前苏联专利SU1110389A3 Method for making catalytically active electrode of fuel cell

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专利摘要:
1. METHOD FOR PRODUCING A catalytically active electrode chemical current source by applying to a metal substrate a homogeneous solution of a nickel compound and a molybdenum compound with posleduyuprsh thermal decomposition of these compounds to sootvetstvuyupschh okislovl-oxides and curing the coated bases in a reducing atmosphere at elevated temperature, wherein, ni and c the fact that, in order to ensure high activity and stability, the homogeneous solution also contains a rare-earth compound at wearing nickel to molybdenum from 1.5: 1 to 6.3: 1 and the atomic ratio of the sum of nickel and molybdenum to the rare-earth element from 2.7: 1 to 19: 1. 2. A method according to claim 1, tl and h and s - g so that, in order to ensure homogeneity of the precipitated alloy, the homogeneous solution is an aqueous solution containing nickel nitrate, ammonium paramolybdate and cerium nitrate or lanthanum nitrate, nitric acid or citric acid.,
公开号:SU1110389A3
申请号:SU813343478
申请日:1981-05-12
公开日:1984-08-23
发明作者:Эммерсон Браун Дэвид；Мартлю Холл Стефен；Ноуралдин Махмуд Махмуд
申请人:Дзе Бритиш Петролеум Компани Лимитед (Фирма)；
IPC主号:

专利说明:

00
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with
The invention relates to a method for producing catalytically active electrodes of a chemical current source.
A known method for producing a catalytically active electrode is a chemical current source by depositing a transition metal compound and a screw 1 on the substrate.
However, thus obtained: the catalyst loses its activity.
The closest to the proposed technical essence and the achieved result is a method of manufacturing a catalytically active electrode chemical current source by applying a homogeneous solution of a nickel compound and a molybdenum compound on a metal base, followed by thermal decomposition of these compounds to the corresponding oxides and solidification of the oxide coated substrate in a reducing medium at a high temperature of 12.
However, such electrodes are not sufficiently active.
The purpose of the invention is to increase the strength and stability of the electrodes.
This goal is achieved in that according to the method of manufacturing a catalytically active electrode a chemical current source by applying a homogeneous solution of a nickel compound and a molybdenum compound to a metal base, followed by thermal decomposition of these compounds to the corresponding oxides and curing the coatings with base oxides in a reducing environment at elevated temperatures, the homogeneous solution contains also a rare-earth compound with an atomic ratio of nickel to molybdenum from 1.5: 1 to 6.3: 1 and the atomic ratio of the sum of nickel and molybdenum to the rare-earth element from 2.7: 1 to 19: 1,
To ensure homogeneity of the precipitated alloy, the homogeneous solution is a water solution containing nickel nitrate, ammonium paramolybate and cerium nitrate or lanthanum nitrate, as well as nitric acid or lidyunic acid.
The homogeneous solution of the alla compounds used for the application of an opening can be a mixture of the corresponding metal compounds in the form of solid particles in a finely dispersed state, a solid solution of metal compounds or a solution of the compounds in solvent. A dense mixture of metal compounds in the form of solid particles can be prepared in advance or the compounds can be mixed immediately before contact with the substrate to be coated. An example of the latter is the simultaneous deposition of the corresponding metal compounds on a substrate; if premixing is performed, the mixture may, for example, be sprayed from a single-jet metallization gun. In accordance with this technique, the metal oxides themselves are directly sprayed onto the metal substrates of the electrodes. When using solutions in solvents, the solvent may be aqueous, for example water, an acid system or an aqueous solution of ethyl alcohol, or an organic solvent, for example methanol, ethanol, propanol, isopropanol, formamide or methylformamide. The choice of particular solvent will depend on the solubility of the desired metal compound in the solvent.
In certain cases, if aqueous systems are used, there may be tendencies for one or more metal compounds to separate during precipitation — in particular, if the solution is allowed to settle even for a relatively short period of time. For example, an aqueous solution containing nickel nitrate, cerium nitrate and ammonium molybdate, may require a small amount of nitric or citric acid to produce a clear solution.
If the homogeneous solution is a liquid, it can be applied to the surface of the substrate to be coated, for example, by dipping, spraying or rubbing with a brush. The coated substrate is then heated at elevated temperature to decompose the metal compounds to the corresponding oxides. The decomposition is expediently carried out in an atmosphere in air at 250-1200, preferably 350-900 ° C. The coating of a homogenous solution on the substrate, accompanied by thermal decomposition, can
be repeated several times to ensure a suitable surface coating of the substrate with metal oxides.
If the homogeneous solution of the metal compound is a mixture of solid particles, it can be applied to the substrate using a melt spraying technique, such as flame spraying or plasma spraying. If such a technique is used, the steps of coating metal substrates on the substrates and thermal decomposition are carried out in one step. This is due to the relatively high temperature associated with this spray technique, with the result that metal compounds can be decomposed into their oxides.
Substrates, coated with metal oxides, regardless of whether they are coated with a homogeneous liquid or a mixture of solid particles, are then heat treated in a furnace in a reducing atmosphere by heating at 250-700 ° C. Hydrogen is preferably the reducing atmosphere, and the heating temperature is 350-600 ° C. The optimum activity of the electrode used as a cathode is achieved when it is restored at a temperature of about EPA, whereas for use as an anode, it is advisable to restore the electrode at a temperature above, preferably bOOC. Some change in the optimal heat treatment temperature can be achieved by changing the duration of the heat treatment.
The electrodes made by the proposed method have a high degree of activity and stability.
The stages of making an electrode are mo- ,. They should be chosen so as to ensure an appropriate level of catalyst filling on the surface of the substrate. The catalyst content is higher than 5 mg / cm (based on the weight of the active materials deposited on the substrate surface), preferably more than 10 mg / cm. The final filling will depend on the mechanical stability and integrity of the coating required, the substrate used and the element in which the electrode is to be used. It has been found that very close electrode potentials (on the order of +1.48 V, depending on the reversible hydrogen electrode) will create oxygen at a current density of 500 mA / cm at TOC in a 30% KOH solution. This reduction in electrode potential will not only ensure the operation of elements at a high current density, but will also significantly increase the economic efficiency of such elements.
One of the more important features of the proposed electrodes is their oxidation resistance. For example, a nickel-molybdenum-lanthanum coated electrode made using a solution stabilized with nitric acid using drying with does not exhibit any increase in overvoltage, i.e. the initial potential depending on the reversible hydrogen electrode at 500 mA / cm is 101 mV and remains substantially unchanged and stable.
Example 1. The manufacture of the electrode (electrode 1-6).
Two homogeneous solutions are prepared, and only the components of the lanthanide group are changed. For example, dosage volumes containing nickel nitrate hexahydrate (2M), paramolybdenum ammonium tetrahydrate (0.143M) and cerium nitrate (1, OM) or lanthanum nitrate (1.0 M) are mixed together to obtain solutions of the required compositions. A few milliliters of concentrated nitric acid is added in each case to obtain a pure homogeneous solution.
Three. Clean woven nickel grids with a 60 mesh weave are coated with corresponding homogeneous; . solutions using the immersion-pyrolysis technology or spraying pyrolysis (see tab. 1). Immersion-PI 50 rolls are made by dipping the spoons in the form of a nickel mesh in a homogeneous solution and then drying in an oven at 3OO-EOO C. This operation is repeated several times until 55 a visible satisfactory film of metal oxides is formed on the substrate. from nickel mesh. An oxide-coated nickel grid is then heated in a furnace in a reducing atmosphere of hydrogen at a temperature of about 500 ° C for 1 hour. Spray-pyrolysis is carried out by applying a coating solution to each side of a clean substrate using a laboratory spray gun. The substrate is heated in an oven at 300900 ° C for 10 minutes and then cooled to room temperature. This operation is repeated several times until the coating of the desired thickness is peeled off. Then, the resulting substrate is heated in an atmosphere of hydrogen for 1 h. The electrodes thus fabricated are used as anodes. In each case, the electrode potential is measured at anodic polarization of 500 mA / cm in a KOH solution at. The electrode potential, measured for various electrodes according to the invention, is compared with the electrode potentials for standard electrodes without a lanthide component. The results are shown in Table. 1. All measured electrode potentials are estimated with respect to a reversible hydrogen electrode. Example 2. The manufacture of electrodes (electrodes 7-18). Samples of nickel mesh size 14x14 mm with a mesh size of 60 mesh (number of holes per inch) are sprayed with a solution of coating material and, before the list of test electrodes and their electrode potentials with anodic polarization 500 mA / cm in 30% KOH at 89 6 constituting an aqueous solution of nickel nitrate, ammonium paramolybdate, and lanthanum nitrate, to which I added nitric acid to obtain a pure green solution. The atomic ratio of nickel, molybdenum, lanthanum in the coating solution is given for each electrode in Table. 2. After sputtering, decomposition is carried out in one of two ways: a) the sprayed samples are dried at 100 ° C in air for 5 minutes and then heated for 5 minutes in a stream of nitrogen; b) the sprayed specimens are heated for a period of time from 30 s to 1 min either in the Bunsen burner or in the air flow in the furnace. These operations are repeated approximately 10 times until the desired catalytic deposition (35-40 mg / cm2) is reached. The samples are then restored within 1 hour in a stream of hydrogen at 150-600 0. Electrochemical measurements (electrodes 7-18). These electrodes are tested in a source containing 30% KOH at 70 ° C. The counter electrode is a nickel mesh. A saturated, nahalome electrode is used as a reference electrode. All electrode potentials are measured at 500 mA / cm-2. The results achieved using electrodes as anodes and cathodes are shown in Table 2. Table 1
one
Ni
"one
Nimo
1.5: 1
Ni - - 1.63 1.78 () Ni 500 30 l, 48 1,585 ()
Continuation of table 1

权利要求:
Claims (2)
[1]
1. METHOD FOR PRODUCING A CATALYTICALLY ACTIVE ELECTRODE OF A CHEMICAL SOURCE OF THE CURRENT by applying a homogeneous solution of a nickel compound and a molybdenum compound to a metal base, followed by thermal decomposition of these compounds to the corresponding oxidation and curing of the oxide-coated base in a reducing medium at elevated temperature, distinguishing I with the fact that, in order Collateral ¹ cheniya'vysokoy activity and stability, homogeneous solution also contains a compound of a rare earth element with an atomic Aspect the ratio of nickel to molybdenum from 1.5: 1 to 6.3: 1 and the atomic ratio of the sum of nickel and molybdenum to rare earth element from 2.7: 1 to 19: 1.
[2]
2. The method according to claim 1, with the exception that, in order to ensure uniformity of the precipitated alloy, the homogeneous solution is an aqueous solution containing nickel nitrate, ammonium paramolybdate and cerium nitrate, or lanthanum nitrate, nitric acid or citric acid. ,

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

GB8015797|1980-05-13|

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