Electrode material

[Detailed Description of the Invention]

The present invention relates to the improved electrode material and its process. Chlorine, alkali metal hydroxide, for example, sodium hydroxide, and a potassium hydrate are industrially manufactured by electrolysis of alkali-metal-salt ghost solution corresponding in an electrolysis vessel. In one method of an electrolysis vessel with which the anode is separated from the negative pole by ion permeability barrier membrane, chlorine is reaction:2C4-->C12+2e. It generates "Be alike" in the anode, and, on the other hand, hydroxyl ion reacts: 2 H20+ 2 e -+H2+ 20 In the negative pole, it generates by H-. The latter reaction is a multi stage reaction in fact, hydrogen is absorbed by the negative pole surface and a hydrogen molecule is emitted from it. If all the hydrogen reactions assumed to be a series of adsorption and a discharge process are Polarity(ed) with oxygen instead of the negative pole in a chlorine tub generating hydrogen, an oxygen reduction reaction will be theory top 0.4. They are about O and S in an alkaline solution so that saving of abbreviation 1.2v may be possible, since V may be produced. V is consumed. The negative pole conventionally developed for the oxygen use as a Polarity agent is characterized by the Hungry sandwiches structure which will comprise the microporous separation board of the plastic which combined with the contact-ized layer, for example, was water-resistance-ized by polytetrafluoroethylene, and was press-fitted on the wire net current collector. In the Polarity(ed) conventional negative pole, oxygen is pushed in a microporous lining and supplied all over a catalyst region. Such the negative pole is used. However, these have various faults like the outflow of separation of various layers or exfoliation, and a microporous layer. The present invention comprises the substrate covered by one copy at least with the mixture of a binding material and an electrochemically active conductive catalyst, and a mean diameter is 0.3. It is related with the electrode material being the covered particles smaller than To 2.5crIl thicker than mm. the present invention comprises solidifying mixing fluid for the mixing fluid of an active conductive catalyst and a binding material on a raw threat substrate electrochemically again, and combining a catalyst -- electrode material -- 2.5 cm of To thicker than 0.3 dish -- until -- it is related with the process of the electrode material forming by particles with a mean diameter. The present invention comprises the substrate which there are also still few electrodes, while was covered with the conductive mixture of one catalyst one copy at least with the hydrophobic substance, and each particle is 0.3. Hardening of a large number with the diameter of diagonal length to To 2.5 CI'rL thicker than mm It is related with the method of electrolyzing solution in an electrolysis vessel with the anode liquid room containing the anode which comprises supplying electrolysis solution to the electrolysis vessel currently formed with the electrode material comprising It was particles, pushing in current between the anode negative poles, and collecting electrolysis output, and the negative pole liquid room containing the negative pole. In the electrolysis vessel in which the present invention has the anode liquid room in which the anode is contained again, a negative pole liquid room containing the negative pole, a means to supply electrolysis solution to an electrolysis vessel, and a means to collect electrolysis output from a male means and a tub in current between the anode negative poles, The substrate by which there is also little anode or negative pole, while one copy is covered at least with the conductive mixture of one catalyst with the hydrophobic substance is comprised, and each particle is Q, 3 It is related with the electrolysis vessel currently formed with the electrode material comprising the particles by which a large number with a mean diameter smaller than To 2.5cIrt thicker than mm were hardened. There may be ion permeability barrier membrane between the anode negative poles of a tub arbitrarily. The tub may have a feeding means of the gas to an electrode arbitrarily. It turns out that these particle floors are convenient as a gas electrode. An electrode can be used as the negative pole or the anode. The substrate which has a tunic attached upwards must be the material which maintains the shape. As the useful method of particle manufacture of the present invention, a substrate is good in it being a substance which does not change substantially, when it heats at the temperature of 350-375"C for 1 hour. The sintered substance, the solid substance, or the condensation connective of a granule may be sufficient as a substrate. Si S1 to whom steel, iron, graphite, nickel, platinum, copper, and silver are in suitable structure material It does not limit to these. Since especially graphite is [ that it is easy to receive ] cheap again, it is preferred. The thing of the composition from which the thing of the same composition as a tunic is also different may be sufficient as a substrate. Conductivity or non-conductivity may be sufficient as a substrate. Since resistance is small for passing electric energy to particles, a conductive substrate is preferred. Since one copy is covered by the conductive film and becomes a current path at least, a non-conductivity substrate can be used. However, electrical load must not be in particles, but must flow through the surrounding film of particles, and a non-conductivity substrate has strong resistance. The mean diameter of particles is 0.3. It is to a To 2.5CrrL dog thicker than mm. Generally for using it as an electrode material, the smaller particles of 2.5 are preferred. This makes surface area the maximum and gives the Kota porosity to a particle floor again. It is 0.7 when using particles as an electrode material. Especially the diameter of a particle of mrrt thru/or 4 Relation is preferred. 0.3 mm and smaller particles serve as high resistance easily to the liquid flow which is got blocked and is in a particle floor. 2 Since the surface area which an electrochemistry reaction starts is the minimum, a larger substrate than *5CrfL is not preferred. The thing of what kind of shape may be sufficient as particles. Irregular form particles can also be used conveniently. However, since globular form particles form a particle floor with the optimal porosity and surface area, they are preferred. Irregular form particles are got blocked and tend to make porosity of a particle floor the minimum. The substrate does not need to be inactivity chemically to the electrolysis solution or output of the electrolyzing method which uses particles. However, a substrate is inactivity chemically, and it will be desirable if a tunic does not need to cover a substrate completely. If a substrate is not inactivity chemically, the tunic to attach is a perfect tunic in order to prevent a reaction with a substrate, an electrolysis solution, or electrolysis output. The tunic on a substrate is a mixture of a binding material and an electrochemically active conductive catalyst. The binding material must be a substance made in the shape of fluid by fusion, distribution, or the dissolution. A binding material needs to be chemically stable also to any electrolysis solutions or output which will contact when using in an electrolysis vessel. A binding material must be stable enough at the operation temperature of the electrochemical tub used. Since the catalyst mixed with a binding material is conductivity, conductive necessity does not have the binding material itself. A porous film or a non-porosity film may be sufficient as a tunic by the structure material of a substrate. As long as a substrate is inactivity chemically to an electrolysis solution, a porous film may be sufficient as a film. However, the film must not be non-porosity in order to prevent the reaction which starts between a substrate, an electrolysis solution, or electrolysis output, if a substrate is not inactivity chemically to an electrolysis solution. The hydrophobic substance of a binding material is preferred. When used as an electrode material, a hydrophobic binding agent makes a particle surface generate a bubble, and most often contacts gas and a fluid. Unless a binding material is hydrophobicity, a particle surface gets wet and a bubble does not arise. Various hydrophobic substances are used as a binding material. A hydrophobic substance is poly fluorocarbon, for example, polytetrafluoroethylene, Polychloro-trifluoroethylene, poly trifluoro ethylene, a polyvinyl Bird ghost, The poly Vinylidene ghost and a copolymer may be sufficient, and Interpolymer and Terpolymer with tetrafluoro ethylene, trifluoro ethylene, chloro trifluoro ethylene, a Vinylidene ghost, and a vinyl Bird ghost may be sufficient. Especially a desirable thing is polytetrafluoroethylene. Particles include an active conductive catalyst electrochemically in a tunic again. Operation method t To spend using electrode material in selection of a catalyst. This example of operation has reduction of oxygen and oxidization of hydrogen. A desirable catalyst has carbon black, platinum, silver, and a thing like activated carbon in reduction of oxygen. Especially carbon black is preferred because of the good physical property and availability. A desirable carbon black catalyst has the surface area of 100 thru/or 1000 mper catalyst Durham '. 150 thru/or soo, and especially a catalyst with the surface area of i/g are preferred. a substrate -- a binding material and a catalyst mixture -- one copy -- or all are covered. It is good for covering to have covered the particle surface substantially. Suitable thickness may be sufficient as a film. Thickness is especially preferred in it being about 1 mil. l This which this covers all the surfaces of particles substantially, and holds a catalyst-binding material required to cover particles moreover -- it becomes suitable enough thin films. Since the substantive part of a catalyst is further covered with a catalyst or a binding material, a thickness of 5 thru/or 6 mil or more serves as nothing and Useless in that it is not used for a reaction. A tunic may also include a peroxide decomposition catalyst arbitrarily. Although it is a place which the present invention expects, a peroxide decomposition catalyst may be in both the enclosure top of particles, and the inside of particles. Since the catalyst which has not been exposed is ineffective, its particles that a peroxide decomposition catalyst is on the external surface of a substance so that a catalyst may not become useless are good. A peroxide decomposition catalyst is a transition metal which is known for this technical field and has hydrogen adsorbent typically. Desirable peroxide decomposition metal is steel, silver, platinum, gold, and those mixtures. Especially the mixture of silver, platinum and those mixtures or a compound, and carbon black is preferred. Especially other desirable kinds of known peroxide decomposition catalyst are the compounds of (1) alkaline metal, alkali Male metal and ■B fellows metal, and the transition metal that (2) compounds have electric contact nature or surface contact nature. Especially a desirable thing is an ashes titanium stone. The process of the covered particles which are suitable for use as an electrode material is within the limits of the present invention. The covered particles generate an electrochemically active granular substrate and conductivity catalyst and joint fluid, and are manufactured. A catalyst is combined with a substrate by solidifying mixing fluid. In this way, particles with a binding material and the substrate covered one copy at least with the catalyst are formed. Mixing fluid mixes a point One granular substrate with a catalyst and a binding material, and is generated. A mixture is made to fluid by one method in some. The binding material itself heats, and it can soften or fuse it. After softening or fusing a binding material, it may mix with a catalyst and a substrate, or may mix it with a catalyst and a substrate on that spot. The various softening temperatures or melting points of the substance which carry out suitable as a binding material are known by the person with the knowledge of this field. These can be known in a chemicals reference book or a manual. The exception method of mixing fluid generation distributes a binding material, a catalyst, and a substrate in a fluid medium. Various fluid media which do not react to three ingredients of a mixture can be used. Especially other fluid material that is not water or a solvent of which ingredient of a mixture, either is preferred. It may be good also as dispersion liquid after three-ingredient mixture, or it may be distributed on the body before and after other ingredient mixture any of an ingredient they are. It is important in a fluid medium to distribute a part for 3 Prestige suitably. The 3rd method of mixed-solution generation is the method of dissolving a binding material in a solvent. The dissolved binding material is next mixable with a catalyst and a substrate. The solvent must have solvent power in neither the substrate nor the catalyst. A binding material dissolves after other ingredient mixtures or before mixture. If mixing fluid is generated, it will be solidified in order to combine a catalyst with a substrate. A mixture can be solidified by one method in some. A solidifying method twists mixing fluid to the method used for generating at first. Mixing fluid only cools generation Sai ↓ shelf The mixture by fusion or softening of a binding material, and can solidify a binding material. If 1 of an ingredient or 2 or more are distributed to a fluid medium and mixing fluid is generated, a fluid medium is removed from a mixture and it can solidify. It can evaporate and remove a fluid medium, a fluid medium heating a mixture, and being able to carry out evaporation removal of the fluid medium, or applying a vacuum to a mixture. If the method of dissolving a binding material in a solvent is taken to liquid compound generation, a solvent is removed and it can solidify. A solvent is removable by the reaction of heating evaporation, vacuum removal or a solvent, and other ingredients. A mixture can be processed so that it may prevent the particles covered during solidification adhering mutually and being united as arbitrarily. Churning is a useful method as particles do not adhere mutually during solidification operation. The amount of churning and grade to be used are the minimum, and are made in Durability which only agitates or shakes a substance during solidification. Churning under solidification promotes the homogeneity of the film on a substrate again. The particles covered to solidification successor mind are heated to the temperature near the softening temperature of a binding material more than softening temperature, and combination of the substance to a substrate can be promoted. If it heats to this temperature, will soften a binding material, and it will be made to further mix with a catalyst, and will be made to join together well with a substrate. Arbitrarily, a particle covering process can be repeated repeatedly. Thus, the quantity and thickness of a tunic are based on the number of times of repetitive operation. Film thickness is not important for the present invention. Arbitrarily, since Wet by the substrate and the binding material of a catalyst is promoted, a surface-active agent can be added to mixing fluid. In this way, even the good distribution of a mixture contacted and averaged is securable. It is good to use the surface-active agent which can be removed from the combined back particles. Since this does not get wet with an electrolysis solution when using the covered particles for electrode material, it is preferred. Gas bubble generating on a particle surface is preferred as indicated above. At this point, existence of a surface-active agent will make bubble generating the minimum, since Wet of the particles by an electrolysis solution is promoted. A surface-active agent desirable as a result is a nonionic surface-active agent which thermal decomposition is carried out and serves as carbon residual substance Durability. this kind -- the surface-active agent is well known in this field -- further -- a detailed explanation -- in short -- there is nothing . Arbitrarily, after-combination particles can all remove the catalyst which is washed and has not been combined with a substrate. Other fluids which are not water and a solvent of the ingredient of a tunic are suitable. Since it is convenient, especially water is preferred. The weight or the capacity ratio to a substrate of a catalyst and a binding material is based on the degree of covering on a substrate to desire. If a little films are desired, a little catalysts and binding materials may be clearly mixed with a substrate to mixing fluid generation. Conversely, if a thick film is desired, it is necessary to increase the quantity of a catalyst and a binding material. The ratio of the amount of catalysts to the amount of binding materials can be changed over the wide range. For example, if polytetrafluoroethylene is used as a binding material again using carbon black as a catalyst, the weight ratio of 4:1 thru/or 1:4 may be sufficient. the desirable ratio of carbon black pair PTFE -- weight -- 1 2 -- it is 1.5 thru/or 1.5:1. Other catalysts and binding materials should also be used by this same general ratio. It is convenient, if metal, for example, silver, platinum, or other metallic powder are used as a catalyst and you denote the rate by capacity instead of weight. A metallic powder versus binding material ratio may be capacity, and may be within the limits of 4= 1 thru/or 1:4. As for the ratio, 1:1.5 thru/or 1.5:1 are preferred by capacity. Arbitrarily, various additional catalysts can be added to mixing fluid. One desirable embodiment of the present invention has addition of a peroxide decomposition catalyst with a carbon black catalyst. When using two sorts of these catalysts, all the the use 1 thru/or 35% of the weight of amounts of catalysts should consider it as a peroxide decomposition catalyst, and it should consider as the carbon black catalyst 65 thru/or 99% of the weight again. It is desirable, if 3 thru/or 10% of all the catalysts are made into a peroxide decomposition catalyst and 90 thru/or 97% is made into a carbon black catalyst again. This catalyst mixture must be used by the ratio which described the catalyst versus binding material ratio previously. The peroxide decomposition catalyst used for mixing fluid generation is usually a catalyst outrider substance. That is, in order to make into the catalyst itself the substance used for mixing fluid, it is a compound of the catalyst which needs to be decomposed thermally or chemically. It can be made to carry out in every stage of this creation-of-particles operation with which it was thermal or chemical splitting was covered. Before mixing a substance with a binding material or a substrate, it is good to decompose thermally or chemically. If it carries out like this, thermal or the chemical splitting of a catalyst outrider substance can be adjusted better, and it is obtained in the maximum contact between carbon black and a peroxide decomposition catalyst. If it is mixed and decomposed before two sorts are mixed with a substrate and a binding material, it will be obtained in the maximum contact between carbon black and a peroxide decomposition catalyst. Since the particles with which the present invention was covered are conductivity and are contact activity, they are suitable for using it for electrode material. These can be conveniently used as a hardened particle floor electrode. It is formed in a particle floor in itself, and is suitably supported within a tub. Electric connection of these is made with the power supply which leads to the tub. Current Co L / Chewy can be used arbitrarily. A wire net pipe, a wire net container, etc. which surround the contact-ized particles and into which it is putting it may be satisfactory for a current collector. If the covered particles include a peroxide decomposition catalyst, particles are applicable to hydroxide generation in an electrolysis vessel. If the covered particles do not include a peroxide decomposition catalyst, particles can be used for peroxide formation in a tub. According to the desirable embodiment of the particle usage of the present invention, alkaline metal halogenation thing solution is supplied to the anode liquid room containing the anode, the negative pole liquid room containing the negative pole, and the electrolysis vessel that has ion permeability barrier membrane arbitrarily. Typically, the anodes are VALVE (valve) metal with the suitable electric contact surface, for example, titanium, tantalum, tungsten, columbium, etc. In this field, the anode electric contact surface which carries out suitable is known, and has transition metals, those oxides and a compound especially platinum group metals, those oxides, and a compound. A compound with oxides, such as a platinum metal metal oxide, VALVE metal, i.e., titanium, tantalum, tungsten, and columbium, is especially preferred. Electrolysis solution permeability barrier membrane, for example, precipitation asbestos barrier membrane, the asbestos barrier membrane formed beforehand, or microporous composition barrier membrane may be sufficient as ion permeability barrier membrane. moreover -- although ion permeability may be sufficient as ion permeability barrier membrane -- palmy Onik of cation selectivity -- (permionic) barrier membrane and Do electrolysis solution impermeableness may be sufficient. general -- cation selectivity -- barrier membrane Onik palmy is a fluorocarbon polymer with the given acid radical. representation -- a target -- a sulfonic group, a carboxylic acid group, a Phosphon acid radical, phosphoric acid machines, those outrider substances, and those reaction products are in Acid group. Anode liquid is pH 1, and 5 thru/or 5.5 in solution containing solution or potassium chloride 180 which generally contains 120 thru/or 250 g/l of sodium chloride thru/or 350g/11. Supply liquid is the saturation or the substantial saturated solution which generally contains 300 thru/or 325 g/l of sodium chloride, or 450 thru/or 500 g/l of potassium chloride. The negative pole liquid collected from an electrolysis vessel is negative pole liquid which contains 15 thru/or 25 % of the weight of sodium chloride or potassium hydrate 15 [ about ] 20 % of the weight and potassium chloride 20 [ about ] thru/or 30 % of the weight for sodium hydroxide 10 [ about ] thru/or 12 % of the weight in electrolysis solution permeability barrier membrane use. the case where ion permeability barrier membrane is the cation selectivity palmy Onik barrier membrane which intervenes between the anode negative poles -- negative pole liquid output -- sodium hydroxide of 10 thru/or 45 weight □ -- moreover (the potassium hydrate of 15 thru/or 65 % of the weight of Up is included.) In order especially to generate the negative pole output of the anode output of chlorine, and alkali metal hydroxide and not to generate hydrogen gas output substantially, supplying current to an anode room from a negative pole room, it is good to supply an oxide, for example, oxygen, air, or air with abundant oxygen to a negative pole room. Especially the present invention is aimed at the hardened desirable particle floor negative pole with the particles with which this specification statement was covered. An electrolysis vessel with the ion permeability barrier membrane which intervenes between the anode liquid room constituted from material which bears salt manufacture matter-ized alkali-metal-salt ghost solution by the present invention, the anode in it, the negative pole liquid room which comprised material which bears concentrated alkali metal hydroxide solution, the negative pole in it, and the anode negative pole is provided. The electrolysis vessel of the present invention is characterized by the To apprehend negative pole from the negative pole liquid rooms and each particles which have a means to supply an oxidizer in the electrolysis solution of the negative pole interior of a room. In other desirable embodiments of the method of using the above-mentioned particles for peroxide formation, hydroxide solution is supplied to the above-mentioned electrolysis vessel except not using an ion-exchange membrane. Anode liquid supply is solution which generally contains 15 thru/or 100 g/l of sodium hydroxide. The negative pole liquid collected from an electrolysis vessel is negative pole liquid containing 3 % of the weight of 0.5 peroxide formation From, and 15 thru/or 100 g/l of Hydroxylate l-IJ Umu. It is characterized by the method of supplying an oxidizer, for example, oxygen, air, or air with abundant oxygen to a negative pole liquid room generating the anode output of oxygen and water, and the negative pole output of alkali metal hydroxide and a peroxide, and not generating hydrogen gas substantially, letting current pass in an anode room from a negative pole room. Especially the present invention is targeting the negative pole for To apprehend reaction promotion from the covered particles which were described here. The anode liquid room constituted from material which bears concentrated alkali metal hydroxide solution by the present invention, the anode in it, the negative pole liquid room which comprised material which bears concentrated alkali metal hydroxide, the negative pole in it, and sun t'! An electrolysis vessel with the ion permeability barrier membrane which intervenes in between very much is provided. The electrolysis vessel considered here is characterized by the To apprehend negative pole from the negative pole liquid room which has a means to supply an oxidizer in the electrolysis solution of the negative pole interior of a room, and each porous particle. Example 1 It is carbon black 0.7 in order to build a tunic active in contact. g was mixed with acetic acid Ginsui solution 20ru1. which contains acetic acid silver 10g per solution liter. In order to improve Wet of carbon black, one drop of surface-active agent (loam Ant Haas product Tori Tong X-100) was added. Subsequently, after drying a mixture in the oven of 100 degreeC, the mixture was heated to 350 degree[ per hour ] in nitrogen atmosphere C, and thermal decomposition of the acetic acid silver was carried out. Subsequently, this substance was mixed with 1=10 turbidity water (they are E and 1. Du Pond in ten copies of water one copy of Nemoru product Teflon 30B1 fluoropolymer) 3.5.9, and it was considered as slurry. After mixing U.S. Country regulation [10-20 mesh graphite grain 10g to this slurry, it dried by about 100 degreeC. Subsequently, the substance was heated by 350in nitrogen atmosphere'C for 1 hour. The generated particles were graphite particles which attached the carbon fluorocarbon silver film to the surface. Example 2 The electrolysis vessel was assembled as given [ this ] in a specification. Between the anode of a tub and the negative poles was separated by porous asbestos barrier membrane. The negative pole was the hardened particle floor which was generated in Example 1. The anode was the ruthenium oxidation thing which carried out titanium covering. Sodium chloride solution of NaC1about 301-/l concentration was passed in the anode room. Oxygen gas was passed with the opening between the particles which constitute the negative pole. Salt solution was electrolyzed through current between the anode negative poles with the voltage of abbreviation 2v, and the current density of about 1 A per square inch. Gaseous chlorine was emitted in the anode and Hydroxylate I-IJ Umu generated by the negative pole.