• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    Electrocatalysts which may be used in the preparation of electrodes for electrochemical cells such as fuel cells comprising a refractory inorganic oxide having a carbonaceous pyropolymer forming at least a monolayer on the refractory oxide, the surface of said pyropolymer having at least one catalytically active metal impregnated thereon may be prepared by treating a refractory inorganic oxide with a pyrolyzable organic compound to form at least a monolayer of a carbonaceous pyropolymer on the surface of said refractory inorganic oxide, thereafter impregnating the resulting composite with a complex of a soluble salt of at least one catalytically active metal and a sulfur-containing carboxylic acid, heating the impregnated composite to remove the solvent, reducing the dried composite and thereafter recovering the resultant electrocatalyst.
    公开号:SU791204A3
    申请号:SU772475082
    申请日:1977-04-19
    公开日:1980-12-23
    发明作者:Брайан Велш Лоренс；Ладислав Герверт Джордж
    申请人:Юоп Инк (Фирма)；
    IPC主号:
    专利说明:

    Calcium hydrochloric acid, or its solution, containing hydrochloric acid and thiomalonic acid in a selected ratio, is carried out after the application of the pyropolymer. This allows platinum to be introduced into the catalyst under conditions where it does not agglomerate with contraction of the active surface.
    The catalyst prepared by this method allows a current density of 50 mA / cm to be obtained when air is passed at a voltage of 0.24 V or oxygen is passed through respectively 155 mA / cm at 0.45 V.
    Example 1. Z-alumina is ground to particle size. 2 µm and calcined at 550 ° C for three hours. Calcined alumina powder is placed in a liquid reactor and treated with benzene, which is passed over alumina at 900 ° C for 1.5 hours. The resulting material is additionally stabilized at atmospheric pressure and at a temperature of about For 1.5 hours, then 53.9 g of the material is mixed with a solution obtained by dissolving 4.9 g of hydrochloric acid containing 24.7% of platinum with 110 grams of deionized water. - -,
    This mixture is stirred at ambient temperature for 0.5 hours, evaporated, and dried at 110 ° C for 6 hours. After drying, the resulting substance is reduced with hydrogen at 535 ° C in a vertical reactor for 1.6 hours. The mixture contains 2 , 24 wt.% Platinum and 40.35 wt.% Carbon, the surface area of the mixture is 82, and the resistance of the substance of the mixture at room temperature is 018 Ohms. cm.
    Example 2 (comparative) In contrast to Example 1, the electrocatalyst is prepared by impregnating the substrate with a catalytically active metal followed by deposition of a pyropolymer layer on the metal surface. For this aluminum, in the form of a powder, is calcined at. For 3 hours. Then, 100 g of PVA oxide is mixed with a solution obtained by diluting 15.75 g of 24.7% hydrochloric acid in 110 g of water for 0.5 h. After that, the WATER is evaporated on a water bath and dried for 1, 5 hours and reduced with hydrogen at a temperature of 543 ° C for 2 hours. 35 g of the recovered Pt / ft Z O- powder are treated with 33.6 g of benzene in a liquid reactor at 901 ° C and atmospheric pressure. The obtained carbonized substance is additionally stabilized for 1.5 h at. The resulting mixture contains
    by weight 2.21% platinum and 40.62% by weight carbon, the surface area is 68, the resistivity is 0.010 ohm-cm.
    Example 3 The electrocatalysts prepared according to examples 1 and 2 are used to make fuel cell electrodes. These electrocatalysts, in their raw form, are mixed in an organic solvent medium with polytetrafluoroethylene powder, filtered and the catalyst layer is prepared by calandrization. This layer is pressed against the surface of the tantalum mesh, which is a current collector and is sintered in a nitrogen atmosphere at. The catalyst layer has a thickness of about 0,012 cm, with a platinum content of 5 mg / cmH
    The evaluation of the efficiency of the electrodes is carried out by assembling a fuel cell in which electrodes are made by molding a mixture of graphite and acid resistant rubber. The fuel cell matrix is a mixed structure consisting of phenolic phenolic binder kinol fibers; this matrix is filled with phosphoric acid, pre-treated with hydrogen peroxide. The electrodes are placed on both sides of the matrix and are tested as cathodes by passing air or oxygen or by passing pure hydrogen as anodes. The electrocatalyst prepared according to the procedure described in Example 1, when tested in a fuel cell with air passing, allows a current density of about 50 mA / cm to be obtained at a voltage of 0.24 V (the voltage drop inside the cell and the voltage drop to be taken into account. conductors). When oxygen is passed through an element, the current density is 155 mA / cm at a voltage of 0.45 V. The electrocatalyst prepared in example 2, by depositing a catalytically active metal on the surface of alumina before the carbonized pyropolymer is deposited on it, when tested as a cathode By air bleeding, a current density of about 16 mA / cm npif voltage of 0.21 V and a current density of -42 mA / cm at a voltage of 0.28 V when oxygen is pumped through the fuel cell, is obtained.
    Example 4. The electrode is made of γ-alumina coated with a pyropolymer as a result of pyrolysis of the mixture with benzene at 900 ° C. The resulting material contains 34 wt.% Carbon and has a surface of 75 m / g, an average particle size of 2 microns and a specific resistance of about 0.014 ohm-cm at 25 ° C. This substance is impregnated with water.
    a solution of platinum hydrochloric acid with a concentration sufficient to ensure that the electrocatalyst, after drying and reduction, contains 10% by weight of platinum. An electrode with a platinum content of 0.5 mg / cm is prepared from this electrocatalyst and tested in a fuel cell at a temperature of about 140 ° C as a cathode with air and oxygen pumping and as an anode with hydrogen pumping. In the case of using an electrode as an air pumping cathode, it is possible to achieve a current density of 100 mA / cm at a voltage of 0.63 V (the voltage drop inside the cell and in the supply conductors is taken into account). In the case of oxygen pumping at the cathode, a current density of about 100 mA / cm is obtained at a voltage of 0.75 V, and in the case of using an electrode as an anode with hydrogen pumping, the current density is 100 mA / cm at a voltage of 0, 62 V.
    Example 5. To illustrate stability, electrodes made of electrocatalysts are used that have properties similar to those of the electrocatalyst described in the example. 4, except that the platinum content of the electrode is 0.25 mg / cm. This electrode is tested in a fuel cell for a period of 24 and 2000 hours of cell operation at a temperature of about 140 s as in Example 4. The test results show that during the test the air cathode operates with gradually increasing efficiency, which means that the electrocatalyst in the fuel cell containing phosphoric acid as an electrolyte is distinguished by good stability.
    The table shows the values corrected for the voltage drop inside the element and the voltage drop in the supply conductors.
    Similarly, these electrodes are tested at temperatures
     instead of 140 g. As a result of these tests, for example the strain xeiig increases by 15% with n.noi nose j;:, about 100 mA / cm.
    Example 6 Isho, centr;: o; j-alumina is crushed to particles ranging in size from 1, 3 to 2.5.; Km with a bulk density of 0.30, - with a surface of 70-7 pores with a diameter of about JLOO .A and calcined at 550 ° C for 3 h. The resulting powder
    is placed in a liquid reactor and treated by passing benzene vapor for 1.5 hours. The carbonized material is stabilized for 1.5 hours at atmospheric pressure, after which it contains 34.1% by weight of carbon and has a specific resistance at room temperature 0.02 ohm-cm,
    Then a complex of platinum (IV) with thiomalonic acid is prepared by
    0 mixing of three moles of thiomononic acid with one gram of platinum in an aqueous solution. To do this, mixing a; .-- g of an aqueous solution of platinum hydroxyhydrogen
    5 acids, containing 27, -19% of the plate, with 6.47 g of thiomalonic acid and 60 g of deionized water, are left to stand for 18 hours at room temperature, as a result of which
    0 the required comp is formed: l: ex. Half of the complexag solution is stirred for 0.5 h at 25 ° С to 25 g of carbonized oxide, and then dried in a thermostat at 110 ° С
    5 for 3.5–,: h0,: is reduced in current at 260 s for 2 h. The resulting electrocatalyst contains 4.9% by weight of platinum g; The size of krnstal litas is not more than 25 A with a degree of agglomeration equal to 1%
    0
    The resulting electrocatalyst is treated with the remaining half of the solution of the platinum (IV) complex with thiomeric acid, dried at 110 ° С for 3.5 h and reconstituted
    5 in a stream of hydrogen for 2 hours at. After the second impregnation, the electrocatalyst contains 9.84% by weight of platinum with a nominal size of platinum crystallites of about 34 A at
    0 degree. Agglomeration 3%,
    Example 7. The carbonized oxide is prepared according to Example 6. It is impregnated with an aqueous solution of platinum. hydrochloric acid that does not contain thiomalonic acid. The dried and reduced impregnated starting material contains 9.73% by weight of platinum, and the crystallite size of platinum does not exceed 76 A, and the degree of agglomeration is 49%.
    Example 8. An electrocatalyst prepared according to Example 6 was used to prepare a fuel cell electrode. An electric calcium analyzer comprising x; d-aluminum oxide containing carbonized pyropolymer impregnated with a complex of platinum hydrochloric acid and thiomalonic acid on the surface was analyzed. it was found that 9.84% by weight of platinum was contained in the electrocatalyst, and the nominal diameter of platinum crystallites was about 34 A with a degree of agglomeration of 3%. The resulting electrocatalyst in a wet state is mixed in an organic dissolution medium with tetrafluoroethylene powder and, after filtration, forms a catalyst layer by means of calendering. This layer is pressed onto the surface of a current collector, which is tantalic acid, and is fixed on this surface in a nitrogen atmosphere at a temperature of about. The catalyst layer has a thickness of 0.005 cm and a catalyst content of 0.50 mg / cm,
    The efficiency of the electrode is carried out by testing a fuel cell in which the electrodes are made by molding a mixture of graphite and acid-resistant rubber. The matrix of the fuel cell is a mixed structure consisting of kinol fibers and a phenolic bond. This matrix is filled with phosphoric acid pretreated with hydrogen peroxide. The electrodes are pressed against the matrix of the fuel cell on both sides and tested in the cathode mode with the flow of air or oxygen. When testing electrocatalyst in a fuel cell with air pumping at
     the current density is approximately 100 mA / cm at a voltage of 0.63 V (the voltage drop inside the cell and the voltage drop in the supply conductors are taken into account). When using the electrode as an oxygen cathode, the current density is 120 mA / cm at a voltage of 0.73 V.
    权利要求:
    Claims (2)
    [1]
    1. Filshtih V. Fuel cells. M., Science, 1968, p. 27.
    [2]
    2. US patent number 3381957,
    cl. 136-121, publ. 1973 (prototype).
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    同族专利:
    公开号 | 公开日
    ZA772257B|1978-03-29|
    US4031292A|1977-06-21|
    CA1083551A|1980-08-12|
    BE853691A|1977-08-16|
    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/678,003|US4031292A|1976-04-19|1976-04-19|Method for the preparation of an electrocatalyst|
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