CN102324533A - Self-breathing direct methanol fuel cell monomer based on porous metal fiberboard - Google Patents
Self-breathing direct methanol fuel cell monomer based on porous metal fiberboard Download PDFInfo
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- CN102324533A CN102324533A CN201110213513A CN201110213513A CN102324533A CN 102324533 A CN102324533 A CN 102324533A CN 201110213513 A CN201110213513 A CN 201110213513A CN 201110213513 A CN201110213513 A CN 201110213513A CN 102324533 A CN102324533 A CN 102324533A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a self-breathing direct methanol fuel cell monomer based on a porous metal fiberboard. The cell monomer comprises an anode fuel chamber, a cell working unit and a cathode open type end plate, wherein the cell working unit comprises an anode collector plate, a membrane electrode and a cathode collector plate; two sides of the membrane electrode are respectively provided with the anode collector plate and the cathode collector plate; the anode fuel chamber and the cathode open type end plate used as a cell shell are respectively arranged at the outer sides of the anode collector plate and the cathode collector plate; the middle part of the anode collector plate is provided with a porous metal fiberboard, the porous metal fiberboard is formed by sintering copper metal fibers with diameter of 20-200 mu m, the porosity is 70%-90%, the permeability is 10<-12>-10<-9>m<2>, and the average pore size is 50 mu m to 500 mu m. According to the invention, because of the adoption of the porous metal fiberboard, the methanol penetration problem can be effectively solved and effective water management is realized, thus the fuel availability of the passive self-breathing direct methanol fuel cell can be improved and the output performance of the cell can be improved.
Description
Technical field
The present invention relates to the fuel cell technology field, specifically is a kind of passive self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate.
Background technology
DMFC (DMFC) be a kind of be the electrochemical appliance that fuel is converted into chemical energy electric energy with methyl alcohol.But therefore characteristics such as that it has is simple in structure, fuel storage safety, the high low-temperature operation of theoretical specific energy have broad application prospects in the portable type electronic product field.Wherein passive self-breathing direct methanol fuel cell can be realized complete autonomous operation; Its anode directly links to each other with fuel storage chamber (hereinafter to be referred as fuel cavity); Negative electrode is directly exposed in the natural air, and fuel (methyl alcohol) and oxidant (oxygen) arrive Catalytic Layer through diffusion transmission forms such as concentration difference diffusion and convection current and carry out electrochemical reaction.Because it does not need auxiliary conveying equipments such as pump, air compressor, air blast, in simplified system, also reduced the additive decrementation of battery output energy.
At present, mainly there are low and low two key issues of power of battery density of methanol fuel utilance in passive self-breathing direct methanol fuel cell.Its main cause is the commercialization dielectric film that generally adopts at present, like the Nafion film etc., fails effectively to stop methanol crossover, and the methyl alcohol of anode end reaction can be penetrated into negative electrode, thereby causes waste of fuel.In addition, methyl alcohol constantly in the accumulation, also can produce mixed potential with oxygen reaction at negative electrode, causes serious polarization, makes the entire cell decreased performance.Owing to the battery performance decline that methanol crossover causes, be to hinder DMFC to realize business-like one of the main reasons.
The electrode and the cell reaction of DMFC are following:
Anode reaction is CH
3OH+H
2O → 6H
++ 6e
-+ CO
2
Cathode reaction is 3/2O
2+ 6H
++ 6e
-→ 3H
2O
The battery overall reaction is CH
3OH+3/2O
2→ 2H
2O+CO
2
Can find out from the reaction of the operation principle of above-mentioned battery and want consume water in anode methyl alcohol generation oxidation reaction, and can produce water, and overall reaction can be given birth to some water by fecund at cathode side when battery operated at the oxygen reduction reaction of negative electrode.For realizing good water management effect, when adopting carbon fiber diffusion media traditionally, need that it is carried out hydrophobic and handle.Traditional handicraft is to adopt hydrophober (like polytetrafluoroethylene PTFE) that carbon paper or carbon cloth are carried out preliminary treatment.This technology is complicacy comparatively, and the content of hydrophober need strictly be controlled, and owing to the existence of hydrophober, possibly cause the obstruction of through hole, and reduce the conductivity of dispersive medium simultaneously.Therefore it is also very helpful to the lifting of fuel battery performance to seek the good dispersive medium of hydrophobic property.
Summary of the invention
For solving the too high problem that causes waste of fuel and battery performance to descend of methanol permeability in the present DMFC; The invention provides a kind of features good methanol diffusion resistance, can effectively improve the passive self-breathing direct methanol fuel cell based on the porous metal fiber plate of energy content of battery density.Simultaneously, the porous metal fiber plate of the present invention's preparation has tangible hydrophobic property, need not any hydrophobic and handles, and have good electrical conductivity, can realize the effective water management and the electric collecting of fuel cell.
The object of the invention is realized through following technical scheme:
A kind of self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate comprises anode fuel chamber, battery operated unit and the open end plate of negative electrode; Battery operated unit comprises anode collector plate, membrane electrode and cathode collector plate; The both sides of membrane electrode are respectively equipped with anode collector plate and cathode collector plate; The open end plate of anode fuel chamber and negative electrode lays respectively at the outside of anode collector plate and cathode collector plate as battery container; Between membrane electrode and anode collector plate and cathode collector plate, between anode collector plate and the anode fuel chamber, and be respectively equipped with seal washer between cathode collector plate and the open end plate of negative electrode; Be provided with the porous metal fiber plate at anode collector plate middle part, said porous metal fiber plate is metallic fiber sintered the forming of copper of 20 μ m-200 μ m by diameter, and porosity is 70%-90%, and permeability is 10
-12m
2-10
-9m
2, average pore size is 50 μ m-500 μ m, thickness 0.5-5mm.
For realizing that further the object of the invention, said porous metal fiber plate are embedded in the groove of left side, anode collector plate middle part or right side cavity.
Said porous metal fiber plate is embedded in the groove that anode fuel chamber open side sets up.
The preparation method of said porous metal fiber plate is: through cutting method the copper raw material metal is processed the continuous type filament that diameter is 20 μ m-200 μ m; Again the metallic fiber of processing is cut into the long segment of fiber of 10mm-20mm; Then; Loose fibres section shop is placed the mould for preparing the porous metal fiber plate, and the cavity structure of mould is identical with porous metal fiber plate shape; Adopt carvel built successively to guarantee that the space of fiber and structure thereof is evenly distributed, mould just can place after assembling in the nitrogen atmosphere protection sintering furnace and carry out sintering, and sintering temperature is that 800 ℃-950 ℃, sintering time are 30min-90min.
The open end plate of said anode fuel chamber and negative electrode is that the polymethyl methacrylate of anti-liquid fuel carbinol corrosion is processed.
Said anode collector plate and cathode collector plate are by graphite cake or have corrosion resistance and the metal material of conductivity is processed; Porose array of processing or grid array passage on anode collector plate and the cathode collector plate, the opening area shape is identical with the shape and the effective area of membrane electrode with effective area.
The diffusion layer of said membrane electrode adopts carbon paper or carbon cloth as supporting layer, and anode-side is through hydrophilic treatment, and cathode side is through hydrophobic treatment.
The present invention also can be battery pack: its form can be symmetrical expression peace face-type structural.Symmetrical structure is made up of two monocells, two monocell common anode fuel cavity, and the negative electrode of two monocells places the battery pack both sides.The plane formula structure is made up of two or more a plurality of monocells, and the electrode of each monocell is arranged on same PEM, and conversion zone does not contact mutually, through lead successively with the both positive and negative polarity of each monocell composition battery pack that is together in series.
Anode fuel chamber groove and anode collector plate or porous metal fiber plate form the fuel storage space, are used for the storaging liquid fuel methanol; It is charging aperture that top is provided with through hole, is used for injecting methanol solution to groove, is used for the discharging of the carbon dioxide of anode reaction generation simultaneously; The cross sectional shape of groove is identical with the shape and the effective area of membrane electrode with effective area.
Collector plate comprises anode collector plate and cathode collector plate, plays effects such as electric current is collected, fuel evenly distributes, fuel sees through, support structure, and material need have strong corrosion resistant property and high conductivity.Porose array of processing or grid array passage on it, the opening area shape is identical with the shape and the effective area of membrane electrode with effective area; Collector plate thickness of the present invention is 0.5mm-5mm; Anode collector plate or be processed with groove in order to embed the porous metal fiber plate, the cross sectional shape of groove is identical with the shape and the effective area of membrane electrode with effective area; The one side that is embedded with the porous metal fiber plate can face the anode fuel chamber and install, and also can face membrane electrode and install.Membrane electrode is made up of anode diffusion layer, anode catalyst layer, PEM, cathode catalysis layer and cathode diffusion layer, can be hot pressing type or non-hot pressing type assembly.The open end plate of negative electrode is a frame structure, and the centre has through hole, and the through hole cross sectional shape is identical with the shape and the effective area of membrane electrode with effective area, is used for obtaining airborne oxygen from the battery external world and gets into the cathode reaction zone.
Porous metal fiber plate of the present invention is formed by metallic fiber sintered, parameter Be Controlled and adjustings effectively such as its thickness, porosity, aperture, permeability; The penetration speed of the structural parameters may command methyl alcohol through regulating this porous metal fiber plate is realized the controllability that battery fuel is carried, and has both guaranteed effective conveying of methanol fuel, again resistance to mass tranfer can be provided, and improves the alcohol-rejecting ability of fuel cell; The cross sectional shape of this porous metal fiber plate is identical with the shape and the effective area of collector plate opening area, membrane electrode with effective area; This porous metal fiber plate can be embedded in the anode current collection board slot, maybe can be embedded in the groove that anode fuel chamber open side sets up.
With respect to prior art, the present invention has following advantage:
(1) the present invention has adopted the porous metal fiber plate; Alleviated the penetration problem of methyl alcohol effectively; The alcohol-rejecting ability and the fuel availability of passive self-breathing direct methanol fuel cell have been improved; Make DMFC under the high methanol concentration condition, to move, when reducing waste of fuel, also improved the output performance of battery.
(2) the surface contact angle scope of its test of porous metal fiber plate of the present invention's preparation has tangible hydrophobic property between 110 °-140 °, and manufacture craft is simple, need not any hydrophobic and handles, and has good electrical conductivity simultaneously again.Adopted this porous metal fiber plate, fuel cell can be realized effective water management and electric collecting.
(3) because parameter Be Controlled and adjustings effectively such as the area of section of this porous metal fiber plate, thickness, porosity, aperture, permeability can this be controlled the penetration speed of methyl alcohol, realize the high controllability that battery fuel is carried.
(4) but the present invention's fuel cell different power requires and operating condition is selected the porous metal fiber plate of different parameters.
(5) the present invention is simple in structure, and is easy to assembly, and production cost is low, particularly has good alcohol-rejecting ability, is fit to high concentration methanol and supplies with, and can effectively improve energy content of battery density, lengthens working hours, and has a good application prospect.
Description of drawings
Fig. 1 is a fuel cell assembling sketch map of the present invention;
Fig. 2 is the SEM figure of porous metal fiber plate of the present invention;
Fig. 3 is the porous metal fiber installation site sketch map of case 1;
Fig. 4 is the hole anode-array collector plate structural representation of case 1;
Fig. 5 is the grid array anode collector plate structural representation of case 1;
Fig. 6 is the fuel cell structure sketch map of case 2;
Fig. 7 is the anode fuel cavity configuration sketch map of case 2;
Fig. 8 is the working curve comparison diagram of case 1.
Embodiment
For further understanding the present invention, below in conjunction with accompanying drawing and embodiment the present invention is further specified, but need to prove, the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Like Fig. 1,3-1,3-2, shown in 6,, comprise the open end plate 10 of anode fuel chamber 1, battery operated unit and negative electrode based on the self-breathing direct methanol fuel cell monomer of porous metal fiber plate; Battery operated unit comprises anode collector plate 6, membrane electrode 8 and cathode collector plate 9; The both sides of membrane electrode 8 are respectively equipped with anode collector plate 6 and cathode collector plate 9; Anode fuel chamber 1 and the open end plate 10 of negative electrode lay respectively at the outside of anode collector plate 6 and cathode collector plate 9 as battery container; Between membrane electrode 8 and anode collector plate 6 and cathode collector plate 9, between anode collector plate 6 and the anode fuel chamber 1, and be respectively equipped with seal washer 4 between cathode collector plate 9 and the open end plate 10 of negative electrode; Be provided with porous metal fiber plate 5 at anode collector plate 6 middle parts, porous metal fiber plate 5 can be embedded in the groove interior (Fig. 3-1,3-2) of left side, anode collector plate 6 middle parts or right side cavity, maybe can be embedded in the groove interior (Fig. 6) that anode fuel chamber open side is set up; Porous metal fiber plate 5 is metallic fiber sintered the forming of copper of 20-200 μ m by diameter, and porosity is 70%-90%, and permeability is 10
-12-10
-9m
2, average pore size is 50 μ m-500 μ m, thickness 0.5-5mm; Porous metal fiber plate 5 is used to control the transfer rate of methyl alcohol; The open end plate of anode fuel chamber 1 and negative electrode 10 is as battery container, and material is the polymethyl methacrylate of anti-liquid fuel carbinol corrosion.
Being provided with groove 2 in the anode fuel chamber 1 with through hole 3 does, groove 2 forms the fuel storage space with anode collector plate 6, is used for the storaging liquid fuel methanol; Through hole 3 is a charging aperture, is used for injecting methanol solution to groove 2, is used for the discharging of the carbon dioxide of anode reaction generation simultaneously; Anode collector plate 6 is preferably graphite cake with cathode collector plate 9; Also can be metal material with strong corrosion resistant property and high conductivity; Porose array of processing or grid array passage on it, the opening area shape is identical with the shape and the effective area of membrane electrode 8 with effective area; The diffusion layer of membrane electrode 8 adopts carbon paper or carbon cloth as supporting layer, and anode-side is through hydrophilic treatment, and cathode side is through hydrophobic treatment.Anode-side adopts platinum ruthenium binary catalyst, and carrying capacity is 4mg/cm
2, cathode side adopts platinum catalyst, and carrying capacity is 2mg/cm
2
Parameter Be Controlled and adjustings effectively such as the thickness of porous metal fiber plate, porosity, aperture, permeability; The penetration speed of the structural parameters may command methyl alcohol through regulating this porous metal fiber plate; Realize the controllability that battery fuel is carried; Both guaranteed effective conveying of methanol fuel; Again resistance to mass tranfer can be provided, improve the alcohol-rejecting ability of fuel cell, can the fuel cell different power require and operating condition is selected the porous metal fiber plate of different parameters; The cross sectional shape of this porous metal fiber plate is identical with the shape and the effective area of collector plate opening area, membrane electrode with effective area.
The preparation method of porous metal fiber plate is following: through cutting method the copper raw material metal is processed the continuous type filament that diameter is 20 μ m-200 μ m, again the metallic fiber of processing is cut into the long segment of fiber of 10mm-20mm.Then, loose fibres section shop is placed the mould for preparing the porous metal fiber plate, the cavity structure of mould is identical with porous metal fiber plate shape; Adopting successively, carvel built guarantees that the space of fiber and structure thereof is evenly distributed.Mould just can place in the nitrogen atmosphere protection sintering furnace after assembling and carry out sintering, and sintering temperature is that 800 ℃-950 ℃, sintering time are 30min-90min.Making porosity after sintering is accomplished is that 70%-80%, average pore size are 50 μ m-500 μ m, and permeability is 10
-12m
2-10
-9m
2, thickness is the porous metal fiber plate of 0.5mm-5mm.
Use this porous metal fiber plate 5 and can realize good water management effect, when adopting carbon fiber diffusion media traditionally, need that it is carried out hydrophobic and handle.Traditional handicraft is to adopt hydrophober (like the PTFE emulsion) that carbon paper or carbon cloth are carried out preliminary treatment.This technology is complicacy comparatively, and the content of hydrophober need strictly be controlled, and owing to the existence of hydrophober, possibly cause the obstruction of through hole, and reduce the conductivity of dispersive medium simultaneously.The fiber board that the present invention processes itself has tangible hydrophobic property, need not any hydrophobic and handles, and the surface contact angle scope of test is between 110 °-140 °, and this porous metal fiber plate 5 also has high conductivity simultaneously.
A plurality of monocells are assembled into battery pack, and its form can be symmetrical expression peace face-type structural.Symmetrical structure is made up of two monocells, and the negative electrode of 1, two monocell of two monocell common anode fuel cavity places the both sides of battery pack.The plane formula structure is made up of two or more a plurality of monocells, and the electrode of each monocell is arranged on same PEM, and conversion zone does not contact mutually, through lead successively with the both positive and negative polarity of each monocell composition battery pack that is together in series.
Through cutting method the copper raw material metal is processed the continuous type fiber that diameter is 100 μ m, again the metallic fiber of processing is cut into the long segment of fiber of 10mm-20mm.Then, 36.7g loose fibres section shop is placed the mould of preparation porous metal fiber plate; Adopting successively, carvel built guarantees that as far as possible the space of fiber and structure thereof is evenly distributed.Mould is placed on nitrogen atmosphere through assembling and protects in the sintering furnace 900 ℃ of sintering 30min.Just can prepare porous metal fiber plate behind the sintering with 80% porosity.The average pore size that is recorded the porous metal fiber plate by bubble method is 120 μ m, and permeability is 2 * 10
-10m
2
As shown in Figure 2, amplify 50 times SEM figure for porous metal fiber plate with 80% porosity 5.Porous metal fiber plate 5 is formed by metallic fiber sintered, and each segment of fiber that constitutes fiber board is the random distribution state, interlaced stack, between the segment of fiber through the sintering neck be linked together, form three-dimensional netted loose structure.
Generally speaking; The installation site of fiber board in fuel cell depended in the selection of fiber board 28mm * 28mm and two kinds of sizes of 32mm * 32mm; If the membrane electrode effective area is 3mm * 3mm, then, fuel cavity adopts the size of 28mm * 28mm when installing, the size of employing 32mm * 32mm when membrane electrode is installed.
Through cutting method the copper raw material metal is processed the continuous type fiber that diameter is 20 μ m, again the metallic fiber of processing is cut into the long segment of fiber of 10mm-20mm.Then, loose fibres section shop is placed the mould of preparation porous metal fiber plate; Adopting successively, carvel built guarantees that as far as possible the space of fiber and structure thereof is evenly distributed.Mould is placed on nitrogen atmosphere through assembling and protects in the sintering furnace 800 ℃ of sintering 60min.Just can prepare porous metal fiber plate behind the sintering with 70% porosity.The average pore size that is recorded the porous metal fiber plate by bubble method is 37 μ m, and permeability is 1.2 * 10
-11m
2
Through cutting method the copper raw material metal is processed the continuous type fiber that diameter is 200 μ m, again the metallic fiber of processing is cut into the long segment of fiber of 10mm-20mm.Then, loose fibres section shop is placed the mould of preparation porous metal fiber plate; Adopting successively, carvel built guarantees that as far as possible the space of fiber and structure thereof is evenly distributed.Mould is placed on nitrogen atmosphere through assembling and protects in the sintering furnace 900 ℃ of sintering 30min.Just can prepare porous metal fiber plate behind the sintering with 80% porosity.The average pore size that is recorded the porous metal fiber plate by bubble method is 580 μ m, and permeability is 3.4 * 10
-9m
2
As shown in Figure 1, a kind of monocell of the passive self-breathing direct methanol fuel cell based on the porous metal fiber plate mainly is made up of the open end plate 10 usefulness fastening bolt method series seals of anode fuel chamber 1, battery operated unit and negative electrode.Battery operated unit comprises anode collector plate 6, membrane electrode 8 and cathode collector plate 9; The porous metal fiber plate 5 that in the anode collector plate 6 of battery operated unit, embeds embodiment 1 preparation is controlled the transfer rate of methyl alcohol; The open end plate of anode fuel chamber 1 and negative electrode 10 is as battery container, and material is the polymethyl methacrylate of anti-liquid fuel carbinol corrosion.
Anode fuel chamber further groove 2 forms the fuel storage space with anode collector plate 6, is used for the storaging liquid fuel methanol; Through hole 3 is a charging aperture, is used for injecting methanol solution to groove 2, is used for the discharging of the carbon dioxide of anode reaction generation simultaneously; The cross sectional shape of groove 2 is identical with the shape and the effective area of membrane electrode 8 with effective area; On the anode collector plate 6 of battery operated unit, be processed with groove 7, its porous metal fiber plate 5 that is embedded in the embodiment preparation is controlled the transfer rate of methyl alcohol; Collector plate comprises anode collector plate 6 and cathode collector plate 9; Be graphite cake, also can be metal material with strong corrosion resistant property and high conductivity; Porose array of processing or grid array passage on it, the opening area shape is identical with the shape and the effective area of membrane electrode 8 with effective area; The diffusion layer of membrane electrode 8 adopts carbon paper or carbon cloth as supporting layer, and anode-side is through hydrophilic treatment, and cathode side is through hydrophobic treatment.Anode-side adopts platinum ruthenium binary catalyst, and carrying capacity is 4mg/cm
2, cathode side adopts platinum catalyst, and carrying capacity is 2mg/cm
2PEM is the Nafion film of E.I.Du Pont Company.Membrane electrode 8 can be hot pressing type or non-hot pressing type assembly; The open end plate 10 of negative electrode is a frame structure, and the centre has through hole 11, and its cross sectional shape is identical with the shape and the effective area of membrane electrode 8 with effective area, is used for obtaining airborne oxygen from the battery external world and gets into the cathode reaction zone; Between the anode-side of anode collector plate 6 and membrane electrode 8, accompany seal washer 4 between the cathode side of cathode collector plate 9 and membrane electrode 8, material is a polytetrafluoroethylene, in order to the sealing methanol liquid, prevents fuel leak; Between anode fuel chamber 1 and the anode collector plate 6, also accompany seal washer 4 between the open end plate 10 of cathode collector plate 9 and negative electrode, material is the silica gel circle, is used to seal methanol fuel, also plays the effect of buffering assembly force simultaneously.
The installation site of the porous metal fiber plate 5 of present embodiment 1 preparation can be in the groove 7 of anode collector plate 6 near anode fuel chamber 1 one sides, shown in Fig. 3-1; Also can be in the groove 7 of anode collector plate 6 near membrane electrode 8 one sides, shown in Fig. 3-2.Present embodiment 1 described anode collector plate 6 is processed with groove 7, is used to embed porous metal fiber plate 5; These groove 7 internal cavity areas are identical with the actual cross-section area of the porous metal fiber plate 5 of embedding, process the area of the opening area of porose array or grid array passage greatly on it, so that all fuel pass through opening area through this porous zone earlier again; Because fluting needs, anode collector plate 6 need have suitable thickness, is generally 2mm-5mm.
Like Fig. 3-1,3-2,4, shown in 5, described anode collector plate 6 is graphite cake, gold-plated corrosion resistant plate or gold,platinized titanium plate with cathode collector plate 9 materials, and its thickness is 0.5mm-5mm; This collector plate has strong corrosion resistant property and high conductivity, plays effects such as electric current is collected, fuel evenly distributes, fuel sees through, support structure; Anode collector plate 6 is provided with the groove 7 in order to inlay porous metal fiber plate 5 than cathode collector plate more than 9; Groove 7 can face the anode fuel chamber and install; At this moment; Its actual area of section should be greater than the area of section of fuel cavity 1 groove 2, can be fixed between anode fuel chamber 1 and the anode collector plate 6 after 5 installations of assurance porous metal fiber plate.Groove 7 also can be installed over against membrane electrode 8, and its actual area of section should can touch anode catalyst layer to guarantee all fuel less than the effective area of membrane electrode 8.
As shown in Figure 8, present embodiment adopts the porous metal fiber plate 5 of embodiment 1 preparation to be positioned at the fuel-cell single-cell of anode fuel chamber 1 one sides, and with the conventional batteries that does not adopt the porous metal fiber plate, the performance curve under the same operation condition contrasts.The same operation condition is: the concentration of methanol solution of 1) supplying with is 2mol/L; 2) atmospheric operation, ambient temperature are 28 ℃, and humidity is 85%.The effective area of membrane electrode, fuel cavity cross section, collector plate opening area is 3mm * 3mm; Anode-side adopts 12 * 12 hole array collector plate, and each bore dia is 1.5mm, and spacing is 1mm; Cathode side adopts 1 * 12 grid array collector plate, each groove width 1.5mm, long 29mm, spacing 1mm.Implementation result is visible by Fig. 8, adopts the porous metal fiber plate as the pure medium of resistance, and maximum power density has improved 62%, and its battery performance is much better than the battery performance that does not adopt the porous metal fiber plate.
Like Fig. 6, shown in 7, be that with embodiment 3 differences porous metal fiber plate 5 is installed in the groove of setting up in anode fuel chamber 1 12 by embodiment 2 preparations.Anode fuel chamber 1 further groove 2 forms the fuel storage space with porous metal fiber plate 5, is used for the storaging liquid fuel methanol; Through hole 1 is a charging aperture, also is gas discharge outlet simultaneously; The cross sectional shape of groove 2 is identical with the shape and the effective area of membrane electrode 8 with effective area; The open side in anode fuel chamber 1 is processed with groove 12, controls the transfer rate of methyl alcohol in order to the controlled sintered type porous metal fiber plate of structural parameters that embeds the present invention's preparation; The area of section of anode fuel chamber 1 further groove 12 is identical with the area of section of the porous metal fiber plate 5 of embedding, all greater than the area of section of groove 2, encapsulates to make things convenient for porous metal fiber plate 5.Collector plate comprises anode collector plate 6 and cathode collector plate 9, and material need have strong corrosion resistant property and high conductivity, porose array of processing or grid array passage on it, and the opening area shape is identical with the shape and the effective area of membrane electrode 8 with effective area; Present embodiment anode collector plate 6 is identical with cathode collector plate 9 thickness, is 2mm.Membrane electrode 8 is made up of anode diffusion layer, anode catalyst layer, PEM, cathode catalysis layer and cathode diffusion layer, can be hot pressing type or non-hot pressing type assembly.The open end plate 10 of negative electrode is a frame structure, and the centre has through hole, and the through hole cross sectional shape is identical with the shape and the effective area of membrane electrode 8 with effective area, is used for obtaining airborne oxygen from the battery external world and gets into the cathode reaction zone.Between the anode-side of anode collector plate 6 and membrane electrode 8, accompany seal washer 4 between the cathode side of cathode collector plate 9 and membrane electrode 8, material is a polytetrafluoroethylene, in order to the sealing methanol liquid, prevents fuel leak; Between anode fuel chamber 1 and the anode collector plate 6, also accompany seal washer 4 between the open end plate 10 of cathode collector plate 9 and negative electrode, material is the silica gel circle, is used to seal methanol fuel, also plays the effect of buffering assembly force simultaneously.Similar with embodiment 3, the present embodiment fuel cell can be battery pack: its form can be symmetrical expression peace face-type structural.Symmetrical structure is made up of two monocells, two monocell common anode fuel cavity, and the negative electrode of two monocells places the battery pack both sides.The plane formula structure is made up of two or more a plurality of monocells, and the electrode of each monocell is arranged on same PEM, and conversion zone does not contact mutually, through lead successively with the both positive and negative polarity of each monocell composition battery pack that is together in series.
Claims (7)
1. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate comprises anode fuel chamber, battery operated unit and the open end plate of negative electrode; Battery operated unit comprises anode collector plate, membrane electrode and cathode collector plate; The both sides of membrane electrode are respectively equipped with anode collector plate and cathode collector plate; The open end plate of anode fuel chamber and negative electrode lays respectively at the outside of anode collector plate and cathode collector plate as battery container; Between membrane electrode and anode collector plate and cathode collector plate, between anode collector plate and the anode fuel chamber, and be respectively equipped with seal washer between cathode collector plate and the open end plate of negative electrode; It is characterized in that: be provided with the porous metal fiber plate at anode collector plate middle part, said porous metal fiber plate is metallic fiber sintered the forming of copper of 20-200 μ m by diameter, and porosity is 70%-90%, and permeability is 10
-12m
2-10
-9m
2, average pore size is 50 μ m-500 μ m, thickness 0.5mm-5mm.
2. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate according to claim 1 is characterized in that: said porous metal fiber plate is embedded in the groove of left side, anode collector plate middle part or right side cavity.
3. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate according to claim 1 is characterized in that: said porous metal fiber plate is embedded in the groove that anode fuel chamber open side sets up.
4. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate according to claim 1; It is characterized in that: the preparation method of said porous metal fiber plate is: through cutting method the copper raw material metal is processed the continuous type filament that diameter is 20 μ m-200 μ m; Again the metallic fiber of processing is cut into the long segment of fiber of 10mm-20mm; Then; Loose fibres section shop is placed the mould for preparing the porous metal fiber plate, and the cavity structure of mould is identical with porous metal fiber plate shape; Adopt carvel built successively to guarantee that the space of fiber and structure thereof is evenly distributed, mould just can place after assembling in the nitrogen atmosphere protection sintering furnace and carry out sintering, and sintering temperature is that 800 ℃-950 ℃, sintering time are 30min-90min.
5. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate according to claim 1 is characterized in that: the open end plate of said anode fuel chamber and negative electrode is that the polymethyl methacrylate of anti-liquid fuel carbinol corrosion is processed.
6. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate according to claim 1; It is characterized in that: said anode collector plate and cathode collector plate are by graphite cake or have corrosion resistance and the metal material of conductivity is processed; Porose array of processing or grid array passage on anode collector plate and the cathode collector plate, the opening area shape is identical with the shape and the effective area of membrane electrode with effective area.
7. the self-breathing direct methanol fuel cell monomer based on the porous metal fiber plate according to claim 1; It is characterized in that: the diffusion layer of said membrane electrode adopts carbon paper or carbon cloth as supporting layer; Anode-side is through hydrophilic treatment, and cathode side is through hydrophobic treatment.
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|---|---|---|---|
| CN201110213513A CN102324533A (en) | 2011-07-28 | 2011-07-28 | Self-breathing direct methanol fuel cell monomer based on porous metal fiberboard |
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| CN201110213513A CN102324533A (en) | 2011-07-28 | 2011-07-28 | Self-breathing direct methanol fuel cell monomer based on porous metal fiberboard |
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| CN104134807A (en) * | 2014-07-25 | 2014-11-05 | 华南理工大学 | Staggered intercommunicating mesh porous structural plate and fabrication method and application thereof |
| CN104676424A (en) * | 2015-01-27 | 2015-06-03 | 华南理工大学 | LED lighting system based on passive direct methanol fuel cells |
| CN105723555A (en) * | 2013-07-30 | 2016-06-29 | 淡马锡理工学院 | Fuel cell assembly |
| WO2017067417A1 (en) * | 2015-10-20 | 2017-04-27 | 西安交通大学 | Passive direct liquid fuel cell and preparation method therefor |
| CN106938334A (en) * | 2017-02-28 | 2017-07-11 | 华南理工大学 | A kind of porous metal fiber sintered plate molding device based on numerical optimization |
| CN108767287A (en) * | 2018-05-04 | 2018-11-06 | 华南理工大学 | For controlling and utilizing direct methanol fuel cell positive C O2Composite flow field plates |
| CN109193014A (en) * | 2018-09-11 | 2019-01-11 | 杭州电子科技大学温州研究院有限公司 | Modularization passive type direct alcohol fuel cell group |
| CN109860654A (en) * | 2019-01-21 | 2019-06-07 | 西安交通大学 | A kind of feed separation transmission fuel cell and its working method |
| CN113066995A (en) * | 2021-03-23 | 2021-07-02 | 中国科学院化学研究所 | PEM fuel cell, high-toughness porous carbon paper and preparation method thereof |
| CN115050983A (en) * | 2021-03-09 | 2022-09-13 | 通用汽车环球科技运作有限责任公司 | Propulsion battery with integrated fuel tank mounting system |
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| CN108767287A (en) * | 2018-05-04 | 2018-11-06 | 华南理工大学 | For controlling and utilizing direct methanol fuel cell positive C O2Composite flow field plates |
| CN109193014A (en) * | 2018-09-11 | 2019-01-11 | 杭州电子科技大学温州研究院有限公司 | Modularization passive type direct alcohol fuel cell group |
| CN109860654A (en) * | 2019-01-21 | 2019-06-07 | 西安交通大学 | A kind of feed separation transmission fuel cell and its working method |
| CN115050983A (en) * | 2021-03-09 | 2022-09-13 | 通用汽车环球科技运作有限责任公司 | Propulsion battery with integrated fuel tank mounting system |
| CN113066995A (en) * | 2021-03-23 | 2021-07-02 | 中国科学院化学研究所 | PEM fuel cell, high-toughness porous carbon paper and preparation method thereof |
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