TW201011963A - Acidic nano-fiber/basic polymer used as composite proton exchange membrane and method for manufacturing the same - Google Patents

Abstract

An acidic nano-fiber/basic polymer used as a composite proton exchange membrane and methods for manufacturing the same are provided. An acid nano-fiber membrane is provided as a matrix. A basic resin for proton exchange is then added to reinforce the acid nano-fiber membrane matrix.

Description

201011963 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a proton exchange membrane and a method of manufacturing the same. More specifically, the present invention relates to a composite proton exchange membrane of an acidic nanofiber/alkaline polymer and a method for producing the same. [Prior Art] Currently, proton exchange membrane fuel cells that can be operated at low temperatures (<100 °C) mostly use perfluorosulfonic acid (PFSA) proton exchange membranes to form membrane electrode sets, commonly used protons. The exchange membrane was a perfluorosulfonic acid resin (Nafion) manufactured by Du Pont Co. The properties of the PFSA proton exchange membrane are high mechanical strength, high chemical stability, high decomposition temperature (>280 °C), and high ion conductivity. However, when the PFSA proton exchange membrane is used in a methanol fuel cell, the fuel sterol is easily penetrated from the anode to the cathode, so that the power generation efficiency is remarkably lowered. Further, when the operating temperature of the fuel cell is higher than 10 °C, the ionic conductivity is lowered due to the evaporation of water and the fuel cell power generation efficiency is poor. In addition, the price of PFSA is very expensive. In recent years, many hydrocarbon polymers have also been developed for use in proton exchange membrane fuel cells, such as polybenzopyrene. Polybenzimidazole (PBI), sulfonated polyarylether ether ketone (S-PEEK), sulfonated poly(ethersulfone), S-PES, rheinated polyphenylene Sulfated poly(phenoxy phosphazene) and blends thereof or modified derived polymers. In general, to increase the power generation of a fuel cell, the ion conductivity of the exchange membrane of Proton 5 201011963 can be increased, or the thickness of the proton exchange membrane can be reduced to reduce the resistance of ion conduction. However, in general, polymers have low mechanical strength, so a proton exchange membrane must be made with a considerable film thickness to provide sufficient support. 'Content of the invention】

Therefore, one aspect of the present invention provides a composite proton exchange membrane of an acidic nanofiber/alkaline polymer and a preparation method thereof, the method comprising the steps of: preparing an acidic nanofiber (four) substrate and a repellent resin to reinforce the above The acidic nanofiber membrane substrate, wherein the above-mentioned test resin is a high molecular polymer and has proton exchange capacity, thereby preparing a composite proton exchange membrane of acidic nanofiber/basic polymer having high mechanical strength and low film thickness. In the specific embodiment of the present invention, a method of preparing two acidic nanofiber membrane substrates is proposed. Both methods utilize the electrospinning (heart-(4)) technique to prepare a polymer nanofiber membrane to obtain an acidic nanofiber membrane substrate. The above two methods are described below. The first preparation method of the acidic nanofiber membrane substrate is to prepare a local nanofiber membrane by electrospinning technology to re-use a chemical modification method to bring the above-mentioned polymer nanofiber membrane with an acidic functional group, and the steps are as follows An electrospinning solution containing (N>N, _dimethyi acetami^ Ac' to be formulated into an electrospinning solution according to a preferred embodiment of the invention having a weight percent concentration of from about 5% to about 5% Then, electrospinning is performed by using an electrospinning solution to obtain a fiber membrane base m, and the fiber membrane substrate is impregnated with an acidified modified liquid, and the weight of the acidified reforming liquid in the crucible is 湲6 201011963 for about 24 hours, so as to be Base (4) derived nanofiber membrane substrate. The acidic nanofiber membrane substrate is rinsed with deionized water to remove acidic molecules. The second preparation method of the organic acid nanofiber membrane substrate The electrospinning technology is used to make an acid-based polymer material into an acidic polymer rice fiber membrane, the steps of which are as follows: preparing an acidified polymer material, adding a high:; material into an acidified upgrading liquid to make Acidification of polymer materials, which is chemicalized The weight of the liquid is from about 5% to about 99%, and the weight of the polymer material and the acidified modifier is different depending on the acidity of the acidification solution and the time and temperature of the modification. The ratio may be from about 1:1 to about 丨: (7)^ Next, distilled water is added to the acidified upgrading solution in a volume ratio of about 1:1 to form an acidified polymer material in the acidification reforming liquid to form a particle. And filtering out the 'particles'. Then 'recorded and dried. The above dried suspension particles are dissolved in DMAc to prepare an electrospinning solution at a concentration of about 5% to about 50% by weight. The solution was electrospun 'to obtain an acidic nanofiber membrane substrate.

According to the specific embodiment, the composite proton exchange membrane of the acidic nanofiber/basic polymer is prepared by preparing an alkaline resin solution having a concentration by weight of about 1% to about 30%, which has a proton exchange. The basic resin of the ability is dissolved in the DMAc solvent. The alkaline resin solution is contacted with an acidic nanofiber membrane substrate produced by the above method, wherein the acidic nanofiber membrane substrate has multiple pores to accommodate the alkaline resin solution. Finally, the residual DMAc solvent in the composite proton exchange membrane of the acidic nanofiber/basic polymer is removed to obtain a composite proton exchange membrane of acidic nanofiber/basic polymer. 7 201011963. A composite proton exchange membrane of an acidic nanofiber/inspective polymer prepared according to a specific embodiment of the present invention comprises an acidic nanofiber membrane substrate, and a plurality of basic resins The acidic functional group of the acidic nanofiber medium substrate is combined with the acidic functional group of the acidic non-fiber fiber membrane substrate, so that the test resin can be distributed throughout the acidic nanofiber/alkali In the composite proton exchange membrane of a polymer, rather than only on the surface of a composite proton exchange of acidic nanofibers/alkaline polymers, to improve the composite proton φ exchange membrane of the acidic nanofiber/basic polymer Ionic conductivity and mechanical strength. Another aspect of the present invention provides a membrane electrode assembly and a method of producing the same, which are produced by using a composite proton exchange membrane of an acidic nanofiber/alkaline polymer according to the above specific embodiment of the present invention. The membrane electrode assembly comprises an anode, a cathode, and a composite proton exchange membrane of the above acidic nanofiber/alkaline polymer. The composite proton exchange membrane of the acidic nanofiber/initial polymer is interposed between the anode and the cathode.实施 [Embodiment] In order to reduce the thickness of the proton exchange membrane and increase the mechanical strength of the proton exchange membrane, the present invention provides a composite proton exchange membrane of an acidic nanofiber/alkaline polymer and a preparation method thereof. Further, another aspect of the present invention provides a membrane electrode assembly and a method for producing the same, which are produced by using the above-described acidic nanofiber/alkaline polymer composite proton exchange membrane. (1) Acid nanofiber/alkaline polymer composite proton exchange membrane and preparation method thereof

S 201011963. Fig. 1 is a schematic cross-sectional view showing a composite nanoporous membrane of an acidic nanofiber/alkaline polymer according to a specific embodiment of the present invention. The acidic nanofiber/basic polymer composite proton exchange membrane 100 comprises an acidic nanofiber membrane 102 and an alkali resin 1〇6 having proton exchange capacity. Among them, the acid nanofiber membrane 102 is composed of a plurality of fiber bundles 1〇4, and can be used as a base material of a composite nanoporous membrane of an acidic nanofiber/alkaline polymer. The above-mentioned basic resin 106 is distributed in the pores formed by the fiber bundles 1〇4, and is combined with the acidic functional groups of the acidic nanofibers/membrane substrate ι2 using the basic functional groups of the basic resin 1〇6. In order to improve the ionic conductivity and mechanical strength of the complex σ proton parent film 100 of the acidic nanofiber/alkaline knife. (1.1) Method for preparing acid nanofiber membrane substrate According to a specific embodiment of the present invention, there are two methods for preparing a polymer nanofiber membrane by electrospinning to obtain an acidic nanofiber membrane substrate 102. The above two methods are described as follows.

1·1·1) First Preparation Method of Acid Nanofiber Membrane Substrate According to the present invention - a specific embodiment, electrospinning is carried out using a high molecular material having no acidic functional group to obtain a nanofiber membrane substrate. Next, the nanofiber membrane substrate is modified with an acidified upgrading liquid, and (4) (d) (iv) a functional functional acid nanofiber membrane substrate 102. In the embodiment of the present invention, the electrospinning solution used in the electrospinning has a concentration of ...% by weight of the material. In addition, the acid in the acidified upgrading solution used in the modification of the fiber membrane substrate may contain a sulfonate 3, a slow acid s (_C00H, please confirm that it is citric acid) or an acidate 9 201011963 - 〇P〇3H2) 'And its weight percent concentration is about 5-99%. The condition for the modification can be adjusted by the conventional means depending on the type and concentration of the acidified upgrading liquid to be used. For example, the reaction time can be @〇.5_24 hours. It should be noted that although in this embodiment, the fiber medium substrate is acidified by the acidification modifying liquid. The person skilled in the art of the present invention has a general knowledge. I can easily use the other principles according to the principle and spirit of the present invention. Preparation = learning hand & or chemical reaction, such that the above nanofiber membrane substrate has an acidic functional group. Therefore, various such variations and modifications are the second preparation method of the (1.1.2) acidic nanofiber enamel substrate of the present invention. According to another embodiment of the present invention, the acidified modified solution is first modified. The polymer material used is formed to form a polymer material having an acidic functional group. Then, electrospinning is carried out using a polymer material having an acidic functional group to obtain an acidic nanofiber membrane substrate 1G2. In the embodiment of the invention, electric, spinning

In the electrospinning solution used for the yarn, the acid polymer material has a concentration by weight of about 5 - 50% by weight. The polymer materials used in the above two preparation methods may be P〇ly (Aryl Ether Ether Ket〇ne), pEEK), polysul W (PSU), polyphenylene phosphate nitride ( P〇(10)^(10) Phosphaz-), polystyrene (P〇lystyrene, ps). The above acidic functional group may be a -SO# group, a -COOH group or a _OP〇3H2 group. According to the above specific embodiment of the present invention, the film thickness of the acidic nanofiber membrane substrate may be about 5 to 70 μπι, and in a preferred case, it may be about 1 〇 _5 ^ ^ ^ · In a better case, 25-40 μηι. '201011963. a It should be noted that although in this embodiment, the acid material is acidified by acidification, the technical field of the present invention can be easily imagined according to the principle and spirit of the present invention. The above polymer material has an acidic = energy group by other suitable chemical means or chemical reaction. Accordingly, various such changes and modifications are within the scope of the invention. 0.2) Preparation of composite proton exchange membrane of acidic nanofiber/basic polymer φ method According to a specific embodiment of the present invention, a preparation method of a composite nanoparticle/basic high molecular composite proton exchange membrane 100 is proposed. For example, the alkaline resin solution is brought into contact with the above-mentioned acidic nanofiber membrane substrate 1〇2 by spraying, coating, screen printing, spin coating, blade coating or dipping to make the basic resin 104 The fiber bundle ι〇4 of the acidic nanofiber membrane substrate ι〇2 is combined to obtain a composite proton exchange membrane of acidic nanofiber/basic polymer. The basic resin 1〇4 contained in the above-mentioned test resin solution is a high molecular polymer having proton exchange capacity. The basic resin 104 may be polypyridylamine or chitosan. , polybenzimidazole (PBI), polyimine, polyaniline, p〇iyamide, p〇iyVinyi alcohol or others containing alkaline Functional polymer branched polymer. The basic functional group contained in the basic resin 104 may be a primary amine group, a secondary amine group, a tertiary amine group or an -OH group. The above basic resin solution has a weight concentration of about 0.1 to 30% (on page 5, 0.1 to 30%). According to another embodiment of the present invention, the above-mentioned acidic naphthalene/macropolymer composite proton exchange membrane 100 can be further immersed in a protonation solution. In this way, the acidic molecules in the acid solution can be filled in the pores of the composite proton exchange membrane of the acidic nanofiber/basic polymer to improve the composite proton exchange membrane 100 of the acidic nanofiber/initial polymer. Ion conductivity. The above acid solution may be a solution of sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid. The electrospinning technique used in the above embodiments of the present invention causes the polymer solution or the melt to have an ejection charge by a high potential, and the dried nanofibers are dried and solidified, and the diameter of the generated fiber bundle 104 is About 20~200 nm. The acidic nanofiber membranes 1〇2 formed by the interlacing of the fiber bundles 104 have the characteristics of a porous hole, a high fiber surface area, and an acidic functional group on the surface of the fiber. Further, these fiber bundles may be joined to each other to form a network structure of fibers which contributes to the mechanical strength of the acidic nanofiber 臈 substrate. On the other hand, since the fiber surface area of the acidic nanofiber membrane 1〇2 is large, the acidic resin solution is reinforced by the alkaline resin solution containing a basic functional group, and the fibrous film substrate 102 is in the test resin solution. The contact area of the functional functional group and the acidic functional group of the fibrous film substrate is large, and the bonding force between the acidic nanofiber medium substrate and the test tree can be further improved. Therefore, the composite nano-matrix/basic polymer composite film 100 prepared according to the specific embodiment of the present invention has a film thickness of only about 5-7 μm, but has a high machine strength. * Due to the above-mentioned acidic nanofiber/basic polymer composite proton exchange. Membrane ι〇0 has a small thickness and high mechanical strength, which can significantly reduce its ion conduction impedance, and thus it is used in the membrane electrode group of a fuel cell. At the time, the performance of the fuel cell will be significantly improved by 12 201011963. (1.3) Example of Composite Proton Exchange Membrane of Acidic Nanofiber/Basic Polymer Here, an example of preparing a composite proton exchange membrane 丨00 of an acidic nanofiber/initial polymer according to the above-described embodiment of the present invention will be described in detail. And the formed analysis and film thickness of the composite proton exchange membrane of the prepared acidic nanofiber/basic polymer. In the following examples, the acidic nanofiber membrane substrate 102 is first prepared by the above two methods, respectively, and then formed into a composite proton exchange membrane of acidic nanofiber/alkaline polymer 100 〇 (1.3.1). Example 1: Preparation of Acid Nanofiber Membrane Substrate This example is a electrospinning technique in which a polymer material PSU is made into a PSU fiber membrane and then a PSU fiber membrane is formed (10) to form a hybrid psu (s. Lysulw, s-PSU) fiber membrane substrate 1〇2, which is prepared as follows: (a) Dissolving PSU in OMAc to clear the electrospinning solution. Medium to weight ratio

(b) electrospinning using the electrospinning solution obtained by obtaining a PSU fiber membrane at a weight concentration of about 250/0 to obtain an S-PSU fiber membrane; 骒(〇s-PSU fiber membrane, Removal (〇) the step ((8) Psu aqueous solution of sulfuric acid was immersed for 2 hours, (d) rinsing the sulfuric acid on the surface of the s-PSU fiber membrane with deionized water. In this example, the re-golden liquid was used as the acidification reforming solution. 1 psnh concentration of about 25% of sulfuric acid water-soluble electrospinning operation parameters such as _ wei film continued acidification. This example used * clothing i shown: 13 201011963 —~—------ Table 1 potential ——— _____j 20 kV working distance ^ flow rate 20 cm 〇 · 5 ml / hr degree 23 ° C mesh humidity 5 1 % RH ^------- Figure 1 and Figure 3 show the psu fiber membrane substrate of this example ❹ and SU fiber membrane substrate 102, a scanning electron miterograph (bribet) photograph. It can be found from Fig. 2 that the fiber bundles of the electrospun fibers in the psu film substrate are interlaced to form a network structure. The fiber membrane substrate is made into a porous molding material, and the diameter of the fiber bundle is about 100 8000 nm. The sulfonated S-Psu fiber membrane substrate 102' is still a porous membrane material. (1.3.2) Example 2: Preparation of an acidic nanofiber membrane substrate • This example utilizes electrospinning technology and will have The acid-based polymer material is made into an acidic nanofiber membrane 1〇2. In this example, a sulfonated poly(ether ether ketcme), s_pEEK polymer material is used to make the s_PEEK fiber membrane 102''. 'The preparation method is as follows: (a) About 1 g of PEEK (purchased from p〇iyscience Co.) is added to about 5 g of a concentration of about 96% H2SO4 solution, and heated and stirred at about 50 ° C. 24 hours to sulfonate PEEK;

201011963 π (b) The distilled water is added to the solution obtained in the step (a) at a ratio of about 1: ϊ (v/v) to cause suspended solid particles in the solution; (C) the treatment step under reduced pressure. (1) The resulting solution is filtered to remove suspended solid particles; (d) The solid particles are washed with steaming water to remove residual sulfuric acid on the surface of the solid particles, followed by about (10). C is heated under vacuum for about 2 hours to know the dried s-PeEK; (e) S_PEEK of step U) is dissolved in dimercaptoacetamide ((1) 邮一ide, DMAc) towel to make a weight Percent concentration spinning solution; (f) Electrospinning using an electrospinning solution of the step (e, yu θ + rain _) to a 4 to s-PEEK fiber membrane substrate. In order to confirm the S_PEEK Weihua in this example, the elemental analysis of s-PEEK was performed in step (e) _ _ r , t

(dement analysis), to obtain the s pEEK ratio, and calculate the weight per singularity of each PEEK monoterpene as shown in the following table, the average score of the acid score, the conclusion: ^ The analysis of the prime, using the prior art, this Explain that in order to be concise, it is no longer detailed: Μβ. The acidification ratio is calculated as the acidification ratio X 100% = (acid radicals / polymer monomer moles)

15 201011963

In the present example, about 96% by weight of HJO4 solution is used as the acidification upgrading solution, the pEEK polymer material is acidified, and then the electric spinning operation parameters used in the present example are shown in Table 3 below;

Liquid flow Operating environment relative humidity 0.5 ml/hr

48% RH Fig. 4 shows an SEM photograph of the s_pEEK fiber membrane substrate 1〇2 according to the present example. It can be found from Fig. 4 that the s_pEEK fiber membrane substrate 1〇2” • the fiber bundles of the towel electrospun fibers are interlaced to form a network structure, and the diameter of the fiber bundle is about 100-8000 nm. (1·3·3) The acidic nanofiber gland substrate prepared in Example i and Example 2 was made into a composite proton exchange membrane of acidic nanofiber/basic polymer. Next, the s_PSU fiber 骐 substrate 102 prepared in Example 1 above was reinforced by PBI. And the s-peek fiber substrate 102'' prepared in Example 2 to make a composite of s_PSU/PBI acid nanofiber/alkaline polymer 201011963 • Proton parent exchange film and s_PEEK/pBI acid nano fiber/ The composite proton exchange membrane of the testable polymer is prepared as follows: (a) preparing a pBl/DMAc solution of about 3% by weight as an alkaline resin solution; (b) a PBI/DMAc solution of the step (a) Coating and spraying on the acidic nanofiber membrane substrate to prepare a composite proton exchange membrane of acidic nanofiber/basic polymer; (c) acid nanofiber/basic polymer of step (b) The composite plasto sub-family was placed in a vacuum oven of about 120 C for about 5 hours to remove Removing the residual DMAc solvent; and (d) impregnating the composite proton exchange membrane of the acidic nanofiber/basic polymer of step (c) in an acid solution (about 85% by weight acid solution) 24 hours, so that the acidic molecules are filled in the pores in the composite proton exchange membrane of the acidic nanofiber/basic polymer. Fig. 5 shows the s_pSU/pBI acid nanofiber/alkaline polymer according to the present embodiment. SEM photograph of the composite proton exchange membrane. Comparing the SEM photographs of Fig. 3 and Fig. 5, it can be found that the S_psu fiber membrane substrate 102' of Fig. 3 has a reticular fiber shape with many pores, and Fig. 5 In the composite proton exchange membrane of s-PSU/PBI acid nanofiber/inspective polymer, almost no pores were observed. It can be proved that the PBI/DMAc solution was sprayed on the third diagram according to the present example. Thereafter, the molecules in the pBI solution are effectively attached to the s-PSU fiber membrane substrate 102, because of the affinity between the sulfonium-based group and the ss3H group on the s-PSU. The following table 4 lists the s-Psu/PBI acid nanofiber/inspective polymer of this example. Composite proton exchange membrane composition and the film thickness. 17 201 011 963 Table 4 component (g) s-PSU 0.356 PBI 0.688 H3PO4 0.650 film thickness (μπι) 38.3

Fig. 6 is a SEM photograph showing a composite proton exchange membrane of s-PEEK/Ppi acid nanofiber/inspective polymer according to this example. Comparing the SEM photographs of Fig. 4 and Fig. 4, it can be found that the s-PEEK fiber membrane substrate 102" of Fig. 4 has a reticular fiber shape with many pores, and the s-PEEK/PBI in Fig. 6 The composite proton exchange membrane of acidic nanofiber/alkaline polymer can hardly see any pores. Therefore, this embodiment is similar to the embodiment shown in Fig. 5, which can be based on the _ bribe and s_pEEK. The affinity between the s〇3H groups is such that the PBI solution can be effectively attached to the WEEK fiber membrane substrate 102". Table 5 below shows the composition of the composite proton exchange membrane of the s-PEEK/PBI acid nanofiber/inspective polymer of this example and the film thickness of 0.

(1) Membrane electrode group and its damage method and single cell test. Further, a preparation electrode group (Membrane Electrode method) of the membrane assembly (MEA) is used. The method utilizes the above example 1 of 18 201011963 s-PSU/PBI acidic nanometer. A composite proton exchange membrane of fiber/inspective polymer and a composite proton exchange membrane of s-PEEK/PBI acidic nanofiber/alkaline polymer of Example 2 were used to prepare a ruthenium electrode group, and the above-mentioned membrane electrode group was used for single cell test. Figure 7 is a schematic view of a membrane electrode assembly 2 according to the present embodiment. The membrane electrode assembly 200 comprises an anode 2, a cathode 202 and a proton exchange membrane 203. The anode 201 comprises a carbon cloth 205 and a catalyst layer 206; The cathode 202 includes a carbon cloth 207 and a catalyst layer 208. The proton exchange membrane 203 is interposed between the anode 2〇1 and the cathode 202, and is in contact with the catalyst layer 2〇6 and the catalyst layer 2〇8, respectively. Membrane electrode group preparation method In the present embodiment, a membrane electrode group 实验 (experimental group), a membrane electrode group 2 (experimental group), and a membrane electrode group 3 (control group) were separately prepared, and proton exchange was performed for the above three membrane electrode groups. The membrane is shown in Table 6 below: __ Table 6 Membrane Electrode-----_ Proton exchange membrane electrode group 1 s-PSU/PBI acid nanofiber (experimental group) Dimensional/inspective polymer composite proton exchange membrane (real 丨 1, membrane electrode group 2 --- \ Only iy_i 1 I s-PEEK/PBI acid nano (experimental group) Fiber/inspective to molecular complex _ proton exchange 1 (眚 you 1 membrane electrode group 3 PBI proton exchange membrane (control group) Known) 19 201011963 . The PBI proton exchange membrane used in the control group of λ is prepared by a conventional method and has a thickness of about 92 μηη because the PBI proton exchange membrane is limited by its own mechanical strength and must have a comparative A large film thickness can provide sufficient support for the proton exchange membrane. The above membrane electrode assembly is prepared as follows: (a) A pBI/DMAc solution having a weight percent concentration of about 2% (wherein the weight ratio of PBI to LiCl is about丨:n Add pt/c (where pt is about 40% by weight, purchased from E_TEKC〇). In the catalyst, adjust the weight ratio of pt/c to pBi • to about 3.5:1 and excite it by ultrasonic 5 Hour to obtain the catalyst slurry; (b) uniformly apply the catalyst slurry prepared in the step (a) to the carbon cloth (purchased from ET ekCo., model: HT25〇〇_w), overcoating to a predetermined pt coating amount to form a catalyst layer, wherein the coating amount of the carbon cloth as an anode is about 0.5 mg/cm as a cathode The coating amount of pt on the carbon cloth is about 〇5 mg/cm2; (c) the anode carbon cloth of step (b) and the cathode carbon cloth are respectively placed at a temperature of about 120 C for about 30 minutes to volatilize the solvent. And then blasting the carbon cloth electrode with distilled water to remove UC1 in the electrode; (d) placing the acidic nanofiber/basic polymer composite proton exchange membrane or proton parent membrane on the anode carbon of step (c) Between the cloth and the cathode carbon cloth, press a contract with a hot press at a pressure of about 140 〇c and about 5 〇 kg/cm 2 for 5 minutes to obtain an individual membrane electrode assembly; (e) the membrane electrode of the step (d) The group was placed in a phosphoric acid solution for about 24 hours at a weight concentration of about 10% to increase the proton conductivity of the catalyst layer, and then stored at room temperature after removal. 20 201011963 (2.2) Single cell test Next, the cell tests of the above-described membrane electrode assembly 膜, membrane electrode group 2, and membrane electrode group 3 were carried out separately. In the present embodiment, the membrane electrode group has an active area of about 5 x 5 cm2. The membrane electrode assembly was activated at a constant current of about 2 mA/cm 2 at about 6 〇〇 c for about 8 hours before the test. Next, the test was carried out using a CHm〇 Fuel ceu Testing system FC 5100 series. The test parameters are shown in Table 7 below: Table 7 Temperature 160 °C Pressure 1 atm Oxygen flow rate 300 ml/min Hydrogen flow rate 300 ml/min

Figure 8 illustrates the potential vs. current density curve (indicated by open circles in the figure) and the power density versus current density curve φ (indicated by solid dots in the figure) at 16 °C. Fig. 9 illustrates the potential vs. current density curve (indicated by open circles in the figure) and the power density versus current density curve (indicated by open squares in the figure) of the membrane electrode group 2 at 160 °C. The first graph illustrates the potential vs. current density curve (indicated by open circles in the figure) and the power density versus current density curve (indicated by open squares in the figure) of the control membrane electrode group 3 at 160 °C. It can be found from Fig. 8 that under the above measurement conditions, the maximum power density of the membrane electrode group 1 (s-PSU/PBI membrane electrode group) can reach about mo 21 201011963 mW/cm, and the maximum current density is about _ women/^ ,

About 2 baht. When the m2 is recognized, the potential of the output can reach ...V. In contrast, J sees Fig. 10, the maximum output power density of the membrane electrode group 3 (the conventional membrane electrode group) is about 90 mw/cm2 'the maximum current density is about mW/cm2' and the current density is about 2 〇〇 (10), the output potential can reach about 0.37 V. That is to say, the electrode group J is superior to the membrane electrode group 3 regardless of the maximum power density or the maximum current density. In addition, the same in the ideal current

膜 At a density of 20 GmW/em2, the membrane electrode group can provide a higher potential than the membrane electrode group 3. Similarly, in the 9th order, the membrane electrode group 2 (s-PEEK/PBI membrane Ray: = the second, the degree can be about - cm2, the maximum current density is about 780 mW / cm, and the current density is about 2 〇 The reading / (^2 potential can reach about 0. 4 V. Compared with the membrane electrode group 3 of the first drawing, the electrode group 2 is superior to the membrane electrode group 3 regardless of the maximum power density or the maximum current density. In addition, also at the ideal current density of 2 〇〇 mW/cm 2 , the membrane electrode group 2 can also provide a higher potential than the membrane electrode group 3. According to the above-described embodiments and related tests of the present invention, according to the principle and spirit of the present invention Compared with a proton exchange membrane made of a single-polymer material such as PBI, the prepared composite nanoproton/alkaline polymer has a significantly smaller film thickness and a remarkable power generation power. In addition, when preparing a proton exchange membrane having an acidic functional group, whether it is electrospinning directly using an acidic polymer, or electrophoresis of the polymer and then acidification, an ideal membrane can be obtained. Composite protons of acid nanofibers/alkaline polymers with thick and power generation The present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention, and any person skilled in the art can make various changes and retouchings without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0009] The above and other objects, features, advantages and embodiments of the present invention will become more apparent. The detailed description is as follows: a first drawing - a schematic cross-sectional view of a composite proton exchange membrane 100 of an acid naphthene/inspective southern molecule according to an embodiment of the present invention; and a diagram showing a PSU fiber according to the present invention - an embodiment SEM photograph of the film substrate; Fig. 3 shows an SEM photograph of the s-PSU fiber membrane substrate obtained by acidifying the PSU fiber membrane substrate of Fig. 2; Fig. 4 shows the s_pE£K fiber according to the present invention - an embodiment SEM photograph of the film substrate; Section 5 shows the SEM image of the composite proton exchange membrane of s-PSU/PBI acid nanofiber/initial polymer made of 帛3® s_PSU fiber membrane substrate; , Figure 6 shows SEM photograph of a composite proton exchange membrane of s-PEEK/PBI acid nanofiber/initial polymer prepared from the s-pEEK fiber membrane substrate of Fig. 4; 'Fig. 7 is not according to an embodiment of the present invention Schematic diagram of the membrane electrode group; Figure 8 illustrates the potential versus current density curve of the s_psu/pBI membrane electrode set made of the composite proton exchange membrane of s-psu(d) acid nanofiber/analytic. The figure shows the power density versus current curve (shown as a hollow square in the figure); 23 201011963 ^ Figure 9 illustrates the s-PEEK/PBI acid nanofiber/alkaline high in Figure 6. The potential of the s_pEEK/Pm membrane electrode group made of the composite proton exchange membrane of the molecule is shown by the current density curve (indicated by a hollow dot in the figure) and the power density versus current density curve (indicated by a hollow square in the figure); 10 Tugeming PBI membrane electrode group (control group) potential vs. current density curve (indicated by open circles in the figure) and power density versus current density curve (indicated by open squares in the figure). [Explanation of main component symbols] 100: Acidic nanofiber/basic high score 200 composite proton exchange membrane 201 102: Acid nanofiber 臈 substrate 2〇2 102' : s-PSU fiber membrane substrate 2〇3 102'' : s-PEEK fiber membrane substrate 2〇5 104: fiber bundle ΖΌό 106: intrinsic resin reference electrode group. anode cathode proton exchange membrane 207: carbon cloth 208: catalyst layer ❹ 24

Claims (1)

201011963 X. Patent application scope: h Preparation method of a composite proton exchange membrane, comprising: (a) preparing an acidic fiber membrane substrate; (b) preparing an alkaline resin solution, and adding about 1% by weight to , force 3 0 /. One of the basic high molecular polymers is dissolved in the dimercaptoacetamide solvent; (c) contacting the basic resin solution with the acidic fibrous film substrate, wherein the acidic fibrous film substrate has multiple pores to accommodate the The alkaline resin solution 'is obtained by combining the basic functional group of the green polymer with the acidic functional group of the acidic fiber membrane substrate; and (d) removing the composite proton exchange Residual dimethylacetamide solvent in the membrane. The method for preparing a composite proton exchange membrane according to claim 1, further comprising impregnating the composite proton exchange membrane with an acid solution to fill the pores of the composite proton exchange membrane with acidic molecules. 3. The method for producing a composite proton exchange membrane according to claim 2, wherein the acid solution is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid or boric acid. 4. The method for preparing a composite proton exchange membrane according to claim 1, wherein the polymerizable polymer is polyamidamine, polyglucamine, polyphenylimide, imidazole, polyaniline, polyfluorene Amines, polyvinyl alcohols, blends thereof or 25 201011963, modified derived polymers. 5. The method of preparing a composite proton exchange membrane according to claim 1, wherein the basic functional group is a primary amine group, a secondary amine group, a tertiary amine group or an -OH group. 6. The method for preparing a composite proton exchange membrane according to claim 1, wherein the step (c) is: coating, spraying, dipping the screen printing, dipping coating or doctor blade coating on the alkaline resin solution. On an acidic fiber membrane substrate. 7. The method of preparing a composite proton exchange membrane according to claim 1, wherein the step (d) is to immerse the composite proton exchange membrane in a vacuum supply tank at about 120 ° C for about 5 hours. 8. The method for preparing a composite proton exchange membrane according to claim 1, wherein the step (a) comprises: ❿ 〇) preparing an electrospinning solution having a weight percentage of @ 6% to about 5% by weight. The molecular polymer is dissolved in dimethylacetamide; (7) electrospinning the electrospinning solution of step (1) to obtain a fiber membrane substrate; and (1) from about 5% to about 99 by weight concentration One of the acid film-modified medium is impregnated with the fiber membrane substrate of the step (2), and the impregnation time is about 5 hours to about 24 hours to obtain the acidic fiber membrane substrate. 9. The method for preparing a composite proton exchange enthalpy according to claim 8, wherein the molecular polymer in the group is poly aryl ether ether, polyether sulfone, polyphenol phosphide, polystyrene, or the like thereof. a compound or a modified derivative thereof. </ RTI> The method for preparing a composite proton exchange membrane according to claim 8, wherein the acid in the bismuth modification solution contains chlorpyrifosate, citrate or cinnamate. The method for preparing a composite proton exchange membrane according to claim 8, wherein the acidified modified liquid is an aqueous sulfuric acid solution having a weight concentration of about 25%. 12. The method for preparing a composite proton exchange membrane according to the claim, wherein the step (a) comprises: (1) adding the molecular weight polymer to a concentration of about 100% to the state of the state, to acidify the modified liquid, Obtaining an acidified high molecular polymer, wherein the weight of the high molecular polymer and the chemical conversion solution is about 1:100; the main (7) is added to the steaming water in a volume ratio of about 1:: "The plurality of acidified high molecular polymers are produced: the floating particles:;" the acidified upgrading liquid of the step (7) is filtered to obtain the suspension (4) to be washed in the steaming water to remove the plurality of drying steps (3). Particles; - I recording and dry operation, the dry (four) of step (4) is dissolved in a ratio of about 5% to about 5 〇 - methyl ethyl amide (6). m electrospinning solution; the electrospinning solution of step (7) is electrospun 27 inch 201011963 to the acid fiber raft substrate. Qin 13. The method for preparing a composite proton exchange membrane according to claim 12, wherein the polymer is poly(aryl ether ether ketone), polyether sulfone, polyphenol nitride, polystyrene, a blend thereof or It is modified to derive a polymer. 14. The method of preparing a composite proton exchange membrane according to claim 12, wherein the acid in the acidification modifying solution contains a sulfonate, a carboxylate or a phosphoric acid. 15. The method for preparing a composite proton exchange membrane according to claim 12, wherein the two molecules of the acidified poly(aryl ether ether ketone), the acidified polyhard, the sulfonated polyphenol phenol phosphide, the sulfonation Polystyrene, blends thereof or modified derived polymers thereof. 16. The method of preparing a composite proton exchange membrane according to claim 12, wherein the acidification modifier is an aqueous solution of sulfuric acid having a weight concentration of about 96%, and is about 50 in the step (1). (: heating and stirring for about 24 hours. 17. A composite proton exchange membrane for use in a proton exchange membrane fuel cell comprising: a plurality of basic resins for proton exchange; and an acidic fiber membrane substrate, wherein the acidic fibers The plurality of ginseng fibers of the film substrate are interlaced to form a network structure having multiple pores to accommodate the alkali resin, wherein the basic functional groups of the basic resin and the acidic fiber film 28 201011963 The composite proton exchange membrane of claim 17 having a thickness of from 5 μηι to about 70 μί. 19. The composite proton exchange membrane of claim 17 having a thickness of about 25 μηι to A composite proton exchange membrane according to claim 17, wherein the material of the acidic fiber membrane substrate is poly(aryl ether ether ketone), polyether sulfone, polyphenol phosphorus nitride, polystyrene, or the like. The composite proton exchange membrane of claim 17, wherein the acidic functional group is a sulfonate, carbonate or phosphate. Composite proton exchange membrane, wherein the materials of the test resins are polyamidoamine, polyglucamine, polybenzimidazole polyimine, poly-amine, polyamine, polyvinyl alcohol, blends thereof or The composite proton exchange membrane of claim 17, wherein the basic functional group is a primary amine group, a secondary amine group, a tertiary amine group or a -hydrazine group. 24. A membrane electrode assembly comprising 29 201011963 an electrode group comprising an anode and a cathode; and a composite proton exchange membrane as claimed in claim 17, interposed between the anode and the cathode. The membrane electrode assembly of item 24, wherein the anode comprises a carbon cloth and a catalyst material disposed thereon. The membrane electrode assembly of claim 24, wherein the cathode comprises - φ carbon cloth and is located therein The membrane electrode assembly of claim 25 or 26, wherein the catalyst material comprises a turn. 28. The membrane electrode assembly of claim 25 or 26 wherein the catalyst material Contains platinum and carbon. 30