TWI250683B - Organic-inorganic hybrid proton exchange membrane and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid proton exchange membrane and manufacturing method thereof, which discloses an organic-inorganic proton exchange membrane (PEM) having low fuel crossover compromising no proton conducting capability. A nano-class inorganic layered material is mainly used and is processed by a swelling agent to make it swelling to be blended with a PEM material. Such inorganic layered material is distributed in the PEM base material to form a nano-class organic/inorganic hybrid structure and alter the nano clustering structure in an electrolyte. Therefore, in addition to strengthening an organic PEM structure, such hybrid structure can also reduce the fuel crossover phenomenon in operation of fuel cell. As the surface of the inorganic layered material is also provided with a functional group capable of conducting proton, the addition of the inorganic layered material won't lower the conductivity of the proton exchange membrane.

Description

1250683 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a proton exchange enthalpy, in particular to an inorganic PEM material impregnated with a nano-scale inorganic layered material, thereby producing a low A proton exchange membrane that is fuel penetrating and does not affect the proton conductivity of PEM. [Prior Art] In recent years, the potential of the application of Proton Exchange Membrar^ Fuel Cell (PEMFC), electrochemical reactors, and sensors has been highly valued. Naf i〇n (Peffluoi Ocartoi Sulphonic Acid Polymer) developed by Dupont is currently a more practical material for the replacement of the scorpion, but the current price of Nafion is still very expensive, and its material properties will be Not _ in direct methanol feed Wei f & (Direet _ survey (

Fuel Cell, DMFC). The direct oxime feed type fuel cell (10) FC) uses an aqueous methanol solution as a fuel for the battery, A_ generates electrons and hydrogen ions (piOt〇n) by the anode catalyst reaction, and hydrogen ions are ions containing no electrons, which are - bare protons. The electrons pass through the circuit outside the pool (4) and return to the cathode of the battery. The hydrogen ions ride through the hunting exchange to the cathode of the battery, and then return to the oxygen and the electrons from the external circuit through the cage S.

The shells are brought together and passed through the PEM to enter the cathode while the cathode, / Xi consumes the catalyst and oxygen, reducing the electrode activity of the cathode 1250683. This phenomenon is called the methan〇i crossover. It also results in the inability to increase the concentration of methanol fuel, which is one of the main reasons for the inefficiency of DMFC and the decline in overall energy density. For the needs of polymer electrolyte fuel cells, proton exchange membranes must have good ionic (proton) conductivity, mechanical strength, thermal and chemical stability, and moderate swelling, and the gases involved in the reaction (for example) The permeation and diffusion of hydrogen or methanol (in direct methanol fuel cells, DMFC) must be low. / See the commercialized Nafion proton exchange membrane, although it is well tolerated, but because of its limitations, its film thickness and conductivity specifications are limited, and the permeability of methanol is too high (at N = fi〇 The penetration of the DMFC methanol of the n film can reach 4% of the feed amount, so it is necessary to seek a new film which can be produced in a large amount and can be produced in a large amount and in a phase. " It is known that some methods for solving the penetration of fuel in ρΕΜ are as follows: - reducing the ionic concentration of bismuth materials or using other materials such as ρΕΜ#, the concentration of ionic groups in strontium is determined by the proton conductivity. The key, but the higher Xuanqi degree is expected to form a hydrophilic group in its structure, which in turn causes the penetration of methanol. Therefore, there are some known techniques and studies that use a different ionic concentration PEM as a layered structure' or use a benzene ring-containing polymer to be acidified to control the concentration of the ionic group, and continue to lower the cap (four) penetration phenomenon; Many of these must be operated at high temperatures to have better feron conductivity, or the literature uses traditional composite concepts to combine electrolytes with another fiber or porous

= The conductivity of the sub-segment is lower with the drop in methanol penetration. In addition, there is also a low electrolyte swellability, but the related prior art is listed as follows: Table 6 1250683 Patent Technology and Technology US 5,525,436 US 5,716,727 US 6,025,085 US 6,099,988 US 6,124,060 US5,599,639 US 6,365,294 US 6,444,343

Acid doped-PBI, which uses the heterocyclic ring of imidazole to provide proton conduction. The monthly b-force is suitable for the environment where the car is suitable for the southerly waterless environment.

PEM PSSA+PVDF cross-linking reaction film using Polyphosphazene substrate can achieve low crossover ° US 4,626,553 US 5,447,636 US5J95.668 US 6,242,122 Two different ionic groups but the same main segment of the high score + layer

Nafion+HDPE, PTFE laminate, film-enhancing film that enhances film selectivity and enhances the mechanical properties of the film. One layer is two or more layers of different ion exchange rates of Pd film-------- laminated film with different EW values _ Second, change the way PEM materials transfer protons; change the way of proton transfer is to change the protons from the original PEM ionic conduction, to the proton hopping method using inorganic solid acid groups (H〇pping (4) conducting conduction. However, since organic materials are difficult to have such a characteristic, inorganic materials have always been inherently hindered in the processability of film formation, and inorganic materials having high proton conductivity at room temperature are dissolved in water. The stagnation is not good, and the breakthroughs and progress of knowing technology in this respect are limited. The known related patent technologies are as follows: _^ Know patent technology - technical means and functions JJS 4,594, 297 Z^llJ^gpolyacid, gas phase use. ___ 1250683 US 4,380,575 one 3 with Zeolite as electrolyte (cafe blood 1) _ organic/inorganic hybrid material - reducing the volume of the hydrophilic cluster of traditional pEM materials; In the early studies of PEM, in order to improve the water saturation of pEM used at high temperature, or to reduce the Crossover phenomenon of helium oxygen, some conventional techniques use a simple synthesis reaction to fill the inorganic metal oxide in the cluster of pEM material, or It is directly infiltrated with PEM materials, and it is expected to enhance the proton conductivity of PEM at high temperatures and reduce the penetration of fuel, such as reducing the sterol permeability of dmfc, but most of the experimental results found that The method is usually difficult to improve greatly, because the use of inorganic substances to reduce the penetration rate of some sterols in pEM reduces the conduction path of protons and reduces the proton conduction capacity due to the reduction of the Cluster volume in the PEM material. The known patented technologies are as follows: Table 3 shows the patent technology - technical means and functions US 4,687,715 J5, 849, 428 PTFE + ΖιΌΡ porous j joined the conductor _______ new method of depositing ZrOP in PEM US 5,919,583 PEM +Inorganic Proton Conductor for DMFC, 1〇w __γ, high conductivity US 6,059,943 and 6,387,230 PEM + ZrOP for high temperature And improve the conductivity, s〇L GEL method US 5,795,496 s-PEEK, s-PES + zeolite using high-performance engineering plastics sulfonation, making the polymer film proton conductive; additionally adding Shen Yi 1 he lowered Crossover US 6,447,943 ------ PEM + Porous + Acid, using porous materials to create a large amount of space 'filling in sorrow or stagnation acid' to reduce Crossover 1250683 [Summary]

The main object of the present invention is to provide a proton exchange with low fuel permeability. The present invention mainly utilizes a meter-scale inorganic layered material uniformly dispersed in a substrate of a proton exchange membrane (pEM) to form an organic /Inorganic hybrid structure and change the structure of the paste in the electrolyte, the effect of the low PEM in the fuel towel to the low fuel penetration. Another purpose of this description is to propose a proton exchange membrane suitable for direct methanol feed fuels, DMFC, which has low methanol permeability and does not affect proton conductivity. (Electrical conductivity). Ming proposed a technique for synthesizing an inorganic nano-layered material, which is swollen by swelling = treatment and blended with a simple material to achieve nano-scale dispersion.最大ίϊΐ The greatest advancement of the prior art is that its nano-dispersed layered material can be made of Li: a 2 ΡΕΜ structure and only requires a small amount of addition, which can reduce the swellability in the u-bucket, so it is not easy to confront the protons. The conductivity causes a change. ==The surface of the rice-level layered structure also has a functional group capable of conducting protons. This does not increase the conductivity of the material. For example, the method for producing a proton exchange membrane basically includes the following steps: The weight ratio is 0·lwt%~20wt%. Preferably, the material is heated to remove the solvent to form a proton exchange membrane. In the selection of the layered material, the compound with cationic cross-linking is 9 1250683 main, and the preferred embodiment disclosed in the present invention uses Zirciumium Phosphate (ZrOP) as the inorganic layer. The material, because it has a phosphate group on its surface that can transport protons, can help proton conduction after mixing with the organic proton conducting membrane. Since the Zr〇p materials obtained on the market are all amorphous structures, the present invention produces two different kinds of Zr〇p by self-synthesis, and is swelled and dispersed by using two different amine salts. The examples are as follows: [Example 1]: Synthesis of zirconium phosphate (Zr〇p) 1. Dissolve about 21 to 23 g of ZrOCL··8 (solid) in 320 ml of deionized water. (22.1846 g) 2. Add 16 ml of Hydrofluoric Acid (HF) (40 ° / 〇). 3. Add 184 ml of 85% phosphoric acid (H3p〇4). 4. The number of water baths at 60 ° C (48) hours. 5. The product was filtered and washed with deionized water (6 mL). 6. Place in a 110 C oven for a few (18) hours of drying. [Example 1] Synthesis of Benzene-ZrOP 1·16 ml (0·〇2 mol) of ZrOCl2 (30% solution, d=L 344) was mixed with 15 ml of a 40% HF solution. 2. Add 6·4828g (〇·〇41mol) phenylphosphonic acid (pre-dissolved in 180ml of deionized water). 3. Place in a water bath at 70~80 °C for a number of (3) days. 4. Filter the product and wash it with deionized water (approach). 5. Place in an oven at 110 ° C for a number of (18) hours. The two synthetic ZrOPs were identified by X-ray Diffractometer (XRD) as shown in Fig. 1. As for the swelling treatment of the swelling agent, the present invention utilizes two different amine salts and swells and disperses, which is a compound having an anion exchange group. The examples are as follows: [Example 1]: Dispersing ZrOP with tetrabutylammonium hydroxide (及0Η) and the result·1·1·0880g ZrOP is dissolved in 100ml of deionized water. 2. Slowly drip in 〇· 5M TBA0H to pH=8. 3. Stir for 18 hours (hr) and centrifuge the solution. The XRD pattern identification results are shown in Fig. 2. [Example 2]: The method of dispersing ZrOP with PPA (propylamine) and the results: : 1 · Take 1·1183 g of ZrOP dissolved in 113 ml of deionized water. '2· Add 18 ml of 0.2 amino apron (Propyl amine) in 4 hours. 3. Stir for 18 hours (hr) and centrifuge the solution. The XRD pattern identification results are shown in "Figure 3". ZrOP is observed by a TEM-Transmission Electron Microscopes before being swelled and dispersed, and a micrograph is shown in Fig. 4 to obtain a nanometer. The graded inorganic layered material has an aspect ratio greater than 50 and a thickness less than i 〇〇 nm. After swelling and dispersing ZrOP, it is uniformly mixed with proton exchange membrane precursor (Nafi〇n Solution, 5wt%, the substrate of the invention using Nafion material as proton exchange membrane), and then heated in an oven. The solvent is removed to complete the organic/inorganic hybrid proton exchange membrane of the present invention, which is produced as follows:

Naf ion/ZrOP blending method: 1. Add the swollen ZrOP material to the Naf ion solution. 2. Add two times the volume of N-decylpyrrolidone (NMp) solution of Naf ion Solution. 3. Vibrate for 30 minutes with ultrasonic waves. 4. Stir the number at 70 ° C for (6) hours. 1250683 5. Pour the above mixed solvent into a Petri dish. ^ Put in the box for heating at 80 °C ((8) hours. ^ j dish into the vacuum box for 3Q minutes (13G °C true S) or 170 °C for 30 minutes (vacuum). I used to t' this organic 7 Proton exchange membranes blended with inorganic materials, tested for capacity (conductivity) and methanol permeability, and protons made with Suixian U7 membranes and different inorganic layered materials Cross = 仃 仃 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The results are shown in Table 4 below: Table 4

Conductivity (S/cm) - Conductivity Methanol Permeability (cm2/s) - Methanol Permeability

Nafion/TBAOH-ZrOP lphr

Nafion/TBAOH-ZrOP 3phr 5.6*10 0·6*10· Nafion/PPA-ZrOP lphr 4.5* ΙΟ Ι.0*1 O'6

Nafion/PPA-ZrOP 3phr

Nafion/PPA-ZrOP 5phr 5.5*10' 2.5*10· 0.4* ΙΟ* 0.6*10" A proton exchange membrane made of Nafi〇n mixed with the above two different inorganic layer materials, Zr0P, and Proton exchange membranes made by Naf ion are traditionally identified by the XRD pattern as shown in Fig. 5. "Figure 5" shows the XRD patterns of three different materials, one is Nafion's original crystal diffraction peak, and the other is Nafion's crystallographic diffraction peak (Nafion/ZrOP), which is mixed with "unmodified" ZrOP. After 1250683, it is the crystal diffraction peak of Nafion and Zr〇p after blending and modifying. It can be found from the map that if ZrOP is not modified, the crystallization peak can still be found after blending (two, mixed spectra of different materials), indicating that the layered crystal structure is not completely dispersed. However, if swelled with a swelling agent, only the original crystalline peak of Nafi〇n remains, indicating that the layered crystalline structure of ZrOP has been completely separated into nano-layered materials. [Effect of the Invention] From the result data of the above examples, it was found that the use of an amine-based swelling agent can increase the interlayer spacing of the ZrOP shell-shaped conductor (the xrd spectrum diffracts the peak toward a small angle) or the knife (such as the TEM result). After blending with Nafion Solution, the layered structure is completely expanded by the force between the molecules to form a nano-scale sheet structure. The experimental results show that after the addition of the dispersed Zr〇p inorganic substance in a small amount, the material can be helped to lower its fuel permeation characteristics without lowering its conductivity. The above description is only the preferred embodiment of the present invention and is not intended to limit the scope of the present invention. That is, the equivalent changes and modifications of the content of the patent application scope of the present invention should be the technical scope of the present invention. [Simple description of the figure] Figure 1 shows the results of the xrd pattern identification of two synthetic Zr〇p. Fig. 2 shows the results of XRD pattern identification of ZrOP dispersed by ΤΒΑ0Η. _ Figure 3, the results of XRD pattern identification of Zr〇p dispersed in ppa. Fig. 4 is a photomicrograph of TEM observed before and after dispersion of ZrOP.

Figure 5 is a comparison of the XRD patterns of the organic/inorganic blend film of the present invention and a conventional Nafion film. [Main component symbol description] 13

Claims (1)

91250683 X. Scope of application for patents·· An organic-inorganic hybrid 交, its structure An organic proton conducting membrane substrate; and a nano-scale inorganic proton film substrate with proton conductivity. 9 + class self-dispersed in the 2nd, as claimed in the scope of patent application, the structure of the base material of the helmet 曰 传导 为 具 阳离子 阳离子 = 贝 贝 贝 贝 贝 贝 | ^ ^ ^ ^ ^ ^ ^ ^ fi fi fi fi fi fi fi fi fi fi fi fi fi fi fi fi , wherein the sub-conducting ability sub-exchange membrane is a smectic layered inorganic oxide. The structure is an organic-inorganic hybrid proton exchange membrane having a cation exchange group of 5.4, the zirconium material, the inorganic grade The layered material is a cation exchange group of oxidized 6· machine to proton exchange membrane, wherein the acid group. The wrong material 枓 its _ sub-exchange group is a phosphate group or benzene continued 7. The fourth organic organic-inorganic mixture A proton exchange membrane, wherein the material such as Shenjing-like inorganic oxide is phosphorus oxidized or benzene-weihuan. The octa 9 匕 (rat ^ rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat rat The method of inorganic mixed proton exchange membrane material is to mix the inorganic layer material with a swelling agent, and to remove the solvent to form a mixed proton exchange membrane material. π. Patent application scope 1G The method of claim 1, wherein the proton exchange membrane precursor solution is a Nafion solution. The method of claim 1, wherein the swelling agent is at least one anion exchange group compound. The method of the present invention, wherein the swelling agent is a Propyl amine (PPA) tablet. The method of claim 1, wherein the swelling agent is Tetrabutylaminehydroxide (TBAOH). The method of claim 1, wherein the inorganic layered material is oxidized by phosphorus. The method of claim 1, wherein the layered material after dispersion of the swell agent has an aspect ratio of at least greater than 5 Å. The method of claim 10, wherein the thickness of the σH layered material dispersed by the swell agent is less than ΙΟΟπιη. The method of claim 10, wherein the inorganic layered material after the inorganic layered proton exchange membrane precursor solution is blended has a weight ratio of G·lwt% to 2 Gwt%. Shouting film material 15 ^25«6S3 H^一,图 L\ rcunium Zi l'cuni uni Phosphate iliriiv Iphi.iSplici l:e 16 1250683 Figure 3 Figure 4 17 1250683 In ten si. i v O I n e 80 in \a f i on \af i ZrOP Naii£v=i 18