CN1879244A - Preservation method of polyelectrolyte type fuel cell stack and preservation treatment object of polyelectrolyte type fuel cell stack - Google Patents
Preservation method of polyelectrolyte type fuel cell stack and preservation treatment object of polyelectrolyte type fuel cell stack Download PDFInfo
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- CN1879244A CN1879244A CNA200580001207XA CN200580001207A CN1879244A CN 1879244 A CN1879244 A CN 1879244A CN A200580001207X A CNA200580001207X A CN A200580001207XA CN 200580001207 A CN200580001207 A CN 200580001207A CN 1879244 A CN1879244 A CN 1879244A
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Classifications
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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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- Fuel Cell (AREA)
Abstract
A storing method for a PEFC stack to suppress the deterioration of the performance of a PEFC stack in a period between an uninstalled state and an installed state in an installation place for use and a storably treated body of the PEFC stack capable of sufficiently preventing the performance of the PEFC stack from being deteriorated in the period between the uninstalled state and the installed state in the installation place for use. The storing method for the PEFC stack (200) is a method for storing the PEFC stack (200) comprising oxidizer flow passages (30) having inlets and outlets and passed through cathodes and reducer flow passages (40) having inlets and outlets and passed through anodes. For storage, the insides of the oxidizer flow passages (30) and the reducer flow passages (40) of the PEFC stack (200) in the uninstalled state are brought into a state where an oxygen concentration is lower than that of the atmosphere.
Description
Technical field
Body is handled in the preservation that the present invention relates to the store method of polymer electrolyte fuel cells group and polymer electrolyte fuel cells group, particularly relates to the store method of polymer electrolyte fuel cells group of the state of setting and the preservation of polymer electrolyte fuel cells group and handles body.
Background technology
In the method for shutting down of existing polymer electrolyte fuel cells (being designated hereinafter simply as PEFC), cut off the supply of oxidant material and reducing agent material, utilize inactive gas such as nitrogen that these materials that residue in the PEFC group are purified (with reference to patent documentation 1) simultaneously.Again, when PEFC stops thereafter, usually also in oxidant stream and reducing agent stream filling inactive gas etc. invade in the PEFC group (with reference to patent documentation 2) to prevent air.Can prevent the electrode catalyst layer generation oxidation in the PEFC group like this, prevent the deterioration of PEFC performance.And the current potential of separator is remained in when having proposed the PEFC generation outage keeping method (with reference to patent documentation 3) of the numerical value of regulation.
On the other hand, at polyelectrolyte membrane-assembly of electrode (MEA; Membrane-Electrode-Assembly) in the making, electrode catalyst layer for example forms the coating that catalyst layer is used by modulation, this coating is coated on the polyelectrolyte membrane surface form.Contain alcohol component as solvent in the coating that the formation catalyst layer is used.With the carbon dust that carries the particle of platinum-ruthenium alloy for example or platinum particle as catalyst fines, this catalyst fines with contain the high molecular alcohol dispersion liquid of perfluoro-hydrocarbon sulfonic acid and mix and form paste.This paste is coated on the polyelectrolyte membrane surface and is formed electrode catalyst layer.The solvent that this alcohol component constitutes enters the electrode catalyst layer of porous matter after making MEA a part left behind.
Here, as the high shortcoming of the polyelectrolyte membrane and the ion resistance at the interface of electrode catalyst layer, also have electrode catalyst layer can not fully engage with diffusion electrode layer, the improvement method of the shortcoming that the electronics resistance at the interface of electrode catalyst layer and diffusion electrode layer is high, there be (for example patent documentation 4 proposes) to clip polyelectrolyte membrane and form the interlayer body, put it into the method for heating and pressurizing formation one in the solvent then with two electrodes.There is (for example patent documentation 5 propose) use to contain the polyelectrolyte membrane and/or the electrode catalyst layer of solvent in advance again, the method that heats and pressurize with the state that not impregnated in fact in the solvent.When adopting such method, the solvent evaporation in integrated operation in the MEA, so the swelling situation of the polyelectrolyte membrane that causes of solvent is suppressed, the engagement state at the interface of polyelectrolyte membrane and catalyst layer can be kept good state.
Patent documentation 1: Japanese kokai publication hei 6-251788 communique.
Patent documentation 2: Japanese kokai publication hei 7-272738 communique.
Patent documentation 3: Japanese kokai publication hei 5-258762 communique.
Patent documentation 4: Japanese kokai publication hei 3-208262 communique.
Patent documentation 5: TOHKEMY 2002-93424 communique.
Summary of the invention
The problem to be solved in the present invention
As illustrated in patent documentation 1～3, knownly reaching under the situation of catalyst activity temperature at generating beginning rear electrode catalyst layer, in case contact with oxidant such as air, oxidation just takes place in electrode catalyst layer, decreased performance.
But the present inventor finds, even PEFC is before beginning generating, if long after the assembly of PEFC group to the time that begins to generate electricity, the voltage rate of descent that performance degradations, particularly output voltage such as output voltage reduction then can the occur significant situation that rises.The present inventor's checking result shows, one of major reason of such performance degradation is the oxide of residual catalyst residual on electrode catalyst.
Always, the performance degradation before beginning for the generating of such PEFC is not even also be concerned about so between the those of ordinary skill of the industry.Therefore the method for shutting down of existing PEFC etc. is the correspondence that begins to provide after using, and is not the deterioration of seeking to prevent after the PEFC group is made the electrode catalyst layer of this section period before be assembled in the PEFC system.That is to say that the method that prevents of the performance degradation of PEFC in the past is the method that prevents the PEFC performance degradation as the PEFC system.Specifically, it is the pipe arrangement that is connected on oxidant stream and the reducing agent stream that forms by the PEFC group etc., provide the structure of inactive gas etc. from being arranged at outside external equipment, before being assembled in the PEFC system, particularly can not be when being stored in the warehouse and during carrying be used in the PEFC group of free state.
Here, the present invention makes for solving above-mentioned existing problems, particularly, its purpose be to provide inhibition never be provided with state to be arranged at till the place be set use during the store method of polymer electrolyte fuel cells group of performance degradation of polymer electrolyte fuel cells group.Again, purpose of the present invention particularly be to provide can fully prevent from never to be provided with state to be arranged at till the place be set use during the preservation of polymer electrolyte fuel cells group of performance degradation of polymer electrolyte fuel cells group handle body.
Solve in-problem means
The present inventor is in order to realize the foregoing invention purpose, result according to research with keen determination infers, the reason of performance degradation that the PEFC group of state is not set is, in the electrode catalyst layer of MEA, residual solvent such as alcohol and the oxygen oxides such as generating acetic acid that reacts, this oxide causes catalyst poisoning, and such murder by poisoning makes the rotten of electrode catalyst layer progressively develop for a long time, and the performance of electrode catalyst progressively descends.And patent documentation 4,5 thinks that because the evaporation of solvent, the swelling of polyelectrolyte membrane can enough suppress when MEA made.But the result of the present inventor's checking shows that the performance degradation of organizing for the PEFC that state is not set does not almost have effect.Estimate that this is because catalyst electrode layer is a porous plastid, the solvent that enters catalyst electrode layer inside does not evaporate and residues in wherein.
The inventor expects the present invention according to these suppositions, and its effect is verified, discovery is effective.
Just, in order to solve above-mentioned existing problems, the store method of the 1st kind of polymer electrolyte fuel cells group, be to possess to have the oxidant stream of entrance and exit through negative electrode, with reducing agent stream with entrance and exit process anode, formation can provide the oxidant material from the inlet of described oxidant stream, provide the reducing agent material from described reducing agent stream inlet, described oxidant material and described reducing agent material carry out the store method of electrochemical reaction with the polymer electrolyte fuel cells group of the structure of generating electricity at described anode and described negative electrode, will not be provided with in the described oxidant stream of described polymer electrolyte fuel cells group of state and remain the state lower than oxygen concentration in atmosphere in the described reducing agent stream.When adopting such structure, lack with the oxygen that reducing agent side catalyst layer contacts with the oxidant side electrode catalyst layer, therefore can fully be suppressed at the oxidation of residual solvent residual on these electrode catalyst layers, particularly can fully suppress never to be provided with the deterioration of state performance of polymer electrolyte fuel cells group during till the place being set use is set.
Here, what is called is not provided with state, is meant the state before being manufactured in after the assembly of polymer electrolyte fuel cells group in the fuel cell system.Specifically, it is the state that connects on the oxidant stream of polymer electrolyte fuel cells group before the oxidant material generator, or connect reducing agent material feeding device state before on the reducing agent stream, for example refer to preserve or carry the state of polymer electrolyte fuel cells group.Also have, carry out the polymer electrolyte fuel cells group that polymer electrolyte fuel cells group after the electro-chemical reaction between short-term also is contained in the state of setting after the manufacturing of polymer electrolyte fuel cells group.Polymer electrolyte fuel cells group after for example the polymer electrolyte fuel cells group after the performance validation tests, following generating are handled just is contained in the polymer electrolyte fuel cells group of the state of setting.Again, pack in the manufacturing process of the polymer electrolyte fuel cells group situation of store method of the present invention also is contained in the polymer electrolyte fuel cells group of the state of setting.For example preserving with the MEA lamination and under the interim state that links, moment before packing into when packing polymer electrolyte fuel cell system into, collector plate, end plate etc. are equipped on two ends, finally be assembled in the manufacture method of polymer electrolyte fuel cells group, this interim state that links is in fact corresponding to the state that is not provided with of polymer electrolyte fuel cells group.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 2nd polymer electrolyte fuel cells group of the present invention is more preferably and has: will not be provided with in the described oxidant stream of described polymer electrolyte fuel cells group of state and the oxygen concentration in the described reducing agent stream is reduced to the sealing step that reduces step and seal the entrance and exit of the entrance and exit of the described oxidant stream that described oxygen concentration reduces and the described reducing agent stream that described oxygen concentration reduces that is lower than in the atmosphere.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 3rd polymer electrolyte fuel cells group of the present invention, be more preferably described and reduce in the step, the oxygen concentration of described oxidant stream and described reducing agent stream is reduced to 10ppm above 1 * 10
4In the scope below the ppm.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 4th polymer electrolyte fuel cells group of the present invention, be more preferably the described step that reduces and undertaken by the filling substitution gas, described sealing step utilization sealing filling the entrance and exit of described oxidant stream of described substitution gas and filling the closed cell used of the entrance and exit of described reducing agent stream of described substitution gas carry out.
The store method of the 5th polymer electrolyte fuel cells group of the present invention, be more preferably at least one in the described closed cell that uses in the described sealing step, be to possess connecting portion and at the oxygen scavenger container of the main part of inner filling oxygen scavenger with the peristome that is connected with described oxidant stream or described reducing agent stream, the mechanism that when described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize air seal.If adopt such structure, can utilize oxygen scavenger continue to remove in the oxidant stream and the oxygen in the reducing agent stream, therefore can make in the oxidant stream and long term maintenance low oxygen concentration more in the reducing agent stream.
The store method of the 6th polymer electrolyte fuel cells group of the present invention, be more preferably at least one in the described closed cell that uses in the described sealing step, be to have the connecting portion of the peristome that is connected with described oxidant stream or described reducing agent stream and at the substitution gas container of the main part of the described substitution gas of inner filling, when described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize air seal, and the ejection pressure of described substitution gas can be maintained at the mechanism in the scope of regulation.When adopting such structure, can utilize the substitution gas container to continue to prevent in the oxidant stream and the decompression in the reducing agent stream, therefore can make in the oxidant stream and long term maintenance low oxygen concentration more in the reducing agent stream.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 7th polymer electrolyte fuel cells group of the present invention, at least one that is more preferably in the described closed cell that uses in the described sealing step is the sealing bolt.
The store method of the 8th polymer electrolyte fuel cells group of the present invention, be more preferably the described step that reduces and utilize water to carry out filling, described sealing step utilization sealing filling the entrance and exit of described oxidant stream of described water and filling the closed cell used of the entrance and exit of described reducing agent stream of described water carry out.When adopting such structure, water soluble ingredient in the residual organic solvent composition in the electrode catalyst layer is dissolved in the outer water of catalyst layer to be diluted, therefore can fully prevent the partial oxidation reaction, dehydration condensation (comprising the reaction of reaction, the reaction between the partial oxide, water soluble ingredient and partial oxide between the water soluble ingredient) of the water-soluble portion in the electrode catalyst layer etc., so can more reliably obtain effect of the present invention.
The store method of the 9th polymer electrolyte fuel cells group of the present invention, be more preferably carry out described sealing after, the polymer electrolyte fuel cells group maintained be higher than 0 ℃ and be less than or equal to 25 ℃.By being maintained at this temperature range, can prevent from more reliably to residue in that the oxygen of oxidant stream and reducing agent stream causes, residue in partial oxidation reaction, the dehydration condensation (comprising the reaction of reaction, the reaction between the partial oxide, organic solvent composition and partial oxide between organic solvent composition) of the organic solvent composition of oxidant stream and reducing agent stream, be more prone to and can prevent more fully the mechanical damage of the MEA under the low temperature simultaneously.
The store method of the 10th polymer electrolyte fuel cells group of the present invention is more preferably after described sealing step, and the encapsulation step of utilizing the described polymer electrolyte fuel cells group of packaging material level Hermetic Package is arranged.Utilize such structure, can suppress oxygen and enter the generation of the situation in oxidant stream and the reducing agent stream, so can suppress the performance degradation of polymer electrolyte fuel cells group more reliably from the polymer electrolyte fuel cells group.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 11st polymer electrolyte fuel cells group of the present invention, being more preferably described packaging material is to have flexual packaging material, utilizes the described polymer electrolyte fuel cells group of joint level Hermetic Package between these packaging material.
The store method of the 12nd polymer electrolyte fuel cells group of the present invention is more preferably described packaging material and is the rigid container that is made of main part and lid, and that utilizes this main part and lid engages the described polymer electrolyte fuel cells group of level Hermetic Package.When adopting such structure, because container is rigid body, thus can prevent that the polymer electrolyte fuel cells group sustains damage under the situation such as carrying, and container can utilize once again.
The store method of the 13rd polymer electrolyte fuel cells group of the present invention, being more preferably described packaging material is the little packaging material of oxygen gas permeability.By utilizing the little packaging material level Hermetic Package polymer electrolyte fuel cells group of oxygen gas permeability like this, even might see through under the situation of a little oxygen from the liner of polymer electrolyte fuel cells group, can prevent more reliably that also block enters polymer electrolyte fuel cells group inside.And owing to the water penetration of the low packaging material of oxygen gas permeability is also low, change so can suppress polymer electrolyte fuel cells group humidity inside, can suppress the damage of polyelectrolyte membrane 1.
The store method of the 14th polymer electrolyte fuel cells group of the present invention has the generating treatment step that makes described polymer electrolyte fuel cells group generating.By making the generating of polymer electrolyte fuel cells group like this, the water that foreign matter such as solvent residual in the polymer electrolyte fuel cells group and metal and electrochemical reaction can be generated comes along and removes, and therefore can further suppress the performance degradation of polymer electrolyte fuel cells group.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 15th polymer electrolyte fuel cells group of the present invention, the current density that is more preferably described generating treatment step is the described catalyst layer 0.1A/cm of per unit area
2Above 0.4A/cm
2Below.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 16th polymer electrolyte fuel cells group of the present invention, the power generation continuous time that is more preferably in the described generating treatment step is more than 3 hours.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 17th polymer electrolyte fuel cells group of the present invention, the power generation continuous time in the described generating treatment step of being more preferably is that change in voltage is reduced to and is the time till below the 2mV/h.
From obtaining the viewpoint of effect of the present invention more reliably, the store method of the 18th polymer electrolyte fuel cells group of the present invention is more preferably described generating treatment step and makes in described polymer electrolyte fuel cells group and carried out with interior in back 300 hours.
Body is handled in the preservation of the 19th polymer electrolyte fuel cells group of the present invention, be more preferably and possess: have the oxidant stream of entrance and exit through negative electrode, with reducing agent stream with entrance and exit process anode, formation can provide the oxidant material from the inlet of described oxidant stream, provide the reducing agent material from described reducing agent stream inlet, described oxidant material and described reducing agent material carry out the polymer electrolyte fuel cells group of electrochemical reaction with the structure of generating electricity at described anode and described negative electrode, and the closed cell of the entrance and exit of the entrance and exit of the described oxidant stream of sealing oxygen concentration reduction and the described reducing agent stream that oxygen concentration reduces.
When adopting such structure, the oxygen that contacts with oxidant side electrode catalyst layer and reducing agent lateral electrode catalyst layer lacks, can suppress to residue in the oxidation of the residual solvent in these electrode catalyst layers, therefore can provide particularly can fully prevent the state that never is provided with till the place is being set use is set during the preservation processing body of polymer electrolyte fuel cells group of performance degradation of polymer electrolyte fuel cells group.
From obtaining the viewpoint of effect of the present invention more reliably, body is handled in the preservation of the 20th polymer electrolyte fuel cells group of the present invention, and the oxygen concentration that is more preferably described oxidant stream and described reducing agent stream is reduced to 10ppm above 1 * 10
4In the scope below the ppm.
From obtaining the viewpoint of effect of the present invention more reliably, body is handled in the preservation of the 21st polymer electrolyte fuel cells group of the present invention, is more preferably in described oxidant stream and the described reducing agent stream and is filled with substitution gas.
Body is handled in the preservation of the 22nd polymer electrolyte fuel cells group of the present invention, be more preferably at least one in the described closed cell, be to have the connecting portion of the peristome that is connected with described oxidant stream or described reducing agent stream and, when described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize the mechanism that seals at the oxygen scavenger container of the main part of inner filling oxygen scavenger.When adopting such structure,, therefore can further keep in the oxidant stream chronically and the low oxygen concentration in the reducing agent stream owing to can utilize oxygen scavenger to continue to remove in the oxidant stream and the oxygen in the reducing agent stream.
Body is handled in the preservation of the 23rd polymer electrolyte fuel cells group of the present invention, be more preferably at least one in the described closed cell, be to have the connecting portion of the peristome that is connected with described oxidant stream or described reducing agent stream and at the substitution gas container of the main part of the described substitution gas of inner filling, when described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize sealing, and the ejection pressure of described substitution gas can be maintained at the mechanism in the scope of regulation.When adopting such structure, utilize the substitution gas container to continue to prevent in the oxidant stream and the decompression in the reducing agent stream, therefore more in the long term maintenance oxidant stream and the low oxygen concentration in the reducing agent stream.
From obtaining the viewpoint of effect of the present invention more reliably, body is handled in the preservation of the 24th polymer electrolyte fuel cells group of the present invention, and at least one that is more preferably in the described closed cell is the sealing bolt.
Body is handled in the preservation of the 25th polymer electrolyte fuel cells group of the present invention, is more preferably filling water in described oxidant stream and the described reducing agent stream.When adopting such structure, water soluble ingredient in the residual organic solvent composition in the electrode catalyst layer is dissolved in the outer water of catalyst layer to be diluted, therefore can fully prevent the partial oxidation reaction, dehydration condensation (comprising the reaction of reaction, the reaction between the partial oxide, water soluble ingredient and partial oxide between the water soluble ingredient) of the water-soluble portion in the electrode catalyst layer etc., so can more reliably obtain effect of the present invention.
Body is handled in the preservation of the 26th polymer electrolyte fuel cells group of the present invention, is more preferably to have the packaging material that level Hermetic Package is equipped with the polymer electrolyte fuel cells group of described closed cell.When adopting such structure, can suppress oxygen and around the polymer electrolyte fuel cells group, enter the generation of the situation in oxidant stream and the reducing agent stream, so can suppress the performance degradation of polymer electrolyte fuel cells group more reliably.
From obtaining the viewpoint of effect of the present invention more reliably, body is handled in the preservation of the 27th polymer electrolyte fuel cells group of the present invention, being more preferably described packaging material is to have flexual packaging material, utilizes the described polymer electrolyte fuel cells group of joint level Hermetic Package between these packaging material.
Body is handled in the preservation of the 28th polymer electrolyte fuel cells group of the present invention, and being more preferably described packaging material is the rigid containers that are made of main part and lid, and that utilizes this main part and lid engages the described polymer electrolyte fuel cells group of level Hermetic Package.When adopting such structure, because container is rigid body, thus can prevent that the polymer electrolyte fuel cells group sustains damage under the situation such as carrying, and container can utilize once again.
Body is handled in the preservation of the 29th polymer electrolyte fuel cells group of the present invention, and being more preferably described packaging material is the little packaging material of oxygen gas permeability.By utilizing the little packaging material level Hermetic Package polymer electrolyte fuel cells group of oxygen gas permeability like this, even might see through under the situation of a little oxygen from the liner of polymer electrolyte fuel cells group, can prevent more reliably that also block enters in the polymer electrolyte fuel cells group.And owing to the water penetration of the low packaging material of oxygen gas permeability is also low, change so can suppress polymer electrolyte fuel cells group humidity inside, can suppress the damage of polyelectrolyte membrane 1.
Body is handled in the preservation of the 30th polymer electrolyte fuel cells group of the present invention, and better described polymer electrolyte fuel cells group is the polymer electrolyte fuel cells group of handling through generating.
Utilize such structure, the water that electrochemical reaction in foreign matters such as solvent in the polymer electrolyte fuel cells group and metal and generating can being handled generates comes along and removes, and therefore can further suppress the performance degradation of polymer electrolyte fuel cells group.Here, so-called " generating is handled " is the processing of instigating the generating of polymer electrolyte fuel cells group.
The invention effect
As mentioned above, adopt the present invention, particularly can provide inhibition never be provided with state to be arranged at be provided with till the use of place during the store method of polymer electrolyte fuel cells group of performance degradation of polymer electrolyte fuel cells group.Again, adopt the present invention, can provide can fully prevent from never to be provided with state to be arranged at till the place be set use during the preservation processing body of polymer electrolyte fuel cells group of performance degradation of polymer electrolyte fuel cells group.
Description of drawings
Fig. 1 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 1st example.
Fig. 2 is the exploded perspective view that the structure of the PEFC group in the body is handled in the preservation that is contained in the PEFC group of the present invention's the 1st example.
Fig. 3 is the schematic diagram of the basic structure of battery unit.
Fig. 4 represents the block diagram of the store method that the PEFC of the present invention's the 1st example organizes.
Fig. 5 represent the embodiment 1-1 of specified operation and embodiment 1-2 the PEFC group the average cell cell voltage over time.
Fig. 6 is that the oxygen concentration with the oxidant stream is a parameter, and the voltage rate of descent of the average cell cell voltage of the specified operating PEFC group of implementing under the condition identical with embodiment 1-2 with embodiment 1-1 changes.
Fig. 7 represent specified operating embodiment 1-5 and embodiment 1-6 PEFC group 200 the average cell cell voltage over time.
Temperature when Fig. 8 represents with the preservation processing conductor preservation of PEFC group is a parameter, and the voltage rate of descent of the average cell cell voltage of the specified operating PEFC group of implementing under the condition identical with embodiment 1-5 or embodiment 1-6 changes.
Fig. 9 represent specified operating embodiment 2 PEFC group the average cell cell voltage over time.
Figure 10 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 3rd example.
Figure 11 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 4th example.
Figure 12 is the schematic diagram of substitution gas container.
Figure 13 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 5th example.
Figure 14 is the block diagram of store method of the PEFC group of the present invention's the 6th example.
Figure 15 represent specified operating embodiment 3, embodiment 6-1 and comparative example 3 PEFC group the average cell cell voltage over time.
Figure 16 represent specified operating embodiment 6-2 and comparative example 3 PEFC group each battery unit average voltage over time.
Figure 17 represent specified operating embodiment 6-3 and comparative example 3 PEFC group each battery unit average voltage over time.
Figure 18 is the block diagram of store method of the PEFC group of the present invention's the 7th example.
Symbol description
1 polyelectrolyte membrane
2 oxidant side electrode catalyst layers
3 reducing agent lateral electrode catalyst layers
4 oxidant side diffusion electrode layers
5 reducing agent side diffusion electrode layers
10 MEA
15 cathode isolation layers
20 anode separators
30 oxidant streams
30a oxidant stream inlet portion
30b oxidant stream way outlet portion
40 reducing agent streams
40a reducing agent stream inlet portion
40b reducing agent flowing path outlet portion
41 collector plates
42 insulation boards
43 end plates
45 coolant flow path
45a coolant flow path inlet portion
45b coolant flow path export department
50 oxygen scavenger containers
51 substitution gas containers
50a, 51a main part
50b, 51b connecting portion
The 51e pressure-reducing valve
60 sealing bolts
80 means of press seals liners
100 battery units
200 PEFC group
300, body is handled in the preservation of 310,320,33,340,350 PEFC group
V average cell cell voltage
H running time
R voltage rate of descent
The X temperature
The P oxygen concentration
Preferred forms
Followingly describe with reference to the example of accompanying drawing to the best of the present invention.
The 1st example
Store method to the PEFC of the present invention's the 1st example group describes below.
Fig. 1 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 1st example.Fig. 2 is the exploded perspective view that the structure of the PEFC group in the body is handled in the preservation that is contained in the PEFC group of the present invention's the 1st example.
Being contained in the PEFC group 200 that the preservation of the PEFC group of the 1st example handles in the body 300 is that single battery (battery unit) 100 laminations that will utilize which generate electricity by electrochemical reaction constitute.As shown in Figure 2, single battery 100 is made of MEA100, cathode isolation layer 15 and the anode separator 20 of the rectangular plate shape that roughly the same plane is arranged each other.And face of MEA10 contacts with cathode isolation layer 15, and another face and anode separator 20 are sandwiched in wherein contiguously.The stack direction end of battery unit (cell) 100 is clipped by end plate 43,43 across collector plate 41,41 and insulation board 42,42, and is fastening with fastening screw (not shown) between the end plate 43,43.PEFC group 200 can be used in the PEFC system of portable electric equipments such as home-use cogeneration system, electric bicycle, electric automobile, hybrid-electric car, household appliances, laptop computer, portable phone, portable audio equipment, portable data assistance etc.
Here, organize at PEFC and form oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a on the end plate 43 of 200 1 sides.Reducing agent stream 40 also forms identical structure.
Also have,, on PEFC group 200, also form the coolant flow path 45 of cooling agents such as circulation water in order to adjust the temperature of PEFC group 200.Coolant flow path 45 is separated formation with oxidant stream 30 and reducing agent stream 40, forming cooling agent can provide to PEFC group 200 from the coolant flow path 45a that enters the mouth, organize 200 internal shunts at PEFC, in 100 circulations of each battery unit of lamination, be discharged to outside structure from the 45b of coolant outlet portion.
Here, battery unit 100 formation are by the structure of MEA10, cathode isolation layer 15, anode separator 20 laminations.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. 3 is the schematic diagram of MEA basic structure.
MEA10 possesses selectively the polyelectrolyte membrane 1 that sees through hydrionic amberplex and constitute, clip that polyelectrolyte membrane 1 forms, and the carbon dust of carrying platinum metal catalysts is the pair of electrodes catalyst layer (oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3) of principal component and a pair of diffusion electrode layer (oxidant side diffusion electrode layer 4 and reducing agent side diffusion electrode layer 5) that is equipped on this pair of electrodes catalyst layer outer surface.This diffusion electrode layer 4,5 forms has the structure of aeration and electron conduction simultaneously.For example form cellular structure.
Then, oxidant side electrode catalyst layer 2, oxidant side diffusion electrode layer 4 and cathode isolation layer 15 constitute negative electrode.
Again, reducing agent lateral electrode catalyst layer 3, reducing agent side diffusion electrode layer 5 and anode separator 20 constitute anode.
Action to the PEFC group 200 that constitutes as mentioned above describes below.30 shuntings offer a battery unit 100 to the oxidant material through the oxidant stream.In each battery unit 100, the oxidant material is provided for negative electrode.Be exposed to oxidant side diffusion electrode layer 4 here.Hydrogen or hydrogeneous reducing agent material are provided for anode too again.Through reducing agent stream 40, be exposed to reducing agent diffusion electrode layer 5 here.
Then, oxidant material permeance oxidant side diffusion electrode layer 4 arrives oxidant side electrode catalyst layer 2.Equally, the reducing agent material also sees through reducing agent side diffusion electrode layer 5 and arrives reducing agent lateral electrode catalyst layer 3.
In case constitute via cathode isolation layer 15, anode separator 20, collector plate 41,41 (with reference to Fig. 1) and external circuit (not shown) electric connected circuit with oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3, at reducing agent electrode catalyst layer 3 hydrogen with regard to ionization.
Hydrogen ion sees through polyelectrolyte membrane 1, combines with oxonium ion in oxidant side electrode catalyst layer 2, generates water.Again, along with the ionization of hydrogen, the electronics that takes place at reducing agent lateral electrode catalyst layer 3 flows through external circuit (not shown) via reducing agent side diffusion electrode layer 5, generates electric output.
From above-described action as can be known, oxidant side electrode catalyst layer 2 is exposed in the oxidant stream 30 with reducing agent lateral electrode catalyst layer 3 and in the material that is full of in the reducing agent stream 40.Thereby, just to make in the good fuel cell, oxidant side electrode catalyst layer 2 is exposed in the oxidant stream 30 with reducing agent lateral electrode catalyst layer 3 and in the air that is full of in the reducing agent stream 40.And, in case oxidant side electrode catalyst layer 2 is exposed in the air with reducing agent lateral electrode catalyst layer 3, oxidation reaction might take place in the residual solvent in oxidant side electrode catalyst layer 2 and the reducing agent lateral electrode catalyst layer 3, makes the oxidant side electrode catalyst layer 2 and the catalyst of reducing agent lateral electrode catalyst layer 3 poison.
Here, the preservation processing body 300 of the PEFC of the present invention's the 1st example group has formation as described below.
The preservation of PEFC group is handled body 300 and is possessed PEFC group 200 and sealing bolt 60.And in the oxidant stream 30 of PEFC group 200 and reducing agent stream 40 filling substitution gas, the oxygen concentrations in oxidant stream 30 and the reducing agent stream 40 are low to 1% (1 * 10
4Ppm) below, the inlet portion 40a of the inlet portion 30a of oxidant stream and the 30b of export department and reducing agent stream and the 40b of export department utilize sealing bolt (closed cell) 60 hermetic closed respectively.Sealing bolt here uses the PPS resin to constitute.
Here, substitution gas is inactive gass such as nitrogen, argon gas, helium or hydrogen etc. can not become oxidant under the operational environment of PEFC a gas.Also have, here, so-called in the present invention inactive gas except rare gas, also comprises nitrogen etc. does not become electrode reaction under the operational environment of PEFC reactive material, reactive low gas.
Again, here, sealing bolt 60 constitutes closed cell, but closed cell also can utilize the open and close valve of airtight construction to constitute.For example can on the inlet portion 40a of oxidant stream inlet portion 30a and 30b of export department and reducing agent stream and the 40b of export department, open and close valve be installed in advance, utilize the switch of these open and close valves can seal oxidant stream 30 and reducing agent stream 40.In this case, closed cell and PEFC group 200 form one and constitute, and do not need other members such as sealing bolt are managed and dispose.Not needing the manual open and close valve of actuating force when in addition, open and close valve is with preservation is ideal.Perhaps also can be that the electricity that forms closed condition, so-called normally closed (normal closed) type when the forfeiture actuating force is led open and close valve.
Here, PEFC group 200 is PEFC groups that state is not set.The so-called state that is not provided with is meant state before the fuel cell system of packing into after the assembly of PEFC group.Specifically, be meant state or the state before connecting the reducing agent material feeding device on the reducing agent stream before connecting the oxidant material feeding device on the oxidant stream of PEFC group, refer to that for example PEFC organizes the state that is saved or carries.Also have, the electrochemical reaction PEFC group afterwards of carrying out the short time after the PEFC group is made also is contained in the PEFC group of the state of setting.PEFC group after for example the generating of the group of the PEFC after the performance validation tests, regulation is handled is contained in the PEFC group of the state of setting.Again, the situation of enforcement store method of the present invention also is contained in the state of setting in PEFC group manufacturing process.For example with the MEA lamination, preserve with interim tightening state, when being assembled in the PEFC system or before moment, collector plate, end plate are disposed at two ends, in the manufacture method of final assembling PEFC group, this interim tightening state is equivalent to the state that is not provided with of PEFC group in fact.
Store method to the PEFC of the present invention's the 1st example group describes below.
Fig. 4 is the block diagram of store method of the PEFC group of expression the present invention the 1st example.
At first, in step (reducing step) S1, will not be provided with in the oxidant stream 30 of PEFC group 200 of state and the oxygen concentrations in the reducing agent stream 40 are reduced to below the oxygen concentration in the atmosphere.Providing oxygen concentration from oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a here, is 1% (1 * 10
4Ppm) Yi Xia substitution gas, will the oxidant stream in 30 and the gases in the reducing agent stream 40 discharge from oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion respectively, simultaneously with the substitution gas filling in oxidant stream 30 in reducing agent stream 40 in.
Then in step (sealing step) S2, seal the entrance and exit of low oxidant stream 30 of oxygen concentration and reducing agent stream 40 airtightly.Here, the oxygen concentration of the substitution gas of discharging from the oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion is reduced to 1% (1 * 10
4When ppm) following, sealing oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion then seal in the oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a.The detection of oxygen concentration can utilize known oxymeter (not shown) to measure.By means of this, the oxygen concentration in oxidant stream 30 and the reducing agent stream 40 can be reduced to below 1%.Specifically, by on the oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion, being connected gas analyzer (for example Japanese hole field makes the portable gas analyzer PG-200 of manufacturing), concentration of oxygen in the PEFC group gas inside is measured, and inlet 30a, 40a and outlet 30b, 40b with oxidant stream 30 and reducing agent stream 40 under the state below 1% seal airtightly.
Again, here as shown in Figure 1, set O shape and encircle isobaric sealing gasket 80 on sealing bolt 60, means of press seals liner 80 is by the gap sealing between the sealing oxidant flowing path outlet 30b of portion, the reducing agent flowing path outlet 40b of portion, oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a and the sealing bolt 60.Also have, the low more then pure oxide of oxygen concentration is not easy to take place, and is desirable therefore.Using purity among the application is that 99.999% nitrogen is confirmed its effect.Thereby the lower limit of oxygen concentration is 10ppm.It is believed that even use than this more highly purified gas, its effect also remains unchanged, but is not easy to obtain, consider the cost of gas, also is unpractical as store method.
Followingly the present invention's the 1st example is specifically described, but the invention is not restricted to following embodiment according to embodiment.
Embodiment 1-1
Be used in the MEA10 making as described below of battery unit 100.At first, in oxidant side electrode catalyst layer 2, acetylene black is that the average particulate diameter of carbon dust (the system デ of Deuki Kagaku Kogyo Co., Ltd Application カ Block ラ Star Network FX-35) employing carrying 25wt% is the catalyst fines of the platinum particle of 30 .And in reducing agent lateral electrode catalyst layer 3, acetylene black is that to adopt the average particulate diameter of carrying 25wt% be that (weight ratio is Pt: Ru=1: the 1) catalyst fines of particle for platinum-ruthenium alloy of 30 to carbon dust (Deuki Kagaku Kogyo Co., Ltd system デ Application カ Block ラ Star Network FX-35).These catalyst fineses are scattered in the isopropyl alcohol, mix the formation pasty state with the alcohol dispersion liquid (the Off レ ミ オ Application FSS-1 that Asahi Glass Co., Ltd makes) of perfluoro-hydrocarbon sulfonic acid powder, it is on 250 microns the interarea of carbon fiber nonwoven fabric (Dongli Ltd. make TGP-H-090) that these pastel are coated thickness respectively with screen plate printing method, makes oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3 respectively.The catalyst metals amount that comprises in these electrode catalyst layers is 0.3mg/cm
2, perfluoro-hydrocarbon sulfonic acid amount is 1.2mg/cm
2
Adopting thickness at polyelectrolyte membrane 1 is 50 microns perfluoro-hydrocarbon sulfonate film (Nafion112 that du pont company is made).
On the both sides interarea of the central part of polyelectrolyte membrane 1, utilize hot pressing to engage oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3 respectively.Also cut the fluorubber sheet of 250 microns of thickness, make a pair of liner, it is done so that oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3 expose, clip polyelectrolyte membrane 1, utilize hot pressing (135 ℃, 1MPa, 10 minutes condition) that they are engaged on the polyelectrolyte membrane 1 and form one.
Substitution gas adopts 99.999% nitrogen.
Provide nitrogen from oxidant stream inlet portion 30a with the flow of 1L/min, the oxygen concentration P of the nitrogen of discharging from the oxidant stream way outlet 30b of portion is 0.08% o'clock, in regular turn oxidant stream way outlet 30b of portion and oxidant stream inlet portion 30a is sealed airtightly.
Provide nitrogen from reducing agent stream inlet portion 40a with the flow of 1L/min, the oxygen concentration P of the nitrogen of discharging from the reducing agent flowing path outlet 40b of portion is 0.08% o'clock, in regular turn reducing agent flowing path outlet 40b of portion and reducing agent stream inlet portion 40a is sealed airtightly.
In the atmosphere of 20 ℃ of temperature, relative humidity 30% body 300 being handled in the preservation of the PEFC of embodiment 1-1 group preserved 3 months.Here, be stored in and utilize the indoor of air conditioner control temperature and humidity.
Embodiment 1-2
40a provides nitrogen with the flow identical with embodiment 1-1 from reducing agent stream inlet portion, the oxygen concentration P of the nitrogen of discharging from the reducing agent flowing path outlet 40b of portion is 0.11% o'clock, seals reducing agent flowing path outlet 40b of portion and reducing agent stream inlet portion 40a in regular turn airtightly.
Under the condition identical, body 300 is handled in the preservation of PEFC group preserved 3 months with embodiment 1-1.Under the condition identical, carry out specified operation then with embodiment 1-1.
The performance evaluation 1 of utilizing specified operation to carry out
Fig. 5 represent specified operating embodiment 1-1 and embodiment 1-2 PEFC group 200 the average cell cell voltage over time.The voltage rate of descent R of the average cell cell voltage V of the PEFC group 200 of specified operating embodiment 1-2 suppresses in 4.6 μ V/h as shown in the figure.And the voltage rate of descent R of the average cell cell voltage V of the PEFC of specified operating embodiment 1-1 group 200 is 1.2 μ V/h, and the decreased performance of PEFC group 200 further is inhibited.
Again, the average cell cell voltage V of PEFC group 200 also is that embodiment 1-1 is higher than embodiment 1-2.
Also have, Fig. 6 represents that the oxygen concentration with oxidant stream 30 is a parameter, the voltage rate of descent situation of change of the average cell cell voltage of the specified operating PEFC group of implementing under the condition identical with embodiment 1-1 or embodiment 1-2 200.As shown in the figure, oxygen concentration P is low more, and then the voltage rate of descent of the voltage V of average cell unit is low more.
If particularly make oxygen concentration P drop to 1% (1 * 10
4Ppm) below, can find out that then the voltage rate of descent R of voltage V of average cell unit is more stable below 2 μ V/h.Thereby if from the lower limit of raising the cost consideration oxygen concentration of above-mentioned high-purity substitution gas, if also consider the upper limit, then the preservation of PEFC group is handled the oxidant stream 30 of body 300 and the oxygen concentration of reducing agent stream 40 eases down to 10ppm above 1 * 10
4The following scope of ppm is proper.
Embodiment 1-3
The PEFC group 200 of present embodiment adopts the PEFC group identical with embodiment 1-1.
Under the condition identical, body 300 is handled in the preservation of PEFC group and preserved for two weeks with embodiment 1-1.Under the condition identical, carry out specified operation then with embodiment 1.
Embodiment 1-4
The PEFC group 200 of this comparative example adopts the PEFC group identical with embodiment 1-1.
Under the condition identical, body 300 is handled in the preservation of PEFC group and preserved for two weeks with embodiment 1-1.Under the condition identical, carry out specified operation then with embodiment 1-1.
The performance evaluation 2 of utilizing specified operation to carry out
The voltage V of the average cell unit of the PEFC of specified operating embodiment 1-4 group 200 with preserve before compare, reduce 7mV, the deterioration of the performance of PEFC group 200 is inhibited.By contrast, the slippage of the voltage V of the average cell unit before and after the preservation of the PEFC of specified operating embodiment 1-3 group 200 is 2 μ V, and the performance degradation of PEFC group 200 further is inhibited.
Therefore, handle in the preservation of PEFC between the storage life of body 300 be 2 weeks with interior situation under, if oxygen concentration P is 1% (1 * 10
4Ppm) below, then the inhibition effect to the voltage deterioration is big especially as can be seen.
Embodiment 1-5
30a provides nitrogen with the flow identical with embodiment 1-1 from oxidant stream inlet portion, the oxygen concentration P of the nitrogen of discharging from the oxidant stream way outlet 30b of portion is 0.08% o'clock, seals oxidant stream way outlet 30b of portion and oxidant stream inlet portion 30a in regular turn airtightly.
40a provides nitrogen with the flow identical with embodiment 1-1 from reducing agent stream inlet portion, oxygen concentration P at the nitrogen of discharging from the reducing agent flowing path outlet 40b of portion is 0.08% o'clock, seals reducing agent flowing path outlet 40b of portion and reducing agent stream inlet portion 40a in regular turn airtightly.
In the atmosphere of 55 ℃ of temperature, relative humidity 30% body 300 being handled in the preservation of PEFC group preserved 3 months.Here, be stored in and utilize the indoor of air conditioner control temperature and humidity.
Use the PEFC group 200 after preserving under the condition identical, to carry out specified operation with embodiment 1-1.
Embodiment 1-6
30a provides nitrogen with the flow identical with embodiment 1-1 from oxidant stream inlet portion, the oxygen concentration P of the nitrogen of discharging from the oxidant stream way outlet 30b of portion is 0.08% o'clock, seals oxidant stream way outlet 30b of portion and oxidant stream inlet portion 30a in regular turn airtightly.
40a provides nitrogen with the flow identical with embodiment 1-1 from reducing agent stream inlet portion, oxygen concentration P at the nitrogen of discharging from the reducing agent flowing path outlet 40b of portion is 0.08% o'clock, seals reducing agent flowing path outlet 40b of portion and reducing agent stream inlet portion 40a in regular turn airtightly.
In the atmosphere of 65 ℃ of temperature, relative humidity 30% body 300 being handled in the preservation of PEFC group preserved 3 months.Here, be stored in and utilize the indoor of air conditioner control temperature and humidity.
Use the PEFC group 200 after preserving under the condition identical, to carry out specified operation with embodiment 1-1.
The performance evaluation 3 of utilizing specified operation to carry out
Fig. 7 represent specified operating embodiment 1-5 and embodiment 1-6 PEFC group 200 the average cell unit voltage over time.The voltage rate of descent R of the voltage V of the average cell unit of the PEFC group 200 of specified operating embodiment 1-6 is 5.4 μ V/h, and the performance degradation of PEFC group 200 is inhibited.And the voltage rate of descent R of the average cell cell voltage V of the PEFC of specified operating embodiment 1-5 group 200 is 1.4 μ V/h, and the performance degradation of PEFC group 200 further is inhibited.This can think because in embodiment 1-5, the temperature that body 300 is handled in the preservation of PEFC group is below 60 ℃, just PEFC group 200 is maintained at below the platinum activity of such catalysts temperature, and therefore the oxidation reaction of alcohol can be alleviated the performance degradation influence that PEFC group 200 causes.
Again, the voltage V of the average cell unit of PEFC group 200 for embodiment 1-5 than embodiment 1-6 height.This can be to think because during preservation in (3 months), in embodiment 1-5, the poisoning influence that the residual solvent oxidation that oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3 are subjected to causes is subjected to suppressing more fully, so the decline of battery performance also is suppressed very lowly.
Also have, the temperature when Fig. 8 represents with the preservation of the preservation processing body 300 of PEFC group is a parameter, the voltage rate of descent situation of change of the average cell cell voltage of the specified operating PEFC group of implementing under the condition identical with embodiment 1-5 or embodiment 1-6 200.As shown in the figure, the temperature X during preservation is low more, and then the voltage rate of descent R of the voltage V of average cell unit is low more.Particularly the temperature X when preserving is that the rate of descent R of the voltage V of average cell unit is more stable below 2 μ V/h under the situation below 60 ℃.
Also have, temperature X during preservation is below 25 ℃ the time, can prevent from more reliably to residue in that the oxygen of oxidant stream and reducing agent stream causes, at the partial oxidation reaction of oxidant stream and reducing agent stream residual organic solvent composition, dehydration condensation (comprising reaction between organic solvent composition, the reaction of reaction, organic solvent composition and partial oxide between the partial oxide), therefore more suitable.Again, if the temperature X when preserving is higher than 0 ℃, then can be more easily and prevent the mechanical damage of MEA10 at low temperatures more fully.Therefore the preservation of PEFC group is handled body 300 and is kept at and is higher than 0 ℃ and is less than or equal to 25 ℃ and gets final product.
The 2nd example
The present invention's the 2nd example is to replace the substitution gas filling in the example of oxidant stream 30 and reducing agent stream 40 with water.
That is to say, body 310 filling water in the oxidant stream 30 of PEFC group 200 and reducing agent stream 40 is handled in the preservation of the PEFC of this example group, utilizes sealing bolt 60 to seal inlet portion 30a and the 30b of export department and the reducing agent stream inlet portion 40a and the 40b of export department of oxidant stream respectively then.Here, hydromining distilled water.
Again, the store method of the PEFC of the present invention's the 2nd example group 310 in the step S1 of Fig. 4 in the oxidant stream 30 of PEFC group 200 and reducing agent stream 40 filling water.Here, oxidant stream inlet portion 30a and the reducing agent stream inlet portion 40a from PEFC group 200 provides distilled water.Then, in the step S2 of Fig. 4, utilize closed cell liquid thickly to seal the oxidant stream 30 of filling water and inlet 30a, 40a and outlet 30b, the 40b of described reducing agent stream 40.Here, the oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion are carried out liquid thickly to be sealed, with the distilled water filling in oxidant stream 30 and in the reducing agent stream 40 time, with oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a in addition liquid thickly seal.Like this, by filling water in oxidant stream 30 and reducing agent stream 40, easily the oxygen concentration in oxidant stream and the reducing agent stream is remained in the concentration lower than the oxygen concentration in the atmosphere.Again, by filling water in oxidant stream 30 and reducing agent stream 40, water soluble ingredient in the residual organic solvent composition in the catalyst layer can be dissolved in catalyst layer is diluted outward, therefore the partial oxidation reaction, dehydration condensation (comprising the reaction between reaction, the reaction between the partial oxide, water soluble ingredient and the partial oxide between the water soluble ingredient) of the water soluble ingredient in the catalyst layer etc. can be fully prevented, therefore effect of the present invention can be obtained more reliably.
Followingly the present invention's the 2nd example is specifically described, but the invention is not restricted to following examples according to embodiment.
Body 310 making as described below are handled in the preservation of PEFC group.Adopt PEFC group 200 with embodiment 1-1 homotype.Distilled water is offered oxidant stream 30 and reducing agent stream 40, sealing oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion, with in the distilled water filling oxidant stream 30 and in the reducing agent stream 40 time, oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a are sealed.By means of this, discharge atmosphere filling distilled water in oxidant stream 30 and in the reducing agent stream 40.
Under the condition identical, the preservation body 300 of PEFC group was preserved 3 months with embodiment 1-1.Under the condition identical, carry out specified operation then with embodiment 1-1.
The performance evaluation 4 of utilizing specified operation to carry out
Fig. 9 represent specified operating embodiment 2 PEFC group 200 the average cell unit voltage over time.The voltage rate of descent R of the voltage V of the average cell unit of the PEFC group 200 of specified operating present embodiment is 1.3 μ V/h, compare with embodiment 1-1 (the voltage rate of descent R of the voltage V of its average cell unit is 4.6 μ V/h), the performance degradation of PEFC group 200 is suppressed.This is considered to owing to the water thereby the oxygen of filling in oxidant stream 30 and in the reducing agent stream 40 lacks, the poisoning situation that the oxidation of the residual solvent of oxidant side electrode catalyst layer 2 and reducing agent lateral electrode catalyst layer 3 causes is inhibited, so the influence that the activity of these electrode catalyst layers of producing in power generation process is reduced reduces.
The 3rd example
Figure 10 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 3rd example.
As shown in the figure, the present invention's the 3rd example is oxygen scavenger container 50 to be installed seal airtightly on oxidant stream inlet portion 30a or the 30b of export department and reducing agent stream inlet portion 40a or the 40b of export department, replaces the example of sealing bolt 60.That is to say that handle in the body 320 in the preservation of the PEFC of this example group, sealing bolt 60 and oxygen scavenger container 50 constitute closed cell.Again, the store method of the PEFC of this example group 200 is identical with the 1st example shown in Figure 4.
Thereby the preservation of the PEFC group of this example is handled the store method of body 320 and PEFC group 200 except oxygen scavenger container 50, and is identical with the 1st example.Therefore, handle body 320, structural element identical with structural element shown in Figure 1 among Figure 10 is marked with identical symbol and omits its explanation, only the oxygen scavenger container 50 as difference is described for the preservation of the PEFC of this example group.Again, the explanation of the store method of the PEFC of this example group is also omitted.
The 4th example
Figure 11 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 4th example.
As shown in the figure, the present invention's the 4th example is substitution gas container 51 promoting the circulation of qi of going forward side by side to be installed thickly seal on oxidant stream inlet portion 30a or outlet 30b and reducing agent stream inlet portion 40a or the 40b of export department, to replace the example of sealing bolt 60.That is to say that handle in the body 30 in the preservation of the PEFC of this example group, sealing bolt 60 and substitution gas container 50 constitute closed cell.Again, the store method of the PEFC of this example group 200 is identical with the 1st example shown in Figure 4.
Thereby the preservation of the PEFC group of this example is handled the store method of body 330 and PEFC group 200 except substitution gas container 51, and is identical with the 1st example.Therefore, handle body 330, structural element identical with structural element shown in Figure 1 among Figure 11 is marked with identical symbol and omits its explanation, only the substitution gas container 51 as difference is described for the preservation of the PEFC of this example group.Again, the explanation of the store method of the PEFC of this example group is also omitted.
Figure 12 is the schematic diagram of substitution gas container.As shown in the figure, substitution gas container 51, its main part 51a are the withstand voltage gas containers of hollow cuboid, and the connecting portion 51b of main part 51 forms the structure that comprises known pressure-reducing valve 51e.Connecting portion 51b is the same with the connecting portion 50b of oxygen scavenger container 50, can simply easily on oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a, load and unload the structure that formation can be sealed airtightly to oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a.By means of this, substitution gas container 51 can utilize the action of pressure-reducing valve 51e corresponding to roughly spraying substitution gas automatically and intermittently with reducing agent stream 40 interior pressure in the oxidant stream 30.That is to say that substitution gas container 51 prevents in the oxidant stream 30 and the decline of the substitution gas pressure in the reducing agent stream 40, therefore can suppress oxygen in the oxidant gas stream 30 and the intrusion in the reducing agent gas flow path 40.Therefore can keep the low oxygen concentration in oxidant stream 30 and the reducing agent stream 40 for more time.
The 5th example
Figure 13 is the schematic diagram that body is handled in the preservation of the PEFC group of the present invention's the 5th example.
As shown in the figure, the present invention's the 3rd example is the promoting the circulation of qi of going forward side by side of oxygen scavenger container 50 and substitution gas container 51 to be installed respectively thickly seal to replace the example of sealing bolt 60 on oxidant stream inlet portion 30a and the 30b of export department and reducing agent stream inlet portion 40a and the 40b of export department.That is to say, handle in the body 340 that the two pairs of oxygen scavenger containers 50 and substitution gas container 51 constitute closed cells in the preservation of the PEFC of this example group.Again, the store method of the PEFC of this example group 200 is identical with the 1st example shown in Figure 4.
Therefore, the example that body 340 is the 3rd example and the combination of the 4th example is handled in the preservation of the PEFC of this example group, so the explanation of the store method of the structure of the preservation processing body of PEFC group and PEFC group is omitted.In the structural element of Figure 13, be marked with identical symbol and omit its explanation for the structural element identical with Fig. 1, Figure 10 and structural element shown in Figure 11 again.Utilize such formation, oxygen scavenger container 50 continues to remove in the oxidant stream 30 and the oxygen in the reducing agent stream 40, and substitution gas container 51 prevents in the oxidant stream 30 and the decompression of the substitution gas in the reducing agent stream 40, therefore can suppress oxygen in the oxidant stream 30 and the intrusion in the reducing agent stream 40.Thereby, can keep in the oxidant stream 30 for more time and the low oxygen concentration state in the reducing agent stream 40.
The 6th example
The 6th example of the present invention is that the preservation of the PEFC group of level Hermetic Package the 1st example～the 5th example is handled body, promptly the example of the PEFC group 200 of closed cell is installed.
At first body 350 being handled in the preservation of the PEFC of this example group below describes.
The preservation of PEFC group is handled body 350 and is utilized packaging material to encapsulate (not shown) airtightly.
Adopt at packaging material under the situation of pliability packaging material, the PEFC that utilizes joint between these packaging material that closed cell will be installed organizes 200 level Hermetic Package.Here, packaging material can use high density polyethylene (HDPE), polyvinyl chloride, polythene-ethenol film or AM aluminum metallization or with its film that forms coated with aluminium foil on film.These packaging material also can be sheets or packed.And the joint between the packaging material can utilize methods such as thermal welding or clamping that the peristome of these packaging material is sealed joint.
Also have, be more preferably in bag with PEFC group 200 and enclose " AGELESS A1 " that oxygen detecting agent, for example silica gel, aerochemistry Co., Ltd. of Mitsubishi make etc.By means of this, can detect the state of the oxygen in the bag, the keeping of body is handled in the preservation of therefore being convenient to the PEFC group.Particularly under the situation that adopts transparent packaging material, do not open bag and just can therefore can more suitably preserve the preservation of PEFC group and handle body from the oxygen condition in the visual examination bag.
Again, the member of handling body 350 in the preservation that PEFC organizes adopts under the situation of the rigid container that is made of main part and lid, utilizes the PEFC group 200 of the joint level Hermetic Package installation closed cell of this main part and lid.Here, rigid container can use the rigid container that aluminium, duralumin constitute.And this main part carries out with engaging by with sealant the junction surface of this main part and lid being sealed of lid.By using rigid container, can prevent that also the preservation of damage PEFC group when carrying from handling body, and container can use once again also.
Can also after handling the body encapsulation, the preservation of PEFC group discharge its inner air.By means of this, can further reduce oxygen and enter the possibility that PEFC organizes 200 inside.
Also have, be more preferably and adopt the little packaging material of oxygen gas permeability.The packaging material that oxygen gas permeability is little, being more preferably the packaging material, particularly oxygen gas permeability that oxygen gas permeability amount and moisture permeability are little on the degree that can realize effect of the present invention film constitutes is 0.01mL/ (m
2Day atmospheric pressure) packaging material that constitute of following film.Specifically, can enumerate packaging material that the laminate film that comprises K coating (polyvinylidene: polychlorostyrene inferior ethene) film constitutes, comprise packaging material that the laminate film of the low film of oxygen gas permeability such as EVOH constitutes, comprise the packaging material that the laminate film of the film that aluminium foil constitutes constitutes.By means of this, can avoid the damage of the polyelectrolyte membrane 1 in the PEFC group 200 of preservation state.That is to say that in case the interior humidity of the preservation processing body of PEFC group changes under the preservation state, the moisture content of polyelectrolyte membrane 1 just changes, and cause that the expansion of polyelectrolyte membrane 1 is shunk, so polyelectrolyte membrane 1 might sustain damage.But packaging material its moisture through performance little owing to oxygen gas permeability is also little, therefore can suppress PEFC and organize the variation of 200 humidity inside, can avoid the damage of polyelectrolyte membrane 1.
Store method to the PEFC of this example group describes below.
Figure 14 is the block diagram of store method of the PEFC group of the present invention's the 6th example.As shown in the figure, the at first the same step S1～step S2 that carries out of store method of the PEFC of this example group with the 1st example～the 5th example.Then, after step S2, in step (encapsulation step) S3, utilize inlet 30a, the 40a of packaging material level Hermetic Package oxidant gas stream 30 and reducing agent gas flow path 40 and the PEFC group 200 that outlet 30b, 40b are closed.
As mentioned above, utilize this example can to oxygen around the PEFC group 200 to oxidant stream 30 in and the intrusion in the reducing agent stream 40 suppress, so can further suppress PEFC and organize 200 performance degradation.According to embodiment the present invention's the 3rd example～the 6th example is specifically described below, but the invention is not restricted to following examples.
In embodiment 3, body 320 making as described below are handled in the preservation of the PEFC of the 3rd example group.
Substitution gas adopts nitrogen.
Be respectively 1000cc/min, 30min from oxidant stream inlet portion 30a and next the providing of nitrogen of reducing agent stream inlet portion 40a.
Oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion go up sealing bolt 60,60 are installed, and oxygen scavenger container 50,50 is installed on oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a, and it is sealed airtightly." AGELESS " that aerochemistry Co., Ltd. of filling Mitsubishi makes among the main part 50a of oxygen scavenger container 50.
During to firm sealing, and dropping under the normal temperature (25 ℃) after the sealing, when measuring through the residual oxygen amounts in the group of the PEFC after 5000 hours 200, be below 0.1% when sealing just, but the residual oxygen amount is increased to about 6% after 5000 hours.Also have, the residual oxygen amount is measured at oxidant stream inlet portion 30a, reducing agent stream inlet portion 40a, the oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion.
Comparative example 3
As a comparative example 3, adopt the PEFC group 200 with embodiment 3 homotypes, in PEFC group 200, remove oxygen, with the state of the not packing preservation of remaining untouched.
Embodiment 6-1
In embodiment 6-1, the preservation processing body 320 usefulness packaging material level Hermetic Package making that body 350 is PEFC groups of embodiment 3 is handled in the preservation of the PEFC of the 6th example group." the GAS BARRIER A1 bag " that packaging material adopt aerochemistry Co., Ltd. of Mitsubishi to make.
Then, during to firm encapsulation, and drop under the normal temperature (25 ℃) after the encapsulation, when carrying out the mensuration identical with embodiment 3 through the residual oxygen amounts in the group of the PEFC after 5000 hours 200, the both almost is identical value below 0.1%.
Body being handled in the preservation of the PEFC of embodiment 3, embodiment 6-1 and comparative example 3 group here, preserved respectively 5000 hours under normal temperature (25 ℃).After preservation, PEFC group 200 is stored in 70 ℃ then, humidification is warmed to 65 ℃ and offer reducing agent stream 40 to the reducing agent material of 65 ℃ of dew points, humidification is warmed to 70 ℃ to the air of 70 ℃ of dew points, and offers oxidant stream 30, carry out the specified operation of PEFC group 200.It is 0.3mA/cm that fuel availability 80%, coefficient of oxygen utilization 40%, current density are adopted in the specified operation of PEFC group 200
2
The performance evaluation 5 of utilizing specified operation to carry out
Figure 15 represent specified operating embodiment 3, embodiment 6-1 and comparative example 3 PEFC group the average cell cell voltage over time.As shown in the figure, compare, even embodiment 3 long-plays also can suppress the decline of the average voltage of each battery unit with comparative example 3.Again, the average voltage of its each battery unit of embodiment 6-1 descends hardly.Like this, utilize the store method of the PEFC group 200 of the 3rd example and the 6th example, can confirm the situation that the deterioration of the endurance quality of PEFC group is inhibited.
Embodiment 6-2
In the present embodiment, preservation processing body 340 making that body 350 is PEFC groups of level Hermetic Package the 5th example are handled in the preservation of the PEFC of the 6th example group.Specifically, utilize the PEFC group 200 with embodiment 3 homotypes, use the gases in the nitrogen replacement PEFC group 200 identical with embodiment 3., utilize oxygen scavenger container 50 sealing oxidant stream way outlet portion 30b and reducing agent flowing path outlet portion 40bs, utilize substitution gas container 51 to seal oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a airtightly thereafter.
The same with the embodiment 6-1 again packaging material that utilize carry out level Hermetic Package to the preservation processing body 340 of PEFC group.
To after firm encapsulation back and the encapsulation through residual oxygen amounts and embodiment 3 the same mensuration in the PEFC group 200 after 5000 hours, the result is below 0.1%, numerical value much at one.
Again respectively under normal temperature (25 ℃) and high temperature (60 ℃), body 350 is handled in the preservation of the PEFC group of present embodiment preserved 5000 hours.Equally with embodiment 3 then carry out specified operation.
The performance evaluation 6 of utilizing specified operation to carry out
Figure 16 represent specified operating embodiment 6-2 and comparative example 3 PEFC group each battery unit average voltage over time.As shown in the figure, even embodiment 6-2 long-play, the average voltage of each battery unit also descends hardly.Can confirm with this, utilize the store method of the PEFC group 200 of the 6th example, can suppress the deterioration of the endurance quality of PEFC group 200.
Embodiment 6-3
In embodiment 6-3, it is to utilize the preservation processing body 330 of the PEFC group of packaging material level Hermetic Package the 4th example to be made into that body 350 is handled in the preservation of the PEFC of the 6th example group.Specifically, the PEFC of utilization and embodiment 3 homotypes group 200 is organized 200 interior gases with the embodiment 3 the same nitrogen replacement PEFC that use.Then, sealing bolt 60,60 is installed on oxidant stream way outlet 30b of portion and the reducing agent flowing path outlet 40b of portion, substitution gas container 51,51 is installed on oxidant stream inlet portion 30a and reducing agent stream inlet portion 40a and it is sealed airtightly.Substitution gas container 51 adopts the container that is filled with nitrogen.
Then, the same with embodiment 6-1, utilize the preservation of packaging material level Hermetic Package PEFC group to handle body 330.
Preserve down the preservation of the PEFC group of present embodiment at normal temperature (25 ℃) and handled body 5000 hours, equally with embodiment 3 then carry out specified operation.
The performance evaluation 7 of utilizing specified operation to carry out
Figure 17 represent specified operating embodiment 6-3 and comparative example 3 PEFC group each battery unit average voltage over time.As shown in the figure, even the PEFC of embodiment 6-3 group 200 long-plays, the average voltage of each battery unit 100 also descends hardly.Can confirm to utilize the store method of the PEFC group 200 of the 6th example can suppress the deterioration of the endurance quality of PEFC group 200 with this.
Also have, in embodiment 3, embodiment 6-1, embodiment 6-2, embodiment 6-3 and comparative example 3, substitution gas adopts helium, argon gas also can access same effect.Again, in these embodiments, substitution gas adopts non-oxidizing gas hydrogen also can access same effect.
The 7th example
The 7th example of the present invention is to handle the same example that carries out step S1 and step S2 with the 1st example～the 6th example in back in PEFC group 200 through generating.That is to say that the structure that body 360 is handled in the preservation of the PEFC group of this example is identical with the 1st example～the 6th example.Therefore, the preservation of the PEFC of this example group is handled the explanation of the structure of body 360 and is omitted, and the store method of the PEFC group of this example is described.
Figure 18 is the block diagram of store method of the PEFC group of the present invention's the 7th example.As shown in the figure, in the store method of the PEFC of this example group, in step (generating treatment step) S0, make the PEFC group 200 of the state of setting continue the power generation continuous time that generating is stipulated with predetermined electric current density.The same with the 1st example～the 6th example then step S1～step S3 that carries out.
Here, in step S0, specifically, make PEFC group 200 be maintained at working temperature, between collector plate 41,41, be electrically connected electric load, and the antianode side provides the reducing agent material respectively, the target side provides the oxidant material, causes the electrochemical reaction of PEFC group 200 with this.Make electrochemical reaction continue the power generation continuous time T of regulation with predetermined electric current density I.
Utilize the store method of the PEFC group 200 of this example, the water that the electrochemical reactions of foreign matter in generating is handled such as solvent residual in the medium PEFC group of MEA catalyst pore and metal generate can be discharged to outside the PEFC group 200, therefore can suppress the performance degradation of PEFC group 200 reliably.
Again, the current density during generating is handled is more preferably the per unit area 0.1A/cm of the catalyst layer 2,3 of MEA10
2More than, 0.4A/cm
2Below.If big or small like this current density just thinks to make the even generation of the water of the electrochemical reaction generation among the MEA10.
Again, the power generation continuous time T of generating processing was suitable with at least 3 hours.This is to need the regular hour because solvent and foreign matter are discharged from PEFC group 200 with the water of generation.
The change in voltage of each battery unit when the power generation continuous time T when again, generating is handled is set at the generating processing and finishes is reduced to (dV/dt) and is advisable for the time of 2mV/h till following.Owing to consider to make voltage stable by removing solvent and foreign matter, can be according to change in voltage reduce to judge the situation of removing solvents and foreign matter from PEFC group 200.
Make in generating processing period and be advisable with interior in back 300 hours with PEFC group 200 again.Because the development of considering the catalyst degradation that solvent and foreign matter cause with and/or the development of polyelectrolyte membrane 1 and the deterioration of the engagement state of electrode catalyst layer 2,3, the generating processing is more preferably the PEFC group period and makes back period relatively early.Specifically, if the PEFC group is made in back 300 hours, then can suppress the performance of PEFC group 200 and carry out deterioration.
Again, more than-10 ℃ of temperature of the MEA10 that the oxidant material during generating is handled and the dew point of reducing agent material are more preferably generating when handling ,+scope below 10 ℃ in.By adopting such dew point, can provide neither too much nor too little moisture to MEA10, and can suppress oxidant stream 30 that water causes and reducing agent stream 40 obstruction, be that what is called is spread unchecked phenomenon, therefore all can guarantee uniform electrochemical reaction among the MEA10.That is to say, all can discharge solvent and foreign matter smoothly among the MEA10, therefore can suppress the performance degradation of PEFC group more reliably.
Followingly the step S0 of the present invention's the 7th example is specifically described, but step S0 of the present invention is not limited to following examples according to embodiment.
Also have, in following embodiment and comparative example, the reducing agent material adopted hydrogen, oxidation material to adopt air during generating was handled.Again, generating is handled PEFC group 200 is remained in 70 ℃, the hydrogen and the air that will add gentle humidification offer oxidant stream 30 and reducing agent stream 40 respectively, regulate the supply of oxidant stream 30 and reducing agent stream 40, making the reducing agent material utilization is 70%, and the oxidant material utilization is 40%.And after generating is handled, in the time in 8 weeks, be stored under the ambient temperature and moisture condition through step S1.(8 week) is the example of the time of the influence of solvent and the foreign matter performance degradation that causes polyelectrolyte membrane 1 between this storage life.
Embodiment 7-1
After PEFC group 200 is made, under ambient temperature and moisture, PEFC group 200 was preserved for 1 week.Then humidification after being warmed to 70 ℃, the hydrogen of 70 ℃ of dew points and air is provided, at current density I=0.4A/cm
2Condition under, adopt power generation continuous time T=3h.After handling, generating under ambient temperature and moisture, preserves the time in 8 weeks through step S1.
Comparative example 7-1
To continue to preserve with the PEFC group 200 usefulness ambient temperature and moistures that the embodiment 7-1 same time makes.That is under ambient temperature and moisture, preserve during till, the preservation after handling expires from beginning after the PEFC group 200 of embodiment 7-1 is made to generating electricity.
Comparative example 7-2
After PEFC group 200 is made, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.After being warmed to 70 ℃, the hydrogen of 70 ℃ of dew points and air provide 3 hours with humidification then.Supply finishes 8 weeks were preserved in the back under ambient temperature and moisture time.The processing of not generating electricity during this period.
Table 1
| ΔV(mV) | |
| Embodiment 7-1 | 10 |
| Comparative example 7-1 | 100 |
| Comparative example 7-2 | 90 |
As known from Table 1, embodiment 7-1 compares with comparative example 7-2 with comparative example 7-1, and V is less for voltage reduction amount Δ.According to this result, can confirm to access more reliable inhibition because the performance degradation of PEFC group is handled in generating.
Embodiment 7-2
After PEFC group 200 is made, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then humidification being warmed to 70 ℃ to 70 ℃ of hydrogen of dew point and air provides then, at current density I=0.1A/cm
2With power generation continuous time T=12h processing of generating electricity.The time that under ambient temperature and moisture, kept for 8 weeks after generating is handled through step S1.
Comparative example 7-3
After PEFC group 200 is made, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then humidification being warmed to 70 ℃ to 70 ℃ of hydrogen of dew point and air provides then, at current density I=0.5A/cm
2With power generation continuous time T=12h processing of generating electricity.The time that under ambient temperature and moisture, kept for 8 weeks after generating is handled through step S1.
Comparative example 7-4
After PEFC group 200 is made, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then humidification being warmed to 70 ℃ to 70 ℃ of hydrogen of dew point and air provides then, at current density I=0.5A/cm
2With power generation continuous time T=3h processing of generating electricity.The time that under ambient temperature and moisture, kept for 8 weeks after generating is handled through step S1.
Comparative example 7-5
After PEFC group 200 is made, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then humidification being warmed to 70 ℃ to 70 ℃ of hydrogen of dew point and air provides then, at current density I=0.4A/cm
2With power generation continuous time T=2h processing of generating electricity.The time that under ambient temperature and moisture, kept for 8 weeks after generating is handled through step S1.
Falling quantity of voltages Δ V when change in voltage (dV/dt) when current density I when table 2 expression embodiment 7-1, embodiment 7-2, comparative example 7-3, comparative example 7-4 and comparative example 7-5 generating are handled and power generation continuous time T, generating processing end and specified operation.
Table 2
| I(A/cm 2) | T(h) | dV/dt(mV/h) | ΔV(mV) | |
| Embodiment 7-1 | 0.4 | 3 | 1.5 | 10 |
| Embodiment 7-2 | 0.1 | 12 | 0.0 | 8 |
| Comparative example 7-3 | 0.05 | 12 | 5.0 | 50 |
| Comparative example 7-4 | 0.5 | 3 | 3.0 | 70 |
| Comparative example 7-5 | 0.4 | 2 | 4.5 | 60 |
From the comparison of embodiment 7-1 and comparative example 7-4, and embodiment 7-2 and comparative example 7-3 more as can be known, embodiment 7-1 compares with comparative example 7-3, comparative example 7-4 with embodiment 7-2, V is less for the falling quantity of voltages Δ.Current density range when therefore generating is handled is with 0.1A/cm
2～0.4A/cm
2Be advisable.This is considered to, if the electrochemical reaction of this current density, then the water of the electrochemical reaction of MEA10 generation can evenly generate.
Again, embodiment 7-1 compares with comparative example 7-3, comparative example 7-4 and comparative example 7-5 with embodiment 7-2, and the change in voltage (dV/dt) when the generating processing finishes drops to below the 1.5mV/h.This thinks because this change in voltage (dV/dt) is in PEFC group 200, particularly the water that produces with electrochemical reaction of the solvent in the pore in the electrode catalyst layer 2,3 and foreign matter is discharged to PEFC generation when organizing outside 200, therefore under change in voltage (dV/dt) drops to situation 1.5mV/h below, PEFC can be organized 200 interior solvent and foreign matters and fully discharge.
Again, as can be known, embodiment 7-1 compares with comparative example 7-5 from the comparison of embodiment 7-1 and comparative example 7-5, and V is smaller for its falling quantity of voltages Δ.Power generation continuous time T when therefore, generating is handled is to be advisable more than 3 hours.This is considered to need 3 hours at least because solvent and foreign matter discharged from PEFC group 200 with the water of generation.
Embodiment 7-3
After making PEFC group 200, under ambient temperature and moisture, PEFC group 200 preserved 300 hours, promptly about 2 weeks.Be designated as generating here, and handle preceding time W (week)=2.Then, humidification after being warmed to 70 ℃, the hydrogen of 70 ℃ of dew points and air is provided, at current density I=0.4A/cm
2Condition under adopt power generation continuous time T=3h processing of generating electricity.After handling, generating under ambient temperature and moisture, preserves the time in 8 weeks through step S1.
Comparative example 7-6
After making PEFC group 200, under ambient temperature and moisture, PEFC group 200 preserved 500 hours, i.e. time about about 3 weeks.Be designated as generating here, and handle preceding time W (week)=3.Then, humidification after being warmed to 70 ℃, the hydrogen of 70 ℃ of dew points and air is provided, at current density I=0.4A/cm
2Condition under adopt power generation continuous time T=3h processing of generating electricity.After handling, generating under ambient temperature and moisture, preserves the time in 8 weeks through step S1.
Falling quantity of voltages Δ V when change in voltage (dV/dt) when time W, current density I when generating is handled before the generating processing of table 3 expression embodiment 7-1, embodiment 7-3 and comparative example 7-6 and power generation continuous time T, generating processing end and specified operation.Also have, as mentioned above, in embodiment 1, under the ambient temperature and moisture condition, PEFC group 200 is preserved the time in about 1 week, preserved more exactly 150 hours.Time W (week) before the generating of embodiment 1 is handled is designated as W=1.
Table 3
| W (week) | I(A/cm 2) | T(h) | dV/dt(mV/h) | ΔV(mV) | |
| Embodiment 7-1 | 1 | 0.4 | 3 | 1.5 | 10 |
| Embodiment 7-3 | 2 | 0.4 | 3 | 2.0 | 12 |
| Comparative example 7-6 | 3 | 0.4 | 3 | 1.5 | 80 |
From embodiment 7-1 and embodiment 7-3 and comparative example 7-6 more as can be known, embodiment 7-1 compares with comparative example 7-6 with embodiment 7-3, approximately slippage Δ V is less.Therefore the time W before generating is handled is advisable with interior with W=2.That is to say, be more preferably the generating processing and make back 300 hours with interior enforcement in PEFC group 200.
Embodiment 7-4
After making PEFC group 200, under ambient temperature and moisture, PEFC group 200 is preserved 1 time-of-week.Then when generating is handled, PEFC group 200 be maintained at 70 ℃ one side humidification to the hydrogen of dew point 60 ℃ and air be warmed to 60 ℃ after provided on one side, at current density I=0.4A/cm
2Condition under adopt power generation continuous time T=3h processing of generating electricity.PEFC group 200 when just handling with generating is that the PEFC group 200 of benchmark and the temperature difference Δ S of oxidant material and reducing agent material are set at-10 ℃.Generating was preserved for 8 weeks under ambient temperature and moisture through step S1 after handling.
Embodiment 7-5
After making PEFC group 200, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then when generating is handled, PEFC group 200 be maintained at 70 ℃ one side humidification to the hydrogen of dew point 80 ℃ and air be warmed to 80 ℃ after provided on one side, at current density I=0.4A/cm
2Condition under adopt power generation continuous time T=3h processing of generating electricity.PEFC group 200 when just handling with generating be the temperature difference Δ S of PEFC group 200 and the oxidant material and the reducing agent material of benchmark be set at+10 ℃.After handling, generating under ambient temperature and moisture, preserves the time in 8 weeks through step S1.
Comparative example 7-7
After making PEFC group 200, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then when generating is handled, PEFC group 200 be maintained at 70 ℃ one side humidification to the hydrogen of dew point 50 ℃ and air be warmed to 50 ℃ after provided on one side, at current density I=0.4A/cm
2Condition under adopt power generation continuous time T=3h processing of generating electricity.PEFC group 200 when just handling with generating is that the PEFC group 200 of benchmark and the temperature difference Δ S of oxidant material and reducing agent material are set at-20 ℃.After handling, generating under ambient temperature and moisture, preserves the time in 8 weeks through step S1.
Comparative example 7-8
After making PEFC group 200, under ambient temperature and moisture, PEFC group 200 is preserved the time in 1 week.Then when generating is handled, PEFC group 200 be maintained at 70 ℃ one side humidification to the hydrogen of dew point 85 ℃ and air be warmed to 85 ℃ after provided on one side, at current density I=0.4A/cm
2Condition under adopt power generation continuous time T=3h processing of generating electricity.PEFC group 200 when just handling with generating be the temperature difference Δ S of PEFC group 200 and the oxidant material and the reducing agent material of benchmark be set at+15 ℃.After handling, generating under ambient temperature and moisture, preserves the time in 8 weeks through step S1.
Table 4
| I(A/cm 2) | T(h) | ΔS(℃) | dV/dt(mV/h) | ΔV(mV) | |
| Embodiment 7-4 | 0.4 | 3 | -10 | 1.5 | 15 |
| Embodiment 7-5 | 0.4 | 3 | +10 | 2.0 | 14 |
| Comparative example 7-7 | 0.4 | 3 | -20 | 3.0 | 55 |
| Comparative example 7-8 | 0.4 | 3 | +15 | 5.0 | 65 |
As known from Table 4, embodiment 7-4 compares with comparative example 7-8 with comparative example 7-7 with embodiment 7-5, and V is smaller for the falling quantity of voltages Δ.Therefore when generating is handled temperature difference Δ S in+10 ℃～-10 ℃ scopes, to be advisable.This be consider temperature difference Δ S than the situation of+10 ℃～-10 ℃ of expanded range under, the generation of moisture is too much or not enough in PEFC group 200, the electrochemical reaction of MEA10 is inhomogeneous, can not make in the PEFC group 200, particularly solvent and the foreign matter in the pore in the electrode catalyst layer 2,3 fully is discharged to outside the PEFC group 200.
Also have, as known from Table 4, the change in voltage (dV/dt) of embodiment 7-4 and embodiment 7-5 is below the 2.0mV/h, and the change in voltage (dV/dt) of comparative example 7-7 and comparative example 7-8 is greater than 2.0mV/h.Result and this result according to above-mentioned table 2 can think, are reduced under the situation of the following degree of 2.0mV/h in change in voltage (dV/dt), and solvent and foreign matter in the PEFC group 200 can fully be discharged.Thereby as can be known, generating is handled to be more preferably and is lasted till that change in voltage (dV/dt) is lower than till the 2.0mV/h.
As mentioned above, body is handled in the preservation of the store method of PEFC group of the present invention and PEFC group, owing to lack the oxygen that contacts with reducing agent lateral electrode catalyst layer with the oxidant side electrode catalyst layer, the oxidation that residues in the residual solvent in these electrode catalyst layers is suppressed, and therefore can suppress the performance degradation of the PEFC group of the state that is not provided with.By processing that the PEFC group that state is not set is generated electricity, can further suppress the performance degradation of PEFC group again.
Also have, the preservation that the store method of PEFC group of the present invention and PEFC organize is handled body and is not restricted to the example of record here, is replaced into the store method of various PEFC groups and the preservation processing body of PEFC group easily according to purport of the present invention.
Industrial applicability
The present invention is useful as the store method that suppresses never to arrange state polymer electrolyte fuel cells group of the performance degradation of polymer electrolyte fuel cells group during till the place setup and use is set. Again, to process body be useful as can fully preventing from never arranging state preservation of the polymer electrolyte fuel cells group of the performance degradation of polymer electrolyte fuel cells group during till the place setup and use is set in the present invention.
Claims (30)
1. the store method of a polymer electrolyte fuel cells group; To possess to have entrance and exit through the oxidant stream of negative electrode; With the reducing agent stream with entrance and exit process anode; Formation can provide from the entrance of described oxidant stream the oxidant material; Provide the reducing agent material from described reducing agent stream entrance; Described oxidant material and described reducing agent material carry out electrochemical reaction with the store method of the polymer electrolyte fuel cells group of the structure of generating electricity at described anode and described negative electrode; It is characterized in that
To not be provided with in the described oxidant stream of described polymer electrolyte fuel cells group of state and remain the state lower in the described reducing agent stream than oxygen concentration in atmosphere.
2. the store method of polymer electrolyte fuel cells group according to claim 1 is characterized in that, has:
Be not provided with in the described oxidant stream of described polymer electrolyte fuel cells group of state and the oxygen concentration in the described reducing agent stream be reduced to be lower than in the atmosphere reduce step and
Seal the sealing step of the entrance and exit of the entrance and exit of the described oxidant stream that described oxygen concentration reduces and the described reducing agent stream that described oxygen concentration reduces.
3. the store method of polymer electrolyte fuel cells group according to claim 2 is characterized in that, reduces in the step described, and the oxygen concentration of described oxidant stream and described reducing agent stream is reduced to 10ppm above 1 * 10
4In the scope below the ppm.
4. the store method of polymer electrolyte fuel cells group according to claim 2 is characterized in that,
The described step that reduces is undertaken by the filling substitution gas,
Described sealing step utilization sealing filling the entrance and exit of described oxidant stream of described substitution gas and filling the closed cell used of the entrance and exit of described reducing agent stream of described substitution gas carry out.
5. the store method of polymer electrolyte fuel cells group according to claim 4 is characterized in that,
In the described closed cell that uses in the described sealing step at least one is to possess connecting portion with the peristome that is connected with described oxidant stream or described reducing agent stream and at the oxygen scavenger container of the main part of inner filling oxygen scavenger,
The mechanism that when described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize air seal.
6. the store method of polymer electrolyte fuel cells group according to claim 4 is characterized in that,
In the described closed cell that uses in the described sealing step at least one is to have the connecting portion of the peristome that is connected with described oxidant stream or described reducing agent stream and at the substitution gas container of the main part of the described substitution gas of inner filling,
When described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize air seal, and the ejection pressure of described substitution gas can be maintained at the mechanism in the scope of regulation.
7. the store method of polymer electrolyte fuel cells group according to claim 4 is characterized in that, at least one in the described closed cell that uses in the described sealing step is the sealing bolt.
8. the store method of polymer electrolyte fuel cells group according to claim 2 is characterized in that,
The described step that reduces utilizes water to carry out filling,
Described sealing step utilization sealing filling the entrance and exit of described oxidant stream of described water and filling the closed cell used of the entrance and exit of described reducing agent stream of described water carry out.
9. the store method of polymer electrolyte fuel cells group according to claim 1 is characterized in that, carry out described sealing after, the polymer electrolyte fuel cells group maintained be higher than 0 ℃ and be less than or equal to 25 ℃.
10. the store method of polymer electrolyte fuel cells group according to claim 2 is characterized in that, after described sealing step, the encapsulation step of utilizing packaging material level Hermetic Package polymer electrolyte fuel cells group is arranged.
11. the store method of polymer electrolyte fuel cells group according to claim 10, it is characterized in that, described packaging material are to have flexual packaging material, utilize the hermetic closed described polymer electrolyte fuel cells group of joint between these packaging material.
12. the store method of polymer electrolyte fuel cells group according to claim 10, it is characterized in that, described packaging material are the rigid containers that are made of main part and lid, utilize the hermetic closed described polymer electrolyte fuel cells group of this main part and engaging of lid.
13. the store method of polymer electrolyte fuel cells group according to claim 10 is characterized in that, described packaging material are the little packaging material of oxygen gas permeability.
14. the store method of polymer electrolyte fuel cells group according to claim 2 is characterized in that, has the generating treatment step that makes described polymer electrolyte fuel cells group generating.
15. the store method of polymer electrolyte fuel cells group according to claim 14 is characterized in that, the current density of described generating treatment step is the described catalyst layer 0.1A/cm of per unit area
2Above 0.4A/cm
2Below.
16. the store method of polymer electrolyte fuel cells group according to claim 14 is characterized in that, the power generation continuous time in the described generating treatment step is more than 3 hours.
17. the store method of polymer electrolyte fuel cells group according to claim 14 is characterized in that, the power generation continuous time in the described generating treatment step is that change in voltage is reduced to and is the time till below the 2mV/h.
18. the store method of polymer electrolyte fuel cells group according to claim 14 is characterized in that, described generating treatment step is made in described polymer electrolyte fuel cells group and was carried out with interior in back 300 hours.
19. body is handled in the preservation of a polymer electrolyte fuel cells group, it is characterized in that possessing
Have the oxidant stream of entrance and exit through negative electrode, with reducing agent stream with entrance and exit process anode, formation can provide the oxidant material from the inlet of described oxidant stream, provide the reducing agent material from described reducing agent stream inlet, described oxidant material and described reducing agent material described anode and described negative electrode carry out electrochemical reaction with the polymer electrolyte fuel cells group of the structure of generating electricity and
The closed cell of the entrance and exit of the described reducing agent stream that the entrance and exit of the described oxidant stream that the sealing oxygen concentration reduces and oxygen concentration reduce.
20. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 19, it is characterized in that, the oxygen concentration of described oxidant stream and described reducing agent stream is reduced to 10ppm above 1 * 10
4In the scope below the ppm.
21. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 19, it is characterized in that, is filled with substitution gas in described oxidant stream and the described reducing agent stream.
22. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 21, it is characterized in that,
In the described closed cell at least one is to have the connecting portion of the peristome that is connected with described oxidant stream or described reducing agent stream and at the oxygen scavenger container of the main part of inner filling oxygen scavenger,
When being installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, described connecting portion setting can realize the mechanism that seals.
23. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 21, it is characterized in that,
In the described closed cell at least one is to have the connecting portion of the peristome that is connected with described oxidant stream or described reducing agent stream and at the substitution gas container of the main part of the described substitution gas of inner filling,
When described connecting portion setting is installed on the entrance and exit of the entrance and exit of described oxidant stream and described reducing agent stream, can realize sealing, and the ejection pressure of described substitution gas can be maintained at the mechanism in the scope of regulation.
24. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 21, it is characterized in that, at least one in the described closed cell is the sealing bolt.
25. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 19, it is characterized in that filling water in described oxidant stream and the described reducing agent stream.
26. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 17, it is characterized in that having the packaging material that level Hermetic Package is equipped with the polymer electrolyte fuel cells group of described closed cell.
27. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 26, it is characterized in that, described packaging material are to have flexual packaging material, utilize the described polymer electrolyte fuel cells group of joint level Hermetic Package between these packaging material.
28. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 26, it is characterized in that, described packaging material are by main part and the rigid container that constitutes of lid, and that utilizes this main part and lid engages the described polymer electrolyte fuel cells group of level Hermetic Package.
29. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 26, it is characterized in that described packaging material are the little packaging material of oxygen gas permeability.
30. body is handled in the preservation of polymer electrolyte fuel cells group according to claim 19, it is characterized in that, described polymer electrolyte fuel cells group is the polymer electrolyte fuel cells group of handling through generating.
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| JP175046/2004 | 2004-06-14 | ||
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| CNB200580001207XA Expired - Fee Related CN100440600C (en) | 2004-06-14 | 2005-06-14 | Preservation method of polyelectrolyte type fuel cell stack and preservation treatment object of polyelectrolyte type fuel cell stack |
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| TWI412173B (en) * | 2011-03-25 | 2013-10-11 | Sumitomo Electric Industries | Redox flow battery and its operation method |
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| US5314762A (en) * | 1992-05-12 | 1994-05-24 | Sanyo Electric Co., Ltd. | Portable power source |
| JP3297125B2 (en) * | 1993-02-25 | 2002-07-02 | 三菱重工業株式会社 | Shutdown storage method of solid polymer electrolyte fuel cell |
| JP4632501B2 (en) * | 2000-09-11 | 2011-02-16 | 大阪瓦斯株式会社 | How to stop and store fuel cells |
| JP2003317771A (en) * | 2002-04-19 | 2003-11-07 | Matsushita Electric Ind Co Ltd | Fuel cell power generation system and operating method for the system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI412173B (en) * | 2011-03-25 | 2013-10-11 | Sumitomo Electric Industries | Redox flow battery and its operation method |
| US8632903B2 (en) | 2011-03-25 | 2014-01-21 | Sumitomo Electric Industries, Ltd. | Redox flow battery and method of operating the same |
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| Publication number | Publication date |
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| CN100440600C (en) | 2008-12-03 |
| CN100589272C (en) | 2010-02-10 |
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