TWI344233B - Method for manufracturinga electrolyte membrane - Google Patents

Description

1344233 MODIFICATION OF ALTERNATE PAGE OF DECEMBER 23, DECLARATION OF THE INVENTION [0001] The present invention relates to the field of fuel cell technology, and more particularly to a method of manufacturing an electrolyte membrane. [Prior Art] [0002] A fuel cell is a battery device that uses an electrochemical reaction to generate electricity. The working principle is that a fuel gas (such as hydrogen) and a combustion-supporting agent (such as oxygen) are respectively supplied to the anode and cathode of the battery to be oxidized. In response to the reduction, the chemical energy is converted into an electrical energy output. The two advantages of high efficiency and low pollution of fuel cells have made the technology widely noticed since its development. At present, the governments of developed countries such as the United States, Japan, and Canada have formulated relevant policies to develop fuel cells. [0003] Proton exchange membrane fuel cell is the fifth generation of advanced fuel cell, in addition to the general characteristics of the fuel cell, such as not limited by Carnot Cycle, high energy conversion efficiency, etc., but also has a normal temperature and quick start, no Outstanding advantages such as electrolyte loss, long life, specific power and specific energy. Proton exchange membrane fuel cells can be divided into two categories according to the fuel they use: one is a hydrogen fuel cell that uses pure hydrogen or reformed hydrogen as a raw material; the other is a direct methanol fuel cell that is directly fueled by methanol (Direct Methanol Fuel Cell). , DMFC). Although hydrogen is an ideal fuel for proton exchange membrane fuel cells, when pure hydrogen is used as fuel, hydrogen storage and transportation are not only dangerous, but also a huge investment in the establishment of hydrogen supply equipment; although reforming hydrogen can avoid new fuel supply equipment, However, it is necessary to add a gas reforming purification process, which will undoubtedly increase the cost of the battery; in addition, the structure of the fuel cell is complicated, so that the upper limit is 094112056. Form No. A0101 Page 3 / Total 12 Page 1003059851-0 1344233 100 February 23 The Japanese nuclear replacement page has made its large-scale application. Relatively speaking, the direct sterol fuel cell is most prominent in that its fuel is replaced by liquid sterol instead of hydrogen as a fuel, which greatly improves the fuel cell portability and safety, and can be conveniently applied to various portable electrical appliances such as notebook computers and PDAs. , GPS and so on. [0004] The problem of methanol permeation of proton exchange membranes is a major technical problem currently present in direct methanol fuel cells. Perfluorosulfonic acid membranes such as the Naf ion membranes widely used in hydrogen fuel cells have a high methanol permeability. The sterol passes through the proton exchange membrane and reaches the cathode. On the one hand, it does not generate electricity with oxygen.

Should cause oxidant waste; in addition, according to the active position of the oxidant, the oxygen can not be reduced, the quality of proton exchange can reduce the permeability of the overall performance of the membrane, and the high performance of the alcohol-resistant energy exchange membrane system can be developed. The key to direct collapse of alcohol fuels. :r:.

[0005] The Chinese Patent No. 0211_5. 7 published on September 15, 2004 discloses a direct sterol sulfonic acid film which is made of polystyrene as a raw material, and an acylating agent and concentrated sulfuric acid are used. The complex is used as a sulfonated 3 琢jf 谬 styrene sulfonic acid membrane. Among them, by controlling the degree of sulfonation and the distribution of sulfonic acid groups during the preparation process, the polystyrene sulfonic acid membrane is modified to reduce the proton conductivity of the membrane and reduce the penetration of sterol in the membrane. The permeability improves the alcohol resistance of the membrane material. [0006] The Fujitsu Institute of Japan announced on December 8, 2004 a prototype of a direct sterol fuel cell for notebook computers. The maximum output power of the battery is 15W, which can be driven when using 300ml of sterol solution. The company's laptop "FMV-BIBLOMG55E" runs for 8 to 10 hours. It uses 094112056 Form No. A0101 Page 4 / Total 12 Page 1003059851-0 1344233 100 February 23 Nuclear: The material of the polymer electrolyte membrane is replaced with an aromatic main chain structure, which is similar to the commonly used fluorinated resin. Compared to the spatial structure of polymers, there is a big difference. The polymer electrolyte membrane has a certain rigidity and is fine, and is as strong as engineering plastics, and the effect of sterol permeation through the electrolyte membrane is increased by about five times. According to this polymer electrolyte membrane, even if the concentration of the decyl alcohol solution is 30%, the permeation phenomenon does not occur and the output power is lowered. [0007] A U.S. Patent Application Publication No. 20050042499, issued Feb. 24, 2005, discloses a DMFC system. Referring to the first figure, the DMFC structure has a cathode 2, an anode 11 and an electrolyte membrane 4, the cathode 2 and the anode 11 are located on the opposite side of the electrolyte membrane 4, and an anode 3 is disposed inside the electric 'decomposition membrane 4 and is connected to the anode. 11 is electrically connected, which divides the electrolyte membrane 4 into a region 12 and a region 13. The methanol needs to pass through the electrolyte membrane 4 from the anode 11 to the cathode 2, passing through the anode 3, and the sterol which reaches the anode 3 will be consumed by the oxidation reaction, so that the sterol which reaches the region 13 will be greatly reduced. Therefore, the DMFC structure utilizes the provision of a plurality of anodes to gradually reduce methanol, effectively preventing methanol from passing through the electrolyte membrane. [0008] In summary, in order to solve the technical difficulty of methanol in the DMFC system, the electrolyte membrane affects the performance of the battery, and provides an electrolyte membrane which can effectively inhibit the penetration of sterol and make the performance of the DMFC better. The method is really necessary. SUMMARY OF THE INVENTION [0009] Hereinafter, a method of manufacturing an electrolyte membrane will be described by way of examples. [〇〇1〇] In order to achieve the above, a method for producing an electrolyte membrane is provided, which comprises the steps of: providing an electrolyte substrate; forming a first metal film layer on the electrolyte substrate by vapor deposition; using electroless plating In the 094112056 Form No. A0101 Page 5 / Total 12 Page 1003059851-0 [0011] [0014] [0017] [0017] 094112056 A second metal layer is formed on a metal film layer . Correction replacement page on February 23, 100 | The electric (four) film manufacturing method of the present technical solution is simple in operation and low in cost. When the prepared electrolyte membrane is used in a fuel cell, the electric (four) membrane can effectively prevent the fuel from passing through the electrolyte, reducing (4) waste, avoiding reduction of the cathode effect flb, and improving the battery power supply efficiency. [Embodiment] Hereinafter, an electrolyte membrane, a method for producing the same, and a fuel cell having the electrolysis (4) will be described in detail in conjunction with the examples. The second figure is a direct smelting smelting squaring. Included is an electric ^ f m 1 ο ο * τ. # 123⁄4 χ ' has an electrolyte base 鼙 110, a gold 110, whose composition usually includes Nji sterol fuel. The p-type film 100 has a 解ι-solvent matrix which can block the electrolyte matrix 110 from being a common proton exchange membrane, and the % sub-exchange membrane-based fuel cell is an electrolyte, 邋, often || polymer film or solid polymer film. At present, the company's total gas sulfonic acid membrane Naf ion series membranes, such as Naf ion'riVh%, 112, 105, etc. The anode 200 and cathode 300 are typically made of graphite, composite carbon or metal. Further, the anode 200 and the cathode 300 include a catalyst, a gas diffusion layer, and the like. The method for producing the electrolyte membrane includes the steps of: first, preparing an electrolyte matrix; and forming a metal film on the electrolyte substrate. First, an electrolyte matrix is provided. Form No. A0101 笫&Page/Total 12 Pages

1003059851-0 1344233 On February 23, 100, the shuttle replacement page [0018] The electrolyte substrate used in this embodiment includes a commonly used perfluorosulfonic acid series membrane, and the alcohol-blocking property disclosed in the prior art can also be used. A proton exchange membrane such as a polyvinylsulfonic acid membrane, or a polystyrene sulfonic acid membrane or the like. [0019] Next, a metal film 120 is formed on the electrolyte substrate 110. [0020] The metal film 120 is mainly used to prevent fuel from passing through the electrolyte substrate to the cathode, avoiding degradation of cathode performance and waste of fuel. The metal film 120 may be formed on the anode side, the cathode side or the anode side and the cathode side of the electrolyte substrate 110. When formed on the anode side, fuel can be prevented from entering the electrolyte substrate 110 to avoid fuel waste; when formed on the cathode side, the fuel can enter the electrolyte matrix 110, but does not pass through to the cathode, avoiding fuel affecting cathode performance, and also preventing the cathode The oxidant enters the electrolyte substrate 110 to avoid waste thereof; when the metal film 120 is formed on both the anode side and the cathode side, neither the fuel nor the oxidant enters the electrolyte matrix 110. [0021] The atomic deposition method is one of the methods for forming a film layer on the surface of a material, and the atomic deposition method can be classified into a liquid phase deposition method and a vapor phase deposition method. Liquid deposition methods include electroplating, electroless plating, electrophoresis, etc.; vapor deposition methods include physical vapor deposition, chemical vapor deposition, and the like. In general, the vapor deposition method has a better film formation effect than the conventional liquid phase deposition method, but the cost is high. [0022] The metal film 120 is formed on the electrolyte substrate 110 of the present embodiment, and physical vapor deposition may be employed. Physical vapor deposition methods include evaporation, sputtering, ion plating, etc. Among them, sputtering is widely used because of its excellent deposition efficiency, controllability of large area deposition thickness, and precise composition control. [0023] The metal film 120 is formed on the electrolyte substrate 110 of the present embodiment, and may also be replaced by a liquid phase deposition method using 094112056 Form No. A0101 Page 7 / 12 pages 1003059851-0 - Γ 344233 In view of the non-conductor of the electrolyte substrate 110, electroless plating is employed. Electroless plating, that is, electroless plating, requires only immersing the material to be plated in a chemical solution and chemically reacting to form a film on the surface of the material. This method is simple to operate and low in cost. In practical applications, vapor deposition is usually used in combination with electroless plating. [0024] The thickness of the metal film 120 has a great influence on its alcohol resistance, and the greater the thickness, the better the alcohol barrier property. In practice, when the fuel cell requires a thick metal film of 120, the vapor deposition cost is high. Therefore, vapor deposition can be combined with chemical plating. Referring to the third image deposition method, a genus is formed on the electrolyte substrate 110, and then a first metal lake metal film H2 is applied by electroless plating.

Second thickness

Therefore, in practical applications, the thickness of the metal film 120 is small, and the vapor deposition can be directly used.

Sheep thin [0026] The following will directly explain the kroner ^

V

[0027] Wince sterol aqueous solution is used as fuel from the anode to the fuel cell system

The sterol reacts with water to produce hydrogen ion (proton) electrons and carbon dioxide under the action of a polar catalyst. The anode reaction equation is as follows: 2CH3〇H + 2H2〇-2C〇2+12H++12e—(1) [0029] Hydrogen ions (protons) generated by the reaction can reach the cathode 300 through the electrolyte membrane 100, and the electrons pass through The circuit reaches the cathode 300, which is the process by which the fuel cell supplies power to the load. 094112056 Form No. A0101 Page 8 / Total 12 Page 1003059851-0 On February 23, 1100, the shuttle is replacing the page with the gift of cathode gas or gas from the cathode input fuel cell system under the action of the cathode catalyst. Hydrogen ions (protons) and electrons combine to form water. The cathode reaction equation is as follows: Just 3〇2 + l2H+ + 12e-—6H2〇(2) 闺 Combining equations (1) and (2) gives the general equation of fuel cell reaction as follows: _] 2CH3〇H + 3〇2, 2 + 4H2〇 ( 3) In the methanol fuel cell of the country I, when the fuel sterol solution reacts at the anode, part of the sterol will diffuse through the electrolyte to the cathode, and the metal film 120 coated with “, pd, Pt or Au can effectively prevent methanol. [0035] In this embodiment, a direct sterol fuel cell is taken as an example, and the electrolyte membrane 100 coated with the metal film 12() can prevent the methanol from reaching the cathode, which reduces the cathode performance and wastes the fuel. The sterol fuel cell performance [0036] The electrolyte membrane 10 本 of the present embodiment is not limited to a direct methanol fuel cell, and for a fuel cell using other fuels such as hydrogen, ethanol, ethylene glycol, ether, etc., the metal film 120 is changed. The composition can also prevent the fuel from passing through the electrolyte membrane 100. In addition, the 'metal membrane 120 not only prevents the fuel from passing through the electrolyte, but also prevents the cathode oxidant such as air or oxygen from passing through the electrolyte membrane to avoid oxygen. The electrolyte membrane of the present invention uses a common proton exchange membrane as a matrix, and a metal membrane is formed on the substrate. When the fuel cell using the electrolyte membrane is operated, the metal membrane layer can effectively prevent the fuel from passing through the electrolyte membrane. Reaching the cathode, reducing fuel waste, avoiding the reduction of the cathode performance, and improving the battery power efficiency 1» 094) 12056 Form No. A0101 Page 9 / Total 12 pages 1003059851-0 1344233 100 years of February 23 g replacement page [0038] As described above, the present invention does not comply with the requirements of the invention patent, and the patent application is filed according to the law. However, the above description is only a preferred embodiment of the present invention, and the scope of the patent application of the present invention cannot be limited thereto. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the present invention are intended to be included in the scope of the following claims. [0040] [0045] [0045] [0045] BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1 is a schematic view showing the structure of an electrolyte membrane disclosed in U.S. Patent Application No. 20050042499. The second drawing is an embodiment of the present invention, Schematic diagram [Main component transfer number description] Thunder glare: 1 ftf) Electrolyte substrate: no Metal film: 120 First metal thin layer: 121 Second metal thin layer: 122 Anode: 200 : *ίηπ

The third figure is the electricity of the present embodiment.

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094112056 Form No. A0101 Page 10 of 12 1003059851-0

Claims (1)

On February 23, 100, Shuttle Replacement Page 1344233 VII. Patent Application Range: 1 · A method for manufacturing an electrolyte membrane, comprising the steps of: providing an electrolyte matrix; forming a first metal on the electrolyte substrate by vapor deposition a film layer; a second metal film layer is formed on the first metal film layer by electroless plating. 2. The method of producing an electrolyte membrane according to claim 1, wherein the electrolyte substrate is a common proton exchange membrane. 3. The method for producing an electrolyte membrane according to claim 2, wherein the common proton exchange membrane comprises a polyvinylsulfonic acid membrane, a polystyrenesulfonic acid membrane or a perfluorosulfonic acid membrane. 4. The method for producing an electrolyte membrane according to claim 1, wherein the first metal film layer is formed on the electrolyte substrate by physical vapor deposition. 094112056 Form No. A0101 Page 11 of 12 1003059851-0