CN108270022A - Proton Exchange Membrane Fuel Cells - Google Patents
Proton Exchange Membrane Fuel Cells Download PDFInfo
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- CN108270022A CN108270022A CN201611240357.2A CN201611240357A CN108270022A CN 108270022 A CN108270022 A CN 108270022A CN 201611240357 A CN201611240357 A CN 201611240357A CN 108270022 A CN108270022 A CN 108270022A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04828—Humidity; Water content
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a proton exchanging film fuel battery, including working electrode, to electrode, proton exchange membrane, humidification unit, constant humidity unit is further included.The humidification unit includes the aqueous sulfuric acid of certain mass concentration.The constant humidity unit is fixed on the fuel battery inside, and including housing, saturated salt solution and waterproof ventilated membrane, the saturated salt solution is placed in the space that housing and waterproof ventilated membrane surround.Reaction gas in fuel cell is no longer simple hydrone by being brought into after humidification unit, but the aqueous solution of sulfuric acid.Due to there is the presence of constant humidity unit, reacting the diluting effect of the water of generation can ignore.The solidification point of aqueous sulfuric acid and saturated salt solution is all below 40 DEG C, even in cold winter, since icing phenomenon will not occur in the solidification point that aqueous sulfuric acid and saturated salt solution is not achieved in temperature, both cold-starting and operation had been solved the problems, such as, original antifreeze anti-icing system is in turn simplified, there is great advantage.
Description
Technical field
The present invention relates to a kind of fuel cells, particularly a kind of to be suitable for the proton exchange membrane run under cryogenic combustion
Expect battery.
Background technology
Proton Exchange Membrane Fuel Cells is one kind of fuel cell, using solid proton exchange membrane 13 serve as electrolyte come
Carry out the transmission of proton, have operating temperature is low, simple and compact for structure, energy density and power density ratio other fuel cells more
The advantages that high, capable of fast starting, easy to maintain；Simultaneously because the event such as electrolyte leakage can be avoided the occurrence of using solid electrolyte
Barrier.
Although Proton Exchange Membrane Fuel Cells has lot of advantages, during it comes into operation and practical application
In the process still there are it is certain the defects of, these defects limit Proton Exchange Membrane Fuel Cells batch use.Wherein most
It is important that cell performance decay under water management and low temperature in battery system：The source of inside battery moisture has at two,
First, the water of reaction generation；It second is that could be into after must combining a certain number of hydrones due to the proton in proton exchange membrane
Row transmits, so its conductivity is related with water content, but moisture is excessively high electrolyte to be caused to flood, and leads to it and is connected
Duct in electrode or gas diffusion layers mass transfer polarization loss is caused by water slug.It is good containing watery in order to be in battery
State, most common method are exactly to carry out humidification process to air or/and hydrogen before reaction gas enters battery, control electric current
Temperature with humidification is aided with air velocity control in certain level, makes water content not only less high but also less low, i.e., in battery
Special water management system is realized to ensure a good water balance relationship, such as Patent No. CN 101699644A in inside
And the Chinese patent of Patent No. 02160497.5.But such method can be such that the structure of Proton Exchange Membrane Fuel Cells becomes more
Add complexity.
Other than carrying out aforementioned levels weighing apparatus management, the application of fuel cell at low temperature is also current research hotspot.
During less than zero degree, the solidification that freezes can occur for the water (coming from water management and reaction product) in system, this is to entire fuel electricity
Pond will generate the influence of non reversibility.Since the freezing process of water can be accompanied by apparent volume change, so phase can be caused
Catalyst layering, diffusion layer breakage and proton exchange membrane breakage etc. may occur after the freezing in the generation for the mechanical stress answered
Irreversibility failure.In order to solve the operation problem under above-mentioned low temperature, now generally using hands such as sweeping method and vacuum drainages
Section (such as Chinese patent, Patent No. US20050181248A1 of Patent No. CN200510136768) is fully dry by battery
Dry or replaced by anti-icing fluid to avoid icing, this needs to stop the humidification to reaction gas before battery is closed.Obvious this method can
Fundamentally to prevent the generation to freeze, and then the physical damage that the solidification of water is avoided to be brought to system, but transported in lower primary cell
Certain moisture must be supplemented before row again, battery is made to reach normal moistening working condition.Either the process of draining is still
Again the process being humidified is required for the consumption regular hour that could complete, this can cause very big shadow to the convenience that battery uses
It rings.
Invention content
The technical problem to be solved in the present invention is to provide a proton exchanging film fuel battery, which has easily water
Management system, and can use at low temperature, the water freezing of inside battery under low temperature can be prevented.
In order to solve the above technical problems, technical solution provided by the invention is：
One proton exchanging film fuel battery including working electrode, to electrode, proton exchange membrane, humidification unit, further includes
Constant humidity unit.
Further, the humidification unit includes the aqueous sulfuric acid of mass concentration 30%-45%.
Further, the humidification unit includes the aqueous sulfuric acid of mass concentration 35%-40%.
Further, the constant humidity unit is fixed on the fuel battery inside, including housing, saturated salt solution and waterproof
Ventilated membrane, the saturated salt solution are placed in the space that housing and waterproof ventilated membrane surround.
Further, the saturated salt solution is K2CO3、Mg(NO3)2Or one kind in NaCl saturated solutions.
Further, the waterproof ventilated membrane is by polytetrafluoroethylene (PTFE), gathered vinyl fluoride, polytetrafluoroethylene (PTFE)/hexafluoro third
Alkene copolymer, the third vinyl ether copolymers of polytetrafluoroethylene (PTFE)/perfluor, polyethylene/TFE copolymer, polyimides, silicon rubber
It is or one or more manufactured in fluorination silicon rubber.
Further, the working electrode and to electrode include catalyst, the catalyst for gold, rhodium, platinum, ruthenium, palladium,
It the mixture of one or more of iridium, silver metal or supports in above-mentioned metal or metal mixture on carrier.
Further, the carrier is the combination of one or more of carbon black, carbon nanotube or activated carbon.
Further, the working electrode and be platinum-ruthenium alloy to the catalyst of electrode, the carrier is received for carbon
The porous support layer that mitron is formed.
Further, the proton exchange membrane is phenolic resin sulfonic acid type film, polystyrene sulfonic acid type film, poly- trichloro-benzenes second
Alkene sulfonic acid type film or perfluorosulfonic acid type film.
Beneficial effects of the present invention：
Reaction gas in fuel cell is no longer simple hydrone by being brought into after humidification unit, but sulfuric acid is water-soluble
Liquid.Due to there is the presence of constant humidity unit, reacting the diluting effect of the water of generation can ignore, specifically, raw in reaction process
Into hydrone can be brought into the aqueous sulfuric acid of humidification unit by reaction gas, when the water dissolution of generation is in aqueous sulfuric acid
In, and when causing the sulfuric acid concentration to change, constant humidity unit can absorb the humidity of the constant aqueous sulfuric acid of moisture from humidification unit.
The solidification point of aqueous sulfuric acid and saturated salt solution is all at -40 DEG C hereinafter, accordingly even when being in cold winter, since temperature reaches
Icing phenomenon will not occur less than the solidification point of aqueous sulfuric acid and saturated salt solution, both solve the numerous developers' of puzzlement
The problem of cold-starting and operation, original antifreeze anti-icing system is in turn simplified, there is great advantage.
Description of the drawings
Fig. 1 is the structure diagram of the Proton Exchange Membrane Fuel Cells in one embodiment of the invention；
Fig. 2 is the structure diagram of the constant humidity unit in one embodiment of the invention；
Fig. 3 is the low-temperature test performance curve of traditional Proton Exchange Membrane Fuel Cells in the embodiment of the present invention 1；
Fig. 4 is the low-temperature test performance curve of the Proton Exchange Membrane Fuel Cells in the embodiment of the present invention 1；
Fig. 5 is the low-temperature test performance curve of traditional Proton Exchange Membrane Fuel Cells in the embodiment of the present invention 2；
Fig. 6 is the low-temperature test performance curve of the Proton Exchange Membrane Fuel Cells in the embodiment of the present invention 2；
Fig. 7 is the low-temperature test performance curve of traditional Proton Exchange Membrane Fuel Cells in the embodiment of the present invention 3；
Fig. 8 is the low-temperature test performance curve of the Proton Exchange Membrane Fuel Cells in the embodiment of the present invention 3；
The structure diagram of Fig. 9 tradition Proton Exchange Membrane Fuel Cells.
Specific embodiment
The present invention is described in detail below in conjunction with attached drawing.
Proton Exchange Membrane Fuel Cells is a kind of fuel cell, is equivalent to " inverse " device of water electrolysis in principle.Fig. 9 is
The structure diagram of traditional Proton Exchange Membrane Fuel Cells, including working electrode, to electrode, proton exchange membrane and humidification unit,
It is pure water in humidification unit, reaction gas hydrogen (H2) and oxygen (O2) before the reaction, humidification unit is first passed through, it is single using humidification
Pure water in member is humidified for reaction gas.
As shown in Figure 1, Proton Exchange Membrane Fuel Cells of the present invention is handed over by working electrode 11, to electrode 12, proton
Film 13, humidification unit 14 and constant humidity unit 15 is changed to form.Working electrode 11 therein is to electrode 12, proton exchange membrane 13
The component used always in conventional fuel cell system is collectively referred to as membrane-electrode unit (MEA).Although humidification unit 14 is proton exchange
The component generally used in membrane cell, but increased in the present invention using aqueous sulfuric acid instead of pure water
It is wet.Constant humidity unit 15 is that water management and the anti-freeze technology of low temperature specially additional component are directed in the present invention.
Working electrode 11 is the place that fuel aoxidizes, and cathode is the place of oxidant reduction, and the two poles of the earth are all containing acceleration
The catalyst of electrode electro Chemical reaction.Working electrode 11 and electrode 12 may be used same catalyst can also use it is not of the same race
Catalyst.In one embodiment of the invention, the catalyst in the two poles of the earth, i.e. active constituent can be golden (Au), rhodium (Rh), platinum
(Pt), it one or more of ruthenium (Ru), palladium (Pd), iridium (Ir), silver-colored (Ag) mixture of metal or supports in carrier
On above-mentioned metal or metal mixture or it is other be capable of catalytic fuel cell reaction catalyst.Carrier therein is leads
Carbon particles can be specifically the combination of one or more of carbon black, carbon nanotube or activated carbon.Preferred tool in the present invention
There is a loaded alloy catalyst of other interference gas such as anti-CO poisoning, one resists the interference gas in environment to fuel cell
The influence of electrical property plays the performance of battery to the greatest extent；Two come the phenomenon that avoiding the occurrence of catalyst poisoning；Three carry to pass through
Body particle aperture in itself and gap caused by being laminated by the loaded catalyst of irregular shape increase the profit of catalyst
With rate and specific surface, increase the current density of fuel cell.
Proton exchange membrane 13 can both serve as electrolyte, the proton of transfer reaction generation, and can serve as isolation barrier, keep away
Exempt from fuel to contact with oxidant.Proton exchange membrane 13 only allows proton to pass through, therefore proton can be straight as the medium for transmitting proton
It connects across proton exchange membrane 13 and directly reaches to electrode 12, and electronics can only get to cathode by external circuit, when electronics leads to
It crosses when external circuit flows to cathode and just produces direct current.Phenolic resin sulfonic acid type film may be used in proton exchange membrane 13 therein,
Polystyrene sulfonic acid type film, poly- trichlorostyrene sulfonic acid type film, perfluorosulfonic acid type film etc..
Working electrode 11 and matter can be firmly fixed to chemical methodes such as deposition, hot pressing, dipping, etchings to electrode 12
MEA is formed on proton exchange 13.
In order to keep proton exchange membrane 13 transmit proton performance, in system set a humidification unit 14, fuel and
Oxidant first reaches humidification unit 14, and pass through from humidification unit 14 before arrival working electrode 11 and to electrode 12, with
Achieve the purpose that fuel and oxidant humidification.For pure water in traditional humidification unit 14, by water come to gas humidification,
It is humidified in the present invention using the sulfuric acid solution with different humidity to reaction gas.The aqueous sulfuric acid of certain concentration has specific
Humidity, correspondence of the table 1 for sulfuric acid solution concentration and relative humidity, its humidity value when in the system for being in a sealing
It will not change, in actual use, the aqueous sulfuric acid of specified moisture be selected to be humidified according to actual needs.
The correspondence of 1 sulfuric acid solution concentration of table and relative humidity
From table 1 it follows that when aqueous sulfuric acid concentration difference, relative humidity becomes in the range of 4%-98%
Change.In this application, the relative humidity of control humidification unit 14 is in the range of 40%-80%, as it can be seen from table 1 controlling
The mass concentration of Sulphuric acid is in the range of 30%-45%.The purpose of humidification, nothing are not achieved when the relative humidity of sulfuric acid is relatively low
Method optimizes the mass-transfer performance of proton exchange membrane 13；Reaction gas can bring a large amount of steam into when humidity is higher, and a large amount of steam coagulates
Knot may block the diffusion admittance of reaction gas, so as to reduce the reactivity worth of battery.It is preferred that relative humidity is in 50%-
In the range of 70%, one side relative humidity performance of proton exchange membrane 13 in the range of this has substantially achieved most preferably；Separately
The range of one side 50%-70% is the universal humidity range of atmospheric environment, selects this humidity section will to the leakproofness of system
Asking can be without so harsh.
A constant humidity unit 15 has also been devised in the fuel cell of the present invention to stablize the humidity of whole system.Due to
Special humidizer is used as using certain density aqueous sulfuric acid in this fuel cell, although the sulfuric acid water when concentration is fixed
The humidity of solution is constant, but this humidity is easy to be influenced by external environment, when the humidity of external environment is more than sulphur
During the humidity of aqueous acid, aqueous sulfuric acid can absorb moisture from environment, so as to by increase the humidity of itself reach with
Extraneous balance；When the humidity of external environment is less than the humidity of aqueous sulfuric acid, the moisture in aqueous sulfuric acid can be from trend
External environment diffusion balances to reach, and in this way when there is exceedingly odious weather condition, the humidity of humidification unit changes greatly,
It cannot keep the performance of entire fuel cell.
To solve the above-mentioned problems, the present invention adds a constant humidity unit 15 in fuel battery inside, molten using saturated salt
The method of liquid constant humidity stablizes the humidity of entire fuel cell.Different saturated salt solutions has different constant humidities, specifically
It is shown in Table 2.In the present invention, as shown in Fig. 2, constant humidity unit 15 includes housing 151, saturated salt solution 152 and waterproof ventilated membrane 153.
Vapor in constant humidity unit 15 can be diffused by waterproof ventilated membrane 153 in entire fuel cell, the water in fuel cell
Steam can also be diffused by waterproof ventilated membrane 153 in constant humidity unit 15, so as to keep the wet of humidification unit and whole system
It spends relative constant.
The constant humidity of saturated salt solution under 2 different temperatures of table
Waterproof ventilated membrane 153 therein can be polytetrafluoroethylene (PTFE) (PTFE) gathered vinyl fluoride (PVDF), polytetrafluoroethylene (PTFE)/
Hexafluoropropylene copolymer (PFEP), the third vinyl ether copolymers of polytetrafluoroethylene (PTFE)/perfluor (PFA), polyethylene/TFE copolymer
(PETFE), one or more combinations in polyimides (PI), silicon rubber (SR) or fluorination silicon rubber (FSR), preferably with
The mode of laminated combinations.
The humidity that keep constant humidity unit 15 as possible in use is consistent with the humidity of humidification unit 14, if the two
Humidity difference it is bigger, moisture can be shifted between, if the humidity of constant humidity unit 15 be more than humidification unit 14,
Then hydrone can be spread from constant humidity unit 15 to humidification unit 14；If the humidity of humidification unit 14 is more than constant humidity unit 15,
Hydrone can be spread from humidification unit 14 to constant humidity unit 15.
Entire fuel cell can be isolated from the outside by way of sealing, can also pass through waterproof ventilated membrane or waterproof
Diaphragm seal is communicated with external environment, and inside can not only be isolated in this way and exchanged with the humidity of external environment but also facilitate the entire fuel of observation
The situation of inside battery.
Reaction gas in fuel cell is no longer simple hydrone by being brought into after humidification unit 14, but the water of sulfuric acid
Solution.Due to there is the presence of constant humidity unit 15, reacting the diluting effect of the water of generation can ignore, specifically, reaction process
The hydrone of middle generation can be brought by reaction gas in aqueous sulfuric acid, when generation water dissolution humidification unit 14 sulfuric acid water
In solution, and when causing the sulfuric acid concentration to change, it is water-soluble that constant humidity unit 15 can absorb the constant sulfuric acid of moisture from humidification unit 14
The humidity of liquid.The solidification point of aqueous sulfuric acid and saturated salt solution all at -40 DEG C hereinafter, accordingly even when be in cold winter,
Since icing phenomenon will not occur in the solidification point that aqueous sulfuric acid and saturated salt solution is not achieved in temperature, it is many both to have solved puzzlement
The problem of cold-starting of more developers and operation, in turn simplifies original antifreeze anti-icing system, has great advantage.
In conclusion it is of the invention by increasing constant humidity unit 15 in traditional Proton Exchange Membrane Fuel Cells, and use sulfuric acid
Aqueous solution instead of pure water be humidified, not only maintained the excellent performance of Proton Exchange Membrane Fuel Cells, but solve low temperature freeze and
The problem of cold-starting and operation.
Embodiment 1
In the present embodiment, working electrode 11 and to electrode 12 include catalyst and carrier, wherein catalyst is Pt-Ru
Alloy-layer, carrier are the porous support layer formed by carbon nanotube.Catalyst layer Pt-Ru alloy-layers therein uniformly support in
On porous support layer.Proton exchange membrane 13 is using phenolic resin sulfonic acid type film, working electrode 11 and to electrode 12 with the side of dipping
Method is securely fixed in proton exchange membrane 13, and infusion process is to prepare the common method of Pt based alloy catalysts.
When battery works, fuel and oxidant are carried on a shoulder pole respectively in working electrode 11 and to being chemically reacted on electrode 12
Supported catalyst significantly increases the stabilization of the specific surface area of catalyst, more conducively airwater mist cooling interface, so that
Catalyst has preferable reactivity.The proton of reaction generation is reached by proton exchange membrane 13 to electrode 12 and oxonium ion knot
Symphysis Cheng Shui reacts the electronics of generation then by external circuit by moving to working electrode 11 to electrode 12, so as to form reaction
Closed-loop type.
In the present embodiment, the sulfuric acid solution mass concentration in humidification unit 14 is 35%., relative humidity is in 60%-
In the range of 70%.
In the present embodiment, saturated salt solution 152 is the saturated solution of NaCl, and as shown in Table 2, constant humidity is single with humidification
The relative humidity difference of member 14 is little.Waterproof ventilated membrane 153 is made of polytetrafluoroethylene (PTFE) (PTFE), and polytetrafluoroethylene (PTFE) (PTFE) is
Latest generation waterproof ventilative material has excellent chemical stability and corrosion resistance.
Low-temperature test is carried out to the Proton Exchange Membrane Fuel Cells in the present embodiment.Traditional fuel is first tested respectively before experiment
The two is placed in -20 DEG C by the fuel cell in battery and the present invention simultaneously to the output performance of 20% hydrogen after test completion
Environment in 8 hours, then warm naturally to room temperature (25 DEG C) and maintain 8 hours, in this way for one cycle, repeat this recycle 9
After secondary, both tests again are specifically shown in Fig. 3 and 4 to the output performance of 20% hydrogen.It is followed as can be seen from Figure by high/low temperature
The output signal of conventional fuel cell reduces 30% after ring test, and the fuel battery performance in the present invention maintains not substantially
Become.
Embodiment 2
In the present embodiment, working electrode 11 and to electrode 12 include catalyst and carrier, the catalyst of working electrode 11
For Pt, the catalyst to electrode 12 is also Pt, and carrier is the porous support layer that activated carbon is formed, and active carbon material has preferable steady
Qualitative and electric conductivity, and the more mature stabilization of production technology, are one of most common fuel-cell catalyst carriers.Proton exchange
Film 13 uses perfluorosulfonic acid type film, working electrode 11 and is securely fixed in proton exchange membrane 13 to electrode 12 in the method for etching
On.
In the present embodiment, the sulfuric acid solution mass concentration in humidification unit 14 is 45%., relative humidity is in 40%-
In the range of 50%.
In the present embodiment, saturated salt solution 152 is K2CO3·2H2The saturated solution of O, as shown in Table 2, constant humidity with
The relative humidity difference of humidification unit 14 is little.Waterproof ventilated membrane 153 is made of polyethylene/TFE copolymer (PETFE),
Have the characteristics that insulate and heat safe.
Low-temperature test similarly to Example 1 is carried out to the Proton Exchange Membrane Fuel Cells in the present embodiment.It is specifically shown in Fig. 5
With 6, the output signal of conventional fuel cell reduces 35% after high/low temperature cyclic test as can be seen from Figure, and this hair
Fuel battery performance in bright remains unchanged substantially.
Embodiment 3
In the present embodiment, working electrode 11 and include catalyst to electrode 12, wherein catalyst is that porous Pd is closed
Gold.Proton exchange membrane 13 uses poly- trichlorostyrene sulfonic acid type film, working electrode 11 and secured in the method for deposition to electrode 12
Ground is fixed in proton exchange membrane 13.
In the present embodiment, the sulfuric acid solution mass concentration in humidification unit 14 is 40%., relative humidity is in 50%-
In the range of 60%.
In the present embodiment, saturated salt solution 152 is Mg (NO3)2·6H2The saturated solution of O is as shown in Table 2, constant wet
Degree is little with the relative humidity difference of humidification unit 14.Waterproof ventilated membrane 153 was by gathering vinyl fluoride (PVDF) and silicon rubber (SR)
It is made of the mode of hot pressing.
Low-temperature test similarly to Example 1 is carried out to the Proton Exchange Membrane Fuel Cells in the present embodiment.It is specifically shown in Fig. 7
With 8, the output signal of conventional fuel cell reduces 25% after high/low temperature cyclic test as can be seen from Figure, and this hair
Fuel battery performance in bright remains unchanged substantially.
Embodiment 4
In the present embodiment, working electrode 11 and to electrode 12 include catalyst and carrier, wherein catalyst is Pt-Au
Alloy-layer, carrier are the porous support layer formed by carbon black.Proton exchange membrane 13 uses polystyrene sulfonic acid type film, working electrode
11 and electrode 12 is securely fixed in the method for hot pressing in proton exchange membrane 13.
When battery works, fuel and oxidant are respectively in working electrode 11 and to being chemically reacted on electrode 12, instead
The proton that should be generated is reached by proton exchange membrane 13 and is combined with oxonium ion generation water to electrode 12, and the electronics for reacting generation then leads to
External circuit is crossed by moving to working electrode 11 to electrode 12, so as to form the closed-loop type of reaction.
In the present embodiment, the sulfuric acid solution mass concentration in humidification unit 14 is 30%., relative humidity is in 70%-
In the range of 80%.
In the present embodiment, saturated salt solution 152 is the saturated solution of NaCl, and as shown in Table 2, constant humidity is single with humidification
The relative humidity difference of member 14 is little.Waterproof ventilated membrane 153 is made of the third vinyl ether copolymers of polytetrafluoroethylene (PTFE)/perfluor (PFA).
Embodiment 5
In the present embodiment, working electrode 11 and to electrode 12 include catalyst and carrier, wherein catalyst is Rh, carry
Body is the porous support layer formed by carbon black and activated carbon.Proton exchange membrane 13 uses polystyrene sulfonic acid type film, working electrode
11 and electrode 12 is securely fixed in the method for deposition in proton exchange membrane 13.
When battery works, fuel and oxidant are respectively in working electrode 11 and to being chemically reacted on electrode 12, instead
The proton that should be generated is reached by proton exchange membrane 13 and is combined with oxonium ion generation water to electrode 12, and the electronics for reacting generation then leads to
External circuit is crossed by moving to working electrode 11 to electrode 12, so as to form the closed-loop type of reaction.
In the present embodiment, the sulfuric acid solution mass concentration in humidification unit 14 is 35%., relative humidity is in 60%-
In the range of 70%.
In the present embodiment, saturated salt solution 152 is Mg (NO3)2·6H2The saturated solution of O is as shown in Table 2, constant wet
Degree is little with the relative humidity difference of humidification unit 14.Waterproof ventilated membrane 153 is by polytetrafluoroethylene (PTFE)/hexafluoropropylene copolymer
(PFEP) it is made.
Embodiment 6
In the present embodiment, working electrode 11 and to electrode 12 include catalyst and carrier, wherein catalyst is Ir, carry
Body is the porous support layer formed by carbon black.Proton exchange membrane 13 is using polystyrene sulfonic acid type film, working electrode 11 and to electricity
Pole 12 is securely fixed in the method for deposition in proton exchange membrane 13.
When battery works, fuel and oxidant are respectively in working electrode 11 and to being chemically reacted on electrode 12, instead
The proton that should be generated is reached by proton exchange membrane 13 and is combined with oxonium ion generation water to electrode 12, and the electronics for reacting generation then leads to
External circuit is crossed by moving to working electrode 11 to electrode 12, so as to form the closed-loop type of reaction.
In the present embodiment, the sulfuric acid solution mass concentration in humidification unit 14 is 40%., relative humidity is in 50%-
In the range of 60%.
In the present embodiment, saturated salt solution 152 is Mg (NO3)2·6H2The saturated solution of O is as shown in Table 2, constant wet
Degree is little with the relative humidity difference of humidification unit 14.Waterproof ventilated membrane 153 is by the third vinyl ether copolymers of polytetrafluoroethylene (PTFE)/perfluor
(PFA) layer and polyimides (PI) layer are made up of hot pressing mode.
More than content is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, in specific embodiments and applications can be with many changes may be made, as long as these variations are without departing from the structure of the present invention
Think, all belong to the scope of protection of the present invention.
Claims (10)
- A 1. proton exchanging film fuel battery, including working electrode (11), to electrode (12), proton exchange membrane (13) and humidification Unit (14), it is characterised in that：Further include constant humidity unit (15).
- A 2. proton exchanging film fuel battery according to claim 1, it is characterised in that：In the humidification unit (14) Include the aqueous sulfuric acid of mass concentration 30%-45%.
- A 3. proton exchanging film fuel battery according to claim 2, it is characterised in that：In the humidification unit (14) Include the aqueous sulfuric acid of mass concentration 35%-40%.
- A 4. proton exchanging film fuel battery according to claim 1, it is characterised in that：The constant humidity unit (15) is solid Due to the fuel battery inside, including housing (151), saturated salt solution (152) and waterproof ventilated membrane (153), the saturation Salting liquid (152) is placed in the space that housing (151) and waterproof ventilated membrane (153) surround.
- A 5. proton exchanging film fuel battery according to claim 4, it is characterised in that：The saturated salt solution (152) it is K2CO3、Mg(NO3)2Or one kind in NaCl saturated solutions.
- A 6. proton exchanging film fuel battery according to claim 4, it is characterised in that：The waterproof ventilated membrane (153) it is by polytetrafluoroethylene (PTFE), gathered vinyl fluoride, polytetrafluoroethylene (PTFE)/hexafluoropropylene copolymer, the third second of polytetrafluoroethylene (PTFE)/perfluor One or more systems in alkene ether copolymer, polyethylene/TFE copolymer, polyimides, silicon rubber or fluorination silicon rubber Into.
- A 7. proton exchanging film fuel battery according to claim 1, it is characterised in that：The working electrode (11) and Include catalyst to electrode (12), the catalyst is the mixed of one or more of gold, rhodium, platinum, ruthenium, palladium, iridium, silver metal It closes object or supports in above-mentioned metal or metal mixture on carrier.
- A 8. proton exchanging film fuel battery according to claim 7, it is characterised in that：The carrier is carbon black, carbon The combination of one or more of nanotube or activated carbon.
- A 9. proton exchanging film fuel battery according to claim 8, it is characterised in that：The working electrode (11) and Catalyst to electrode (12) is platinum-ruthenium alloy, and the carrier is the porous support layer that carbon nanotube is formed.
- A 10. proton exchanging film fuel battery according to claim 1, it is characterised in that：The proton exchange membrane (13) it is phenolic resin sulfonic acid type film, polystyrene sulfonic acid type film, poly- trichlorostyrene sulfonic acid type film or perfluorosulfonic acid type film.
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| CN201611240357.2A CN108270022A (en) | 2016-12-28 | 2016-12-28 | Proton Exchange Membrane Fuel Cells |
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|---|---|---|---|
| CN201611240357.2A CN108270022A (en) | 2016-12-28 | 2016-12-28 | Proton Exchange Membrane Fuel Cells |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651919A (en) * | 2021-08-30 | 2021-11-16 | 上海应用技术大学 | Cold-resistant solar-driven photothermal effect hydrogel electrolyte and preparation and application thereof |
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2016
- 2016-12-28 CN CN201611240357.2A patent/CN108270022A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651919A (en) * | 2021-08-30 | 2021-11-16 | 上海应用技术大学 | Cold-resistant solar-driven photothermal effect hydrogel electrolyte and preparation and application thereof |
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