CN102117920A - Organic/inorganic mixed proton exchange membrane - Google Patents
Organic/inorganic mixed proton exchange membrane Download PDFInfo
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Abstract
The invention discloses an organic/inorganic mixed proton exchange membrane which comprises the following components by weight percentage: 0.5 to 30 percent of inorganic material and 99.5 to 70 percent of organic material. The surface area of the inorganic material is 50 to 3000 square meters per gram. The organic material comprises a copolymerized high polymer containing a sulfoacid base or a polymer doped with phosphoric acid. The organic/inorganic mixed proton exchange membrane has excellent water-retaining property, excellent mechanical strength and excellent conductivity, and does not expand or deform easily in high-temperature water.
Description
Technical field
The present invention relates to a kind of proton exchange membrane, relate in particular to a kind of can be in the low wet environment of the high temperature proton exchange membrane that the organic-inorganic done blendes together of finishing drilling.
Background technology
Fuel cell (Fuel Cell, FC) be a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) of utilizing chemical energy directly to be converted to electric energy, under traditional generation mode comparison, fuel cell has low pollution, low noise, high-energy-density and higher advantages such as energy conversion efficiency, be to have following prospective clean energy, applicable scope comprises various fields such as portable electric product, household system, means of transportation, military equipment, space industry and small power generation system.
Each types of fuel cells has different application markets according to the difference of its operation principles and operating environment, application on the packaged type energy mainly is with hydrogen Proton Exchange Membrane Fuel Cells (Proton ExchangeMembrane fuel Cell, PEMFC) and direct methanol fuel cell (Direct Methanol FuelCell, DMFC) be main, the both belongs to the cold-starting type fuel cell that the use proton exchange membrane is carried out proton conduction mechanism.With this type of Proton Exchange Membrane Fuel Cells operating principle,, produce hydrogen ion (H for hydrogen carries out oxidation reaction at the anode catalyst layer
+) and electronics (e
-) (PEMFC principle), or methyl alcohol and water carries out oxidation reaction at the anode catalyst layer, produces hydrogen ion (H
+), carbon dioxide (CO
2) and electronics (e
-) (DMFC principle), wherein hydrogen ion can be passed to negative electrode via proton-conductive films, electronics is passed to negative electrode after then transferring to the load work done via external circuit again, and the oxygen that supply with cathode terminal this moment can carry out reduction reaction and produce water in the cathode catalysts layer with hydrogen ion and electronics.The performance of this type of Proton Exchange Membrane Fuel Cells is decided by catalyst phase reaction efficient, involve electrical conductivity, ionic conduction and fuel efficiency of transmission, the three is of equal importance in fuel cell design, and any conducting path is hindered, and fuel cell performance promptly is affected.And wherein leading ionic conduction speed person is a proton exchange membrane.
Though fuel cell has the electrical characteristic of multinomial excellence and uses speciality, because its cost costliness becomes comprehensive business-like maximum bottleneck, thereby how to promote fuel battery performance, simplified system design, become the task of top priority to reduce the fuel cell cost.Thereby hydrogen fuel cell moves towards in low humidification operating system, and direct methanol fuel cell then trends towards the exploitation of passive type direction of operating, and both most important key problem in technology then are to have the high water holding capacity and the proton exchange membrane of proton conducting fast.
Low humidified hydrogen makings proton exchange film fuel cell, mainly be to adopt low relative humidity (＜65%RH) fuel system, to replace the full humidification fuel-feed of present 100%RH mode, the humidifier design of this type of low humidification design can simplification fuel cell reduces BOP (Balance of Plant) and consume electric power, and then reduces the system cost of hydrogen fuel cell.And passive direct methanol fuel cell, then use the fuel of high concentration methanol as generating, its advantage is that system component can simplify, methyl alcohol is easy to carry, high-energy source density, all keep liquid under various environment, and does not need process and assembly as the complicated vaporization generation hydrogen of indirect type fuel cell needs.
Yet, because passive direct methanol fuel cell is to come charging with the methanol vapor of high concentration, and water system is another anode fuel of direct methanol fuel cell, to face the awkward situation of anhydrous participation reaction, be ionic conduction impedance rising problem, will the performance of passive direct methanol fuel cell significantly decayed; Low humidification hydrogen fuel cell then uses the extremely low fuel of relative humidity to come charging, and amberplex shrinkage problem causes catalyst layer to peel off problem under proton conduction impedance problems and the operation of dried wet environment in same facing.Thereby, be how to continue under the high-temperature operation to have stability and the flexibility and the mechanical strength of good water-conserving capacity, dimensional stability, electrochemistry and chemical resistance no matter be to use the passive direct methanol fuel cell of concentration methanol vapor or the technical bottleneck of low its proton exchange membrane that is made of humidified hydrogen makings proton exchange film fuel cell.Therefore need badly and a kind ofly can have in the wet environment that high water holding capacity dimensional stability adds and the proton exchange membrane of proton conducting fast in high temperature low adding.
Summary of the invention
The proton exchange membrane that provides a kind of organic-inorganic to blend together is provided technical problem to be solved by this invention, and it has good water-retaining property, mechanical strength and electrical conductivity and be difficult for dilatancy in the water of high temperature.
For achieving the above object, the present invention proposes the proton exchange membrane that a kind of organic-inorganic blendes together, and comprises 0.5wt%-30wt% inorganic material and 99.5wt%-70wt% organic material.The surface area of inorganic material is the 50-3000 meters squared per gram.Organic material comprises the copolymerized macromolecule of tool sulfonate radical or the polymer of doping phosphoric acid.
Described according to the embodiment of the invention, the surface area of above-mentioned inorganic material is 2100,800 or 210 meters squared per gram.
Described according to the embodiment of the invention, above-mentioned inorganic material comprises the carbon material.
Above-mentioned inorganic material is no upgrading carbon material.No upgrading carbon material comprises activated carbon, middle hole carbon material (mesoporous carbon), carbon nanometer shell (nanoshell carbon), carbon nanohorn (nanohorncarbon), carbon nanosheet (nanosheet carbon), agraphitic carbon or crystalline carbon.
Described according to the embodiment of the invention, the copolymerized macromolecule of above-mentioned tool sulfonate radical comprises perfluorinated sulfonic resin (Nafion), sulfonated polyether-ether-ketone (sulfonated poly (ether ether ketone), s-PEEK), sulfonated polyimide (sulfonated polyimides, s-PI), sulfonation polyoxygenated dimethylbenzene (sulfonated poly (phenylene oxide), s-PPO), sulfonated polyether sulphone (sulfonatedpoly (arylene ether sulfone), s-PES), or poly-(the 4-phenoxy group 1 of sulfonation, 4-phenylbenzyl ester) (sulfonated poly (4-phenoxybenzoyl-1,4-phenylene), s-PPBP).
Described according to the embodiment of the invention, the polymer of above-mentioned doping phosphoric acid comprise doping phosphoric acid polyphenyl imidazoles macromolecule (phosphoric acid doped polybenzimidazole, PBI).
The water-retaining property of the proton exchange membrane of the embodiment of the invention is good, mechanical strength is excellent, electrical conductivity is good and be difficult for dilatancy in the water of high temperature.
Description of drawings
Fig. 1 is that the glass transition temperature (Tg point) of proton exchange membrane of the activated carbon of various content changes.
Fig. 2 is the solid water rate of proton exchange membrane of the activated carbon of various content.
Fig. 3 moistens swollen rate for the water of the proton exchange membrane of the activated carbon of various content.
Fig. 4 illustrates the electrical conductivity of proton exchange membrane under various relative humidity of the activated carbon of various content.
Embodiment
The present invention proposes a kind of proton exchange membrane, it is the proton exchange membrane that is blended together by a kind of organic-inorganic that organic material and inorganic material blend together, it has the ability of high water holding capacity and quick proton conducting, can be applied to the PEMFC proton exchange membrane of the low humidified condition of high temperature, also can be applied to the passive type DMFC of high concentration methanol vapor feed mode.
In one embodiment, the content of inorganic material is 2.5wt% in the proton exchange membrane that above-mentioned organic-inorganic blendes together, and the content of organic material is 97.5wt%.In another embodiment, the content of inorganic material is 5wt% in the proton exchange membrane that above-mentioned organic-inorganic blendes together, and the content of organic material is 95wt%.In another embodiment, the content of inorganic material is 10wt% in the proton exchange membrane that above-mentioned organic-inorganic blendes together, and the content of organic material is 90wt%.In another embodiment, the content of inorganic material is 20wt% in the proton exchange membrane that above-mentioned organic-inorganic blendes together, and the content of organic material is 80wt%.
Organic material in the proton exchange membrane that above-mentioned organic-inorganic blendes together comprises the copolymerized macromolecule of tool sulfonate radical or the polymer of doping phosphoric acid.The example of the copolymerized macromolecule of tool sulfonate radical comprises perfluorinated sulfonic resin (Nafion), sulfonated polyether-ether-ketone (sulfonated poly (ether ether ketone, s-PEEK), sulfonated polyimide (sulfonated polyimides, s-PI), sulfonation polyoxygenated dimethylbenzene (sulfonated poly (phenylene oxide), s-PPO), sulfonated polyether sulphone (sulfonatedpoly (arylene ether sulfone), s-PES), or poly-(the 4-phenoxy group-1 of sulfonation, 4 phenylbenzyl esters) (sulfonated poly (4-phenoxybenzoyl-1,4-phenylene), s-PPBP).The example of the polymer of doping phosphoric acid comprise doping phosphoric acid polyphenyl imidazoles macromolecule (phosphoric acid dopedpolybenzimidazole, PBI).
Inorganic material in the proton exchange membrane that above-mentioned organic-inorganic blendes together comprises the absorbent material with high surface.The surface area of absorbent material is 50 meters squared per gram (m
2/ g) more than.In one embodiment, the surface area of absorbent material is 2100 meters squared per gram.In another embodiment, the surface area of absorbent material is 800 meters squared per gram (m
2/ g).In another embodiment, the surface area of absorbent material is 210 meters squared per gram (m
2/ g).Absorbent material comprises the carbon material.In one embodiment, absorbent material is no upgrading carbon material, and the example of no upgrading carbon material comprises activated carbon, middle hole carbon material, carbon nanometer shell, carbon nanohorn, carbon nanosheet, agraphitic carbon or crystalline carbon.
(Proton exchange membrane fuel cells, proton conduction mechanism PEMFCs) comprises Vehicular mechanism and Grotthuss mechanism to Proton Exchange Membrane Fuel Cells.Vehicular mechanism is that the proton and the hydrone that utilize strong acid to dissociate form H
3O+ (hydronium ion), proton conducts against the transmission between hydrone, uses proton exchange membrane easy dehydration when high temperature of Vehicular mechanism proton conducting, and it is low that proton conductive is spent, and the problem that methanol crossover is arranged, thereby can't under high methanol concentration and the low humidified condition of high temperature, operate.Therefore the proton exchange membrane such as the desire of this class promote its high temperature proton conductive degree characteristic, and its key is the moisture content hold capacity of how at high temperature to possess in the proton exchange membrane.Grotthuss mechanism utilizes proton to supply with between the position in protons different on the exchange membrane, work jumps (hopping) continuously and conducts, and do not need water to exist promptly to have certain proton conductivity, on the structure of this type of proton exchange membrane, have usually bronsted acid alkali to (
Acid base pairs, Ionic liquids) or the Bronsted acid temperature of mixing excessive then its ionic conductance higher (especially more than 130 ℃) of height of healing, therefore, its characteristic lower temperature operating system that is applied to high temperature PEMFCs system is good.
Nafion is that the most normal making is used as Proton Exchange Membrane Fuel Cells (Proton exchangemembrane fuel cells, the material of proton-conductive films PEMFCs).The proton exchange membrane of tool sulfonate radicals such as Nafion promptly belongs to the representative of Vehicular mechanism.Nafion must contain sufficiently high water content could represent effective proton conductive degree by tool, and therefore, its operating temperature all (mostly is being 70～80 ℃) below 90 ℃.But PEMFC operates regular meeting at a lower temperature causes two large problems: the Pt catalyst is very easily poisoned by the CO of denier in the hydrogen fuel and causes the catalyst efficiency variation during first low-temperature operation; Moreover, be the problem of water management difficulty, proton-conductive films more easily dewaters and has reduced the ionic conduction degree during low current density.So often need, but when high current density operate, cause the negative electrode waterflooding again easily, and then cause oxygen to conduct causing the catalyst surface, caused matter to pass the problem that limits (mass transport limitation) with the fuel humidification.
The polyphenyl imidazoles (PBI) of doping phosphoric acid is the material of another kind as the proton-conductive films of Proton Exchange Membrane Fuel Cells.The polyphenyl imidazoles (PBI) of doping phosphoric acid promptly is the main representative of using Grotthuss mechanism transmission mechanism, but its when high temperature the ionic conductance of (160 ℃) still not as the proton conductive degree of Nafion at 80 ℃.Generally speaking, the technical bottleneck of high temperature proton exchange film is how to continue under the high-temperature operation to have stability and the flexibility and the mechanical strength of good water-conserving capacity, dimensional stability, electrochemistry and chemical resistance.
The proton exchange membrane of the embodiment of the invention has also blended together inorganic material except having used organic material (for example being Nafion or s-PEEK), because inorganic material has high surface, has excellent water absorption character, therefore, blending together the proton exchange membrane that made organic-inorganic blendes together with organic material (for example being Nafion or s-PEEK) and inorganic material has high water holding capacity and has the ability of proton conducting fast, and have better structural strength and temperature tolerance, therefore, can be applied to the PEMFC proton exchange membrane of the low humidified condition of high temperature, also can be applied to the passive type DMFC of high concentration methanol vapor feed mode.
The preparation of proton exchange membrane:
Example 1
The no upgrading porous carbon (activated carbon) of 20wt% (with respect to whole solid content) is loose in perfluorinated sulfonic resin Nafion (NAF, DE2020CS commodity by E.I.Du Pont Company's manufacturing) in the solution, to form slurries (ink), stir, after slaking in 12 hours, be coated on made slurries on glass and with solvent evaporates (evaporated).The H that to be dipped in 80 ℃ of concentration again be 1N
2SO
4(aq) 1 hour or a few hours are carried out the proton substitution reaction among.Then, be soaked in 1 hour or a few hours among 80 ℃ the excessive pure water,, obtain the black mantle with abundant cleaning.Afterwards, the characteristic of film is measured.The result that flexibility, glass transition temperature are measured is as shown in table 1, along with the size change amount of temperature as shown in Figure 1, water-retaining property and moisten swollen result such as table 2 and Fig. 2 and shown in Figure 3, the table 3 as a result that the electrical conductivity under various relative humidity is measured is with shown in Figure 4.
Example 2 is to example 4
Being same as the method system film of example 1, but the content that does not have a upgrading porous carbon (activated carbon) is changed into 10wt%, 5wt% and 2.5wt% respectively.
Example 5, example 6
To be same as the method system film of example 1, do not change ECP 600 (carbon black, NSA (Net Surface area): 1200m respectively into but will there be the upgrading porous carbon
2/ g) with CL-08 (carbon black, NSA:210m
2/ g is by the manufacturing of Chinese synthetic rubber company) its content is 5wt%.
Example 7
Being same as the method system film of example 1, but the content that macromolecule makes s-PEEK into by NAF and do not have a upgrading porous carbon (activated carbon) is 5wt%.
Comparative example 1
Being same as the method system film of example 1, but do not contain inorganic material-no upgrading porous carbon (activated carbon).
Comparative example 2
Being same as the method system film of example 1, but macromolecule makes s-PEEK into by NAF, but does not contain inorganic material-no upgrading porous carbon (activated carbon).
Table 1
| The content of porous carbon (activated carbon) | Flexibility | Glass transition temperature (Tg) | |
| Example 1 | 20wt％ | Deflection | 116 |
| Example 2 | 10wt％ | Deflection | 94 |
| Example 3 | 5wt％ | Deflection | 91 |
| Example 4 | 2.5wt％ | |
80 |
| Comparative example 1 | 0wt％ | Deflection | 73 |
Table 3
Table 2
| The content of porous carbon (activated carbon) | Original size | Solid water rate (%) | Water moistens swollen size (water volume swelling size) | Water moistens swollen ratio | |
| Example 1 | 20wt％ | ?(50mm×50mm×39μm) | 688.38 | ?(54mm×55mm×55μm) | 27.4％ |
| Example 2 | 10wt％ | ?(50mm×50mm×25μm) | 330.00 | ?(53mm×53mm×35μm) | 32.38％ |
| Example 3 | 5wt％ | ?(50mm×50mm×29μm) | 73.22 | ?(54mm×55mm×34μm) | 39.28％ |
| Example 4 | 2.5wt％ | ?(50mm×50mm×25μm) | 43.08 | ?(55mm×56mm×29μm) | 42.91％ |
| Comparative example 1 | 0wt％ | ?(50mm×50mm×30μm) | 29.66 | ?(56mm×57mm×35μm) | 48.96％ |
The content that shows activated carbon by the result of table 1 is at 2.5-20wt%, and formed exchange membrane all has good flexibility.In addition, the glass transition temperature of exchange membrane increases along with the increase of the content of no upgrading activated carbon, can promote the mechanical strength of high-temperature fuel cell.
The glass transition temperature (Tg point) that is shown film by the result of Fig. 1 increases along with the increase of the content of no upgrading activated carbon.
Result by table 2 and Fig. 2 shows that adding no upgrading activated carbon can promote exchange membrane solid water rate, and exchange membrane solid water rate increases along with the increase of the content of no upgrading activated carbon, helps the increase of electrical conductivity, the lifting of battery efficiency.Show that by the result of table 2 and Fig. 3 adding no upgrading activated carbon can improve the swollen situation of water profit, and the swollen ratio of water profit reduces along with the increase of the content of no upgrading activated carbon, can be so as to the malformation of minimizing battery.
The result of Fig. 4 shows that the no upgrading activated carbon of interpolation can promote the electrical conductivity of exchange membrane.When the addition of no upgrading activated carbon was 10wt%, its electrical conductivity reached capacity.Relative humidity is lower, the electrical conductivity amplitude that promotes bigger.When spending humidity mutually and be 30RH%, the exchange membrane that adds the activated carbon with high surface can significantly promote compared to Nafion temperature 70-80 ℃ electrical conductivity.
Confirm from experimental result no matter the proton exchange membrane of the embodiment of the invention is solid water coefficient and mechanical strength, all be better than merely, and also be difficult for dilatancy in the water of high temperature with the proton exchange membrane of Nafion as material.This representative is added and to be had can gain the really usefulness of proton exchange membrane of inorganic material that high surface has water absorption character, and it can obviously improve the swelling of film.Moreover the present invention adds the inorganic material of the high surface with porous can utilize the hole water conservation, keeps the proton conductive under the low wet environment, and therefore, the usefulness of the proton exchange membrane that not only can gain also can significantly promote electrical conductivity.The proton exchange membrane of adding the inorganic material with high surface can significantly promote compared to Nafion in the electrical conductivity of temperature 70-80 ℃ low humidity (30RH%), very has competitive advantage.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (7)
1. the proton exchange membrane that organic-inorganic blendes together is characterized in that, comprising:
0.5wt%-30wt% inorganic material, the surface area of this inorganic material are the 50-3000 meters squared per gram; And
The 99.5wt%-70wt% organic material comprises the copolymerized macromolecule of tool sulfonate radical or the polymer of doping phosphoric acid.
2. the proton exchange membrane that organic-inorganic according to claim 1 blendes together is characterized in that, the surface area of this inorganic material is the 50-3000 meters squared per gram.
3. the proton exchange membrane that organic-inorganic according to claim 1 blendes together is characterized in that this inorganic material comprises the carbon material.
4. the proton exchange membrane that organic-inorganic according to claim 1 blendes together is characterized in that, this inorganic material comprises no upgrading carbon material.
5. the proton exchange membrane that organic-inorganic according to claim 4 blendes together is characterized in that, this no upgrading carbon material comprises activated carbon, middle hole carbon material, carbon nanometer shell, carbon nanohorn, carbon nanosheet, agraphitic carbon or crystalline carbon.
6. the proton exchange membrane that organic-inorganic according to claim 1 blendes together, it is characterized in that, the copolymerized macromolecule of this tool sulfonate radical comprises that perfluorinated sulfonic resin, sulfonated polyether-ether-ketone, sulfonated polyimide, sulfonation polyoxygenated dimethylbenzene, sulfonated polyether sulphone or sulfonation gather (4-phenoxy group-1,4 phenylbenzyl ester).
7. the proton exchange membrane that organic-inorganic according to claim 1 blendes together is characterized in that, the polymer of this doping phosphoric acid comprises the polyphenyl imidazoles macromolecule of doping phosphoric acid.
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Cited By (1)
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| CN103358612A (en) * | 2012-03-26 | 2013-10-23 | 上海中科高等研究院 | Methanol rejective membrane for direct methanol fuel cell as well as preparation method and application thereof |
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| CN101414686A (en) * | 2007-10-17 | 2009-04-22 | 中国科学院大连化学物理研究所 | Compound film and application thereof for high-temperature fuel battery with proton exchange film |
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| US20050233183A1 (en) * | 2004-03-15 | 2005-10-20 | Hampden-Smith Mark J | Modified carbon products, their use in electrocatalysts and electrode layers and similar devices and methods relating to the same |
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| CN103358612A (en) * | 2012-03-26 | 2013-10-23 | 上海中科高等研究院 | Methanol rejective membrane for direct methanol fuel cell as well as preparation method and application thereof |
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