promptly, above-mentioned first embodiment is, be positioned at above-mentioned electrode film 12, above-mentioned gas diffusion layer 14 on 13 and on the solid polyelectrolyte membrane 11,15, promptly, than above-mentioned electrode film 12, the above-mentioned gas diffusion layer 14 of 13 big sizes, in 15, at solid polyelectrolyte membrane 11 and the gas diffusion layers 14 that is positioned on this solid polyelectrolyte membrane 11, between 15 and this gas diffusion layers 14,15 peripheries are provided with above-mentioned insulating barrier 18,19, but the present embodiment is, be not positioned on the solid polyelectrolyte membrane 11 and exist only in above-mentioned electrode film 12, on 13, promptly using and above-mentioned electrode film 12, the above-mentioned gas diffusion layer 34 of 13 same sizes, in the time of 35, with perimeter sides and the above-mentioned gas diffusion layer 34 that is clipped in solid polyelectrolyte membrane 11, mode between the 35 periphery ends is provided with above-mentioned spacer 39.
In the solid macromolecular electrolyte type fuel cell 30 that such the present embodiment relates to, by obtaining electric power with the same running of above-mentioned first embodiment.
Here, when fuel gas and oxidizing gas are supplied to inside battery or when carrying out above-mentioned reaction etc., even generate hydrogen peroxide (H
2O
2) wait side reaction to generate material, because above-mentioned gas diffusion layer 34,35 and above-mentioned electrode film 12,13 are same size, promptly, directly do not contact with solid polyelectrolyte membrane 11, therefore can not produce the supply of electronics equally with above-mentioned first embodiment, therefore can be suppressed at significantly to produce on the above-mentioned gas diffusion layer 34,35 and come from hydrogen peroxide (H to solid polyelectrolyte membrane 11
2O
2) wait side reaction to generate the hydroxyl radical free radical free radicals such as (OH) of material.
Therefore, same according to the present embodiment with first, second above-mentioned embodiment, can suppress the deterioration of perimeter sides of solid polyelectrolyte membrane 11 and the gas leakage between inhibition and fuel electrodes film 12 sides and oxidation utmost point film 13 sides.
In addition, even because solid polyelectrolyte membrane 11 is because of the moisture swelling, make the perimeter sides of solid polyelectrolyte membrane 11 lax, above-mentioned gas diffusion layer 34,35 the periphery end and the perimeter sides of solid polyelectrolyte membrane 11 become state of contact, but owing to perimeter sides and above-mentioned gas diffusion layer 34 at solid polyelectrolyte membrane 11, sandwiched above-mentioned spacer 39 between 35 the periphery end, therefore can prevent perimeter sides and this gas diffusion layers 34 from solid polyelectrolyte membrane 11, this gas diffusion layers 34 at (interface) between 35 the periphery end, the supply of the electronics of 35 ends, be suppressed at this gas diffusion layers 34, the reaction of the above-mentioned formula (2) on 35 the periphery end can also prevent perimeter sides and this gas diffusion layers 34 at solid polyelectrolyte membrane 11, produce from hydrogen peroxide (H between 35 the periphery end
2O
2) wait side reaction to generate the hydroxyl radical free radical free radicals such as (OH) of material.
[the 4th embodiment]
The 4th embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 4.Fig. 4 is the summary pie graph of the major part of solid macromolecular electrolyte type fuel cell.In addition, for the first～three above-mentioned part that embodiment is same owing to use the identical symbol of symbol that uses in the explanation with the first～three embodiment, the explanation of the item repetition that illustrates in Therefore, omited and above-mentioned the first～three embodiment.
As shown in Figure 4, the fuel electrodes film 42 of battery, the size of the in-plane of vertical with stack direction (craspedodrome) is bigger than this size of first gas diffusion layers 44.The oxidation utmost point film 43 of battery, the size of the in-plane vertical with stack direction is bigger than this size of second gas diffusion layers 45.
Promptly, in the 3rd the above-mentioned embodiment, above-mentioned electrode film 12,13 and above-mentioned gas diffusion layer 34,35 are same size, but in the present embodiment, above-mentioned gas diffusion layer 44,45 is littler than above-mentioned electrode film 42,43, in other words, the edge of above-mentioned electrode film 42,43 is that edge from above-mentioned gas diffusion layer 44,45 prolongs out and is provided with.
In the solid macromolecular electrolyte type fuel cell 40 that such the present embodiment relates to, similarly turn round by situation with above-mentioned first～the 3rd embodiment, can obtain electric power.
Here, when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., even generate hydrogen peroxide (H
2O
2) wait side reaction to generate material, because above-mentioned electrode film 42,43 edge is from above-mentioned gas diffusion layer 44,45 edge prolongs out and is provided with, therefore, same with the situation of above-mentioned the 3rd embodiment, solid polyelectrolyte membrane 11 does not only directly contact above-mentioned gas diffusion layer 44,45 marginal end, and, same with the situation of above-mentioned second embodiment, can suppress significantly to generate the free radical that material produces hydroxyl radical free radical (OH) etc. by side reactions such as this hydrogen peroxide, and can reduce significantly because the deterioration of the edge side of the solid polyelectrolyte membrane 11 that this free radical causes prevents the gas leakage between fuel electrodes film 42 sides and oxidation utmost point film 43 sides.Its reason is described as follows.
As in above-mentioned first embodiment, illustrating, the deterioration of the solid polyelectrolyte membrane that free radical causes, compare with the edge side (place that contacts with the above-mentioned gas diffusion layer) of solid polyelectrolyte membrane, the center side of solid polyelectrolyte membrane (place that contacts with above-mentioned electrode film) is considerably less, in above-mentioned first embodiment, illustrating, this be because, hydrogen peroxide (H
2O
2) wait side reaction to generate material between solid polyelectrolyte membrane and electrode film, by the above-mentioned catalyst metals in this electrode film, before hydroxyl radical free radical free-radical generating such as (OH), just be decomposed into water and oxygen (with reference to above-mentioned formula (1)).
Here, in the present embodiment, the edge of above-mentioned electrode film 42,43 is prolonged out setting from the edge of above-mentioned gas diffusion layer 44,45, promptly, by the edge of above-mentioned electrode film 42,43 is replaced the first hydrogen peroxide decomposes layer 28a, 28b in second above-mentioned embodiment as the first degradation inhibiting material, same with the occasion of above-mentioned second embodiment, from hydrogen peroxide (H
2O
2) wait side reaction to generate the hydroxyl radical free radical free-radical generating such as (OH) of material before just with this hydrogen peroxide (H
2O
2) wait side reaction generation material to be decomposed into water and oxygen, preventing from hydrogen peroxide (H
2O
2) when waiting side reaction to generate the generation of hydroxyl radical free radical free radicals such as (OH) of material, because above-mentioned gas diffusion layer 44,45 does not directly contact with solid polyelectrolyte membrane 11, therefore same with the occasion of above-mentioned the 3rd embodiment, the supply of electronics to solid polyelectrolyte membrane 11 can not take place, and then can prevent on above-mentioned gas diffusion layer 44,45 from hydrogen peroxide (H
2O
2) wait side reaction to generate the generation of the hydroxyl radical free radical free radicals such as (OH) of material.
Therefore, same according to the present embodiment with the first～three above-mentioned embodiment occasion, can suppress solid polyelectrolyte membrane 11 edge side deterioration and suppress and fuel electrodes film 42 sides and oxidation utmost point film 43 sides between gas leakage.
In addition, even solid polyelectrolyte membrane 11 swelling owing to moisture, make the edge side of solid polyelectrolyte membrane 11 lax, thus, the marginal end of above-mentioned gas diffusion layer 44,45 and the edge side of solid polyelectrolyte membrane 11 become state of contact, because the edge of above-mentioned electrode film 42,43 is the edges from above-mentioned gas diffusion layer 44,45 to be prolonged out and is provided with, therefore, the contacting of edge side that can suppress the marginal end of above-mentioned gas diffusion layer 44,45 and solid polyelectrolyte membrane 11.
[the 5th embodiment]
The 5th embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 5.Fig. 5 is the summary pie graph of the major part of solid macromolecular electrolyte type fuel cell.In addition, for the first～four above-mentioned part that embodiment is same owing to use the identical symbol of symbol that uses in the explanation with the first～four embodiment, the explanation of the item repetition that illustrates in Therefore, omited and above-mentioned the first～four embodiment.
As shown in Figure 5, at the marginal end of above-mentioned gas diffusion layer 44,45, the spacer 59 of the conduct second degradation inhibiting material with electrical insulating property is set and is located on the above-mentioned electrode film 42,43 that prolongs to come out to be provided with and between the dividing plate 16.
As the material of above-mentioned spacer 59, can enumerate and same fluororesin or other resins or the polysiloxane-based material etc. of above-mentioned insulating barrier 18,19 occasions, but be not limited to these.
Promptly, the solid macromolecular electrolyte type fuel cell 50 that the present embodiment relates to is, in above-mentioned the 4th solid macromolecular electrolyte type fuel cell that embodiment relates to 40, identical with above-mentioned the 3rd embodiment, the solid macromolecular electrolyte type fuel cell of spacer 59 is set at the marginal end of above-mentioned gas diffusion layer 44,45.
Therefore, according to the present embodiment, same with above-mentioned the first～four embodiment, the deterioration of the edge side of inhibition solid polyelectrolyte membrane 11 and the gas leakage between inhibition and fuel electrodes film 42 sides and oxidation utmost point film 43 sides are certain, even solid polyelectrolyte membrane 11 swelling owing to moisture, make the edge side of solid polyelectrolyte membrane 11 lax, thus, above-mentioned gas diffusion layer 44, the edge side of 45 marginal end and solid polyelectrolyte membrane 11 becomes state of contact, compare with the 4th above-mentioned embodiment, can prevent above-mentioned gas diffusion layer 44 more effectively, contacting of the edge side of 45 marginal end and solid polyelectrolyte membrane 11.
[the 6th embodiment]
The 6th embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 6.Fig. 6 is the summary pie graph of the major part of solid macromolecular electrolyte type fuel cell.In addition, for the first～five above-mentioned part that embodiment is same owing to use the identical symbol of symbol that uses in the explanation with the first～five embodiment, the explanation of the item repetition that illustrates in Therefore, omited and above-mentioned the first～five embodiment.
As shown in Figure 6, the 3rd insulating barrier 69 of conduct the 3rd degradation inhibiting material with electrical insulating property is set, and makes itself and aforementioned barriers 16 adjacency at above-mentioned cushion space 10a.
As the material of above-mentioned the 3rd insulating barrier 69, can enumerate fluororesin or other resin or the polysiloxane-based material etc. same, but be not limited to these with the occasion of above-mentioned insulating barrier 18,19.
Promptly, the solid macromolecular electrolyte type fuel cell 60 that the present embodiment relates to is, in the solid macromolecular electrolyte type fuel cell 10 that above-mentioned first embodiment relates to, the 3rd insulating barrier 69 is set in abutting connection with ground with these dividing plate 16 parts with the isolated above-mentioned cushion space 10a of solid polyelectrolyte membrane 11 and dividing plate 16.
In the solid macromolecular electrolyte type fuel cell 60 that such the present embodiment relates to, even when supplying to fuel gas and oxidizing gas in the battery or when carrying out above-mentioned reaction etc., hydrogen oxide (H generated
2O
2) wait side reaction to generate material, just in case when being diffused into aforementioned barriers 16, solid polyelectrolyte membrane 11 swelling owing to water, the edge side of solid polyelectrolyte membrane 11 is lax, the edge side of solid polyelectrolyte membrane 11 becomes the state that touches aforementioned barriers 16, owing to be provided with the 3rd insulating barrier 69 in abutting connection with ground with these dividing plate 16 parts with the isolated above-mentioned cushion space 10a of solid polyelectrolyte membrane 11 and dividing plate 16, therefore can prevent the electronics supply between solid polyelectrolyte membrane 11 and the dividing plate 16 from this dividing plate, suppress the reaction of the above-mentioned formula (2) on this solid polyelectrolyte membrane 11, and prevent between solid polyelectrolyte membrane 11 and dividing plate 16, to produce self-generating hydrogen peroxide (H
2O
2) wait side reaction to generate the hydroxyl radical free radical free radicals such as (OH) of material.
Therefore, according to the present embodiment, same with the occasion of above-mentioned the first～five embodiment, suppress solid polyelectrolyte membrane 11 edge side deterioration and suppress fuel electrodes film 12 sides and oxidation utmost point film 13 sides between gas leakage be certain, even solid polyelectrolyte membrane 11 swelling owing to moisture, make the edge side of solid polyelectrolyte membrane 11 lax, thus, the edge side of solid polyelectrolyte membrane 11 becomes the state that touches aforementioned barriers 16, compare with the first～five above-mentioned embodiment, can prevent the deterioration of the edge side of solid polyelectrolyte membrane 11 more effectively.。
In addition, special problem can not take place even form the gap between the aforementioned barriers 16 of above-mentioned the 3rd insulating barrier 69 and adjacency yet.
[the 7th embodiment]
The 7th embodiment of the solid macromolecular electrolyte type fuel cell that explanation the present invention relates to based on Fig. 7.Fig. 7 is the summary pie graph of the major part of solid macromolecular electrolyte type fuel cell.In addition, for the first～six above-mentioned part that embodiment is same owing to use the identical symbol of symbol that uses in the explanation with the first～six embodiment, the explanation of the item repetition that illustrates in Therefore, omited and above-mentioned the first～six embodiment.
As shown in Figure 7, the 3rd insulating barrier 79 of conduct the 3rd degradation inhibiting material with electrical insulating property is set, and makes itself and above-mentioned solid polyelectrolyte membrane 11 adjacency at above-mentioned cushion space 10a.
Promptly, above-mentioned the 6th solid macromolecular electrolyte type fuel cell that embodiment relates to 60 is, with these dividing plate 16 parts the 3rd insulating barrier 69 is set in abutting connection with ground with the isolated above-mentioned cushion space 10a of solid polyelectrolyte membrane 11 and dividing plate 16, relative therewith, the solid macromolecular electrolyte type fuel cell 70 that the present embodiment relates to is, with these solid polyelectrolyte membrane 11 parts with the isolated above-mentioned cushion space 10a of solid polyelectrolyte membrane 11 and dividing plate 16 the 3rd insulating barrier 79 is set in abutting connection with ground.
Therefore, according to the present embodiment, can obtain and the above-mentioned same effect of the 6th embodiment occasion.
In addition, special problem can not take place even form the gap between the above-mentioned solid polyelectrolyte membrane 11 of above-mentioned the 3rd insulating barrier 79 and adjacency yet.
[other embodiments]
The above-mentioned the 3rd, in five embodiments, used above-mentioned spacer 39 with electrical insulating property, 59, but by using the spacer for example contain the conduct second degradation inhibiting material that promotes catalyst metals that hydrogen peroxide decomposes to water and oxygen and active carbon etc. to replace this spacer 39,59, even solid polyelectrolyte membrane 11 is swelling and lax in the edge side generation of solid polyelectrolyte membrane 11 owing to moisture, above-mentioned gas diffusion layer 34,35,44, the edge side of 45 marginal end and solid polyelectrolyte membrane 11 becomes state of contact, comes edge side and this gas diffusion layers 34 of comfortable solid polyelectrolyte membrane 11,35,44, hydrogen peroxide (the H that generates between 45 the marginal end
2O
2) wait side reaction to generate before the hydroxyl radical free radical free-radical generating such as (OH) of material, just with this hydrogen peroxide (H
2O
2) wait side reaction generation material to resolve into water and oxygen, thereby be suppressed at the reaction of the above-mentioned formula (2) between the marginal end of the edge side of solid polyelectrolyte membrane 11 and this gas diffusion layers 34,35,44,45, also can prevent from the hydrogen peroxide (H between the marginal end of the edge side of comfortable solid polyelectrolyte membrane 11 and this gas diffusion layers 34,35,44,45
2O
2) wait side reaction to generate the generation of the hydroxyl radical free radical free radicals such as (OH) of material.
In addition, the above-mentioned the 6th, in seven embodiments, used the 3rd insulating barrier 69 with electrical insulating property, 79, but promote headed by catalyst metals that hydrogen peroxide decomposes to water and oxygen and the active carbon etc. by using for example to contain, contain for example Ce, Tl, Mn, Ag, Yb, at least a oxide among the W, carbonate or phosphate, or Ce, Tl, Mn, Ag, the 3rd hydrogen peroxide decomposes layer of conduct the 3rd degradation inhibiting material of at least a tungstates etc. replaces the 3rd insulating barrier 69 among the Yb, 79, also can similarly prevent from hydrogen peroxide (H with above-mentioned situation
2O
2) wait side reaction to generate the generation of the hydroxyl radical free radical free radicals such as (OH) of material.
In addition, the above-mentioned the 6th, in seven embodiments, for with these dividing plate 16 parts of the isolated above-mentioned cushion space 10a of solid polyelectrolyte membrane 11 and dividing plate 16 or this solid polyelectrolyte membrane 11 parts are provided as the 3rd degradation inhibiting material in abutting connection with ground the 3rd insulating barrier 69,79 solid macromolecular electrolyte type fuel cell 60,70 situation is illustrated, but also can make for example shown in Figure 8ly, use the encapsulant 87b of these dividing plate 16 parts extend to the isolated above-mentioned cushion space 10a that makes solid polyelectrolyte membrane 11 and dividing plate 16 to replace above-mentioned the 3rd insulating barrier 69 of the side as a side the 3rd degradation inhibiting material, 79 solid macromolecular electrolyte type fuel cell 80.Here, for forming above-mentioned cushion space 10a really, the encapsulant 87a that preferably will have the thickness bigger than above-mentioned encapsulant 87b of the side uses the opposing party.In addition, as above-mentioned encapsulant 87a, 87b, can enumerate, have both the polysiloxane-based rubber of electrical insulating property and sealing or fluorine class rubber (for example, デ ュ Port Application ダ ゥ elastomer ジ ャ パ Application Co., Ltd. " the バ ィ ト Application (registered trade mark) " made etc.) etc.
In addition, in the first～three above-mentioned embodiment, marginal end at above-mentioned gas diffusion layer 14,15,34,35 is provided with above-mentioned insulating barrier 19 or above-mentioned hydrogen peroxide decomposes layer 29a, 29b or above-mentioned spacer 39, but when the edge side of the marginal end of above-mentioned gas diffusion layer 14,15,34,35 and solid polyelectrolyte membrane 11 can not produce state of contact, also can omit above-mentioned insulating barrier 19 or above-mentioned hydrogen peroxide decomposes layer 29a, 29b or above-mentioned spacer 39.But,,,, above-mentioned insulating barrier 19 or above-mentioned hydrogen peroxide decomposes layer 29a, 29b or above-mentioned spacer 39 are set preferably as the first～three above-mentioned embodiment in order to improve fail safe even under these circumstances.
In addition, in above-mentioned the first～seven embodiment, at fuel electrodes film 12,42 and oxidation utmost point film 13,43 both sides are provided with above-mentioned insulating barrier 18,19,69,79 or above-mentioned hydrogen peroxide decomposes layer 28a, 28b, 29a, 29b or above-mentioned spacer 39,59, perhaps, used and this electrode film 12,13 same sizes or than this electrode film 42, the above-mentioned gas diffusion layer 34 of 43 little sizes, 35,44,45, but sometimes only in fuel electrodes film 12 sides of the reaction that on current potential, causes above-mentioned formula (2) easily, above-mentioned insulating barrier 18 only is set, 19,69,79 or above-mentioned hydrogen peroxide decomposes layer 28a, 28b or above-mentioned spacer 39,59, perhaps, only use first gas diffusion layers 34 with these fuel electrodes film 12 same sizes or the size littler than this fuel electrodes film 42,44, just can obtain effect of sufficient.In addition, difference according to various conditions, sometimes only on oxidation utmost point film 13, above-mentioned insulating barrier 18,19,69,79 or above-mentioned hydrogen peroxide decomposes layer 28b, 29b or above-mentioned spacer 39,59 only are set, perhaps, only use second gas diffusion layers 35,45 with oxidation utmost point film 13 same sizes or the size littler, just can obtain effect of sufficient than oxidation utmost point film 43.But, even under these circumstances, in order to improve fail safe, preferably as the first～seven above-mentioned embodiment, both sides at fuel electrodes film 12,42 and oxidation utmost point film 13, above-mentioned insulating barrier 18,19,69,79 or above-mentioned hydrogen peroxide decomposes layer 28a, 28b, 29a, 29b or above-mentioned spacer 39,59 preferably are set, perhaps, use above-mentioned gas diffusion layer 34,35,44,45 with these electrode film 12,13 same sizes or the size littler than this electrode film 42,43.
In addition, for example, as shown in Figure 9, on the edge part 91a of the solid polyelectrolyte membrane 91 that the above-mentioned electrode film 12,13 from battery exposes, as water and oxygen and the degradation inhibiting material that suppresses free-radical generating (for example contain by using hydrogen peroxide decomposes, at least a metal ion among Ce, Tl, Mn, Ag, Yb, the W) solid macromolecular electrolyte type fuel cell 90, also can suppress solid polyelectrolyte membrane 91 edge part 91a deterioration and suppress and fuel electrodes film 12 sides and oxidation utmost point film 13 sides between gas leakage.
Its industrial applicibility is: the solid macromolecular electrolyte type fuel cell that the present invention relates to is various Industrial can very effectively utilizing.
Claims (3)
1. solid macromolecular electrolyte type fuel cell, this battery is to comprise: the solid polyelectrolyte membrane assembly of electrode that electrode film is set at the one side and the another side of solid polyelectrolyte membrane, with first gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the side that is coated on above-mentioned solid polyelectrolyte membrane assembly of electrode, with second gas diffusion layers that is provided with in the mode on the above-mentioned electrode film of the opposite side that is coated on above-mentioned solid polyelectrolyte membrane assembly of electrode, solid macromolecular electrolyte type fuel cell with the dividing plate that is provided with at a side of above-mentioned solid polyelectrolyte membrane assembly of electrode and opposite side respectively by the above-mentioned gas diffusion layer, it is characterized in that, for in the above-mentioned solid polyelectrolyte membrane that prevents above-mentioned solid polyelectrolyte membrane assembly of electrode and above-mentioned first gas diffusion layers and above-mentioned second gas diffusion layers at least one directly contacts, possess between at least one that is arranged in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers and be suppressed at the first degradation inhibiting material that produces free radical between in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers at least one;
Have at least one the periphery end that is arranged in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers, and suppress the second degradation inhibiting material of generation free radical between in this solid polyelectrolyte membrane and this first gas diffusion layers and this second gas diffusion layers at least one;
Above-mentioned degradation inhibiting material is to be the material of water and oxygen with hydrogen peroxide decomposes.
2. according to the solid macromolecular electrolyte type fuel cell of claim 1 record, it is characterized in that, between the above-mentioned solid polyelectrolyte membrane of above-mentioned solid polyelectrolyte membrane assembly of electrode and aforementioned barriers, be provided with the space.
3. according to the solid macromolecular electrolyte type fuel cell of claim 2 record, it is characterized in that, for above-mentioned solid polyelectrolyte membrane and the direct of aforementioned barriers that prevents above-mentioned solid polyelectrolyte membrane assembly of electrode contacts, have and be arranged on above-mentioned space, and suppressing between this solid polyelectrolyte membrane and this dividing plate to produce the 3rd degradation inhibiting material of free radical, above-mentioned degradation inhibiting material is to be the material of water and oxygen with hydrogen peroxide decomposes.
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| US8999595B2 (en) * | 2010-11-30 | 2015-04-07 | GM Global Technology Operations LLC | Fuel cells having improved durability |
| JP5928979B2 (en) * | 2012-01-27 | 2016-06-01 | 日産自動車株式会社 | Fuel cell |
| JP7456374B2 (en) * | 2020-12-25 | 2024-03-27 | トヨタ自動車株式会社 | Method for manufacturing fuel cell and membrane electrode assembly plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335112B1 (en) * | 1998-09-30 | 2002-01-01 | Aisin Seiki Kabushiki Kaisha | Solid polymer electrolyte fuel cell |
| CN1411088A (en) * | 2001-09-27 | 2003-04-16 | 松下电器产业株式会社 | Polymer electrolyte type fuel cell and preparing process thereof |
| CN1459134A (en) * | 2001-01-31 | 2003-11-26 | 松下电器产业株式会社 | High polymer electrolyte fuel cell and electrolyte film-gasket assembly for fuel cell |
| WO2004114444A1 (en) * | 2003-06-24 | 2004-12-29 | Asahi Glass Company, Limited | Membrane electrode assembly for solid polymer fuel cell and method for producing same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335112B1 (en) * | 1998-09-30 | 2002-01-01 | Aisin Seiki Kabushiki Kaisha | Solid polymer electrolyte fuel cell |
| CN1459134A (en) * | 2001-01-31 | 2003-11-26 | 松下电器产业株式会社 | High polymer electrolyte fuel cell and electrolyte film-gasket assembly for fuel cell |
| CN1411088A (en) * | 2001-09-27 | 2003-04-16 | 松下电器产业株式会社 | Polymer electrolyte type fuel cell and preparing process thereof |
| WO2004114444A1 (en) * | 2003-06-24 | 2004-12-29 | Asahi Glass Company, Limited | Membrane electrode assembly for solid polymer fuel cell and method for producing same |
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