CN110055548B - Electrode for electrolyzing ozone, preparation method thereof and electrolytic ozone water module device - Google Patents
Electrode for electrolyzing ozone, preparation method thereof and electrolytic ozone water module device Download PDFInfo
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- CN110055548B CN110055548B CN201910311987.1A CN201910311987A CN110055548B CN 110055548 B CN110055548 B CN 110055548B CN 201910311987 A CN201910311987 A CN 201910311987A CN 110055548 B CN110055548 B CN 110055548B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/13—Ozone
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
Abstract
The invention relates to the technical field of electrode components for electrolyzing ozone, in particular to an electrode for electrolyzing ozone, a preparation method thereof and an electrolytic ozone water module device, wherein the electrode for electrolyzing ozone comprises a substrate component and a catalytic coating formed by coating an electrode catalyst material on the substrate component, and the substrate component is made of an inert conductive material; the inert conductive material comprises titanium-plated niobium; the components in the catalytic coating include organometallic compounds, metal oxides; the organic metal compound is a nano tin dioxide organic metal compound modified by at least 72 to 82 percent of perfluorosulfonic acid; the metal oxide includes at least iridium metal oxide and ruthenium metal oxide; the catalytic coating has a composition in which the proportion of the substance constituting the dielectric substance to the surface area of the coating member is more than 81%. Compared with the prior art, the invention improves the electrolysis efficiency; the replacement and the solubility of tin dioxide metal ions are avoided in the electrolytic process, and no meson film or liquid medicine or additive is needed to be added into water.
Description
Technical Field
The invention relates to the technical field of electrode components for electrolyzing ozone in water, in particular to an electrode for electrolyzing ozone, a preparation method thereof and an electrolyzed ozone water module device.
Background
As a method for removing bacteria, molds, pathogenic protozoa, and other microorganisms from drinking water at home and water used in kitchen appliances, personal hygiene, and the like, a method of sterilizing and purifying using a chloride-based chemical such as sodium hypochlorite has been used. However, chlorine-resistant bacteria, sporophytes and pathogenic protozoa are present in the treated water. See Bruno Langlais, davida. reckhow, Deborah r. brimk; ozong in Water treatment and engineering, Lewis Publishers, INC.1991, and references discussed therein. Chlorination is commonly used in similar applications, but leaves an objectionable chlorinated organic residue. Instead, the ozonated water will slowly disappear by itself to become oxygen and water, leaving little harmful residue. There are generally two main types of techniques for producing ozone:
the first type of technology, which relates to the corona discharge process, is mainly to produce ozone from oxygen in the air by corona discharge in an intense and high frequency alternating electric field, and this type of technology achieves very low ozone concentrations, about 2% to 5% of oxygen, and can produce harmful nitrogen oxides, ozone being produced in the gas phase, and the amount of dissolved ozone being limited by the concentration and solubility of the gaseous ozone in order to obtain gaseous ozone in contact with water. Therefore, the amount of ozone dissolved in the water to be treated is small, and the effect of sterilization by ozone water is not good. The method has the advantages of complex process, large equipment volume and high cost.
The second type is a type in which an electrode formed by coating lead oxide on the surface of a substrate made of titanium is used as an anode in an electrolysis electrode, which is an electrode capable of efficiently generating ozone and active oxygen and is considered to be particularly effective when water to be treated is treated with high-concentration ozone or active oxygen. However, in the titanium-based coated lead oxide electrolysis electrode, lead oxide is specified as a lead compound by regulations such as the water pollution prevention law as a harmful substance, and therefore, various obstacles and damages are caused by water outside the electrolysis electrode when taken in by the human body.
In addition, the problem of infectious diseases caused by harmful bacteria in domestic life and personal hygiene care is being emphasized, for example, the generation of mold and the propagation of bacteria such as legionella pneumophila are accelerated in the humidity and temperature environment of a bathroom, the mold and legionella pneumophila which have invaded into the human body become the cause of infectious diseases, the mold and legionella pneumophila which have propagated in the high-temperature and humid environment of a bathroom are attached to a bathtub, a tile, etc. and mixed into hot water in the bathtub, and the bacteria are caused to enter the human body by the inhalation of moisture generated from the hot water.
In addition, the bacteria such as legionella pneumophila blow out the bacteria from the blow-out port of the apparatus into the room, causing the bacteria to float in the air, and causing infection of people by the floating bacteria, and people generally use chlorine-dispersed disinfectants for killing mold and preventing further propagation of bacteria, and the chlorine-dispersed disinfectants are generally adjusted by adding a chemical such as sodium hypochlorite, and are often adjusted to be alkaline, and toxic chlorine gas is generated by mixing with an acidic chemical, and there is a problem that dangerous accidents occur during use, and it is difficult for chlorine-containing disinfectants to remove chlorine-resistant bacteria, sporophytes, pathogenic protozoa, and the like.
There is also a problem that the method of sterilization by electrolytic silver ion water is high in cost because expensive noble metal is used as an electrode.
Some other sterilization methods are methods of generating electrolyzed water containing sodium hypochlorite at a high concentration by electrolysis using an electrode to sterilize, and for example, in the case of using electrolyzed water containing sodium hypochlorite, salt remains afterward, and in the case of finger sterilization using the electrolyzed water, there is a problem that water must be used for washing after sterilization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an electrolytic capacitor and a manufacturing method thereof, which can efficiently generate ozone and have durability, and have high safety to human bodies and small pollution to shallow layers of the environment when being discarded; the manufactured module device can be directly placed into tap water without a meson film or adding liquid medicine or additives into the water, and no residual pollutants are left after disinfection.
In order to achieve the purpose, the electrode for electrolyzing ozone is designed, which comprises a substrate member and a catalytic coating formed by coating an electrode catalyst material on the substrate member, and is characterized in that:
the base component is made of inert conductive material; the inert conductive material comprises titanium-plated niobium;
the components in the catalytic coating comprise organic metal compounds and metal oxides; the organic metal compound is nanometer stannic oxide modified by perfluorosulfonic acid; the metal oxide at least comprises iridium metal oxide and ruthenium metal oxide;
the proportion of the dielectric formed by high-temperature 500 ℃ thermal decomposition in the components of the catalytic coating in the surface area of the coating member is more than 81%.
A preparation method of the electrode is characterized by adopting the following method:
(1) preparing perfluorosulfonic acid modified nano tin dioxide: weighing perfluorinated sulfonic acid resin and pretreated nano tin dioxide; putting the ingredients into a solvent, dissolving the ingredients in a high-pressure reaction kettle at constant temperature and constant pressure, wherein the temperature of the reaction kettle is 180-260 ℃, the pressure of the reaction kettle is 4.5-9 MPa, the stirring speed is set to be 1500-2800 r/min, and closing the reaction kettle after reacting for 5-8 hours; cooling to room temperature and room pressure to obtain a primary solution of the perfluorosulfonic acid modified nano tin dioxide for later use; the perfluorinated sulfonic acid resin: nano tin dioxide: the solvent adopts the following mixture ratio: 100 g: 32 g: 320 ml; the solvent is prepared by mixing the following solvent raw materials in volume ratio: 36-65% of water: 26-55% of n-propanol: 9% of methanol;
(2) weighing 72-82% of perfluorosulfonic acid modified nano tin dioxide, 13-18% of manganese-containing oxide, 0.5-2% of titanium-containing catalytic cross-linking agent, 1.5-3% of ruthenium-containing chloride and 3-5% of iridium oxide hydrate by mass as raw materials of a catalytic coating;
(3) putting the raw materials into a container, and stirring for 1 hour at the rotating speed of 500-900 rpm by a magnetic stirrer at the environmental temperature of 23-26 ℃ to form an electrode catalyst coating;
(4) coating the electrode catalyst coating on the surface of a substrate member, drying at 100-140 ℃ for 5-10 minutes, and then performing heat treatment in an atmosphere furnace at 260-650 ℃ for 15-20 minutes;
(5) and (4) repeating the step (4) for 20-30 times to prepare a catalytic coating with density on the surface of the substrate member to form the electrode for electrolyzing ozone.
Further, the manganese-containing oxide includes any one of manganese monoxide, manganese nitrate and manganese chloride;
the titanium-containing catalytic cross-linking agent comprises any one of tetrabutyl titanate, titanium tetrachloride and titanium trichloride hydrochloric acid solution;
the ruthenium-containing chloride comprises any one of ruthenium trichloride and ruthenium dodecacarbonyl;
the iridium oxide hydrate comprises any one of iridium oxide dihydrate, ammonium chloroiridate and chloroiridate;
the alcohol solvent comprises any one of ethanol, isopropanol and n-butanol;
the ether solvent includes turpentine.
Furthermore, the pretreated nano tin dioxide is prepared by cleaning the surface of the nano tin dioxide by using hydrogen and then drying the nano tin dioxide to improve the surface affinity of the nano tin dioxide.
Further, the step (4) of applying the electrode catalyst coating on the surface of the base member is performed by a brush or a spraying or dipping method.
An electrolytic ozone water module device, characterized in that it adopts any one of the following two electrode connection structures:
a first electrode connection structure including 1 anode, 2 cathodes, 1 anode conductor, and 1 cathode conductor; one end of the conductor for the anode is connected with the positive electrode of the power supply, and the other end of the conductor for the anode is connected with the anode; one end of the conductor for the cathode is connected with the negative pole of the power supply, and the other end of the conductor for the cathode is connected with 2 cathodes in parallel;
a second electrode connection structure including 1 cathode, 2 anodes, 1 anode conductor, and 1 cathode conductor; one end of the conductor for the cathode is connected with the negative pole of the power supply, and the other end of the conductor for the cathode is connected with the cathode; one end of the conductor for the anode is connected with the positive electrode of the power supply, and the other end of the conductor for the anode is connected with 2 anodes in parallel;
the anode is an electrode for electrolyzing ozone prepared by the preparation method of the electrode; the cathode is made of stainless steel or inert oxidation-resistant conductive materials, and the inert oxidation-resistant conductive materials comprise titanium-plated niobium and titanium-plated platinum.
Further, the anode adopts a pore-shaped or net-shaped anode sheet; the cathode adopts a pore-shaped or mesh-shaped cathode sheet; the anode conductor adopts an anode conductive screw; the conductor for the cathode adopts a cathode conductive screw.
Further, the method also comprises the following steps:
the electrode group bracket base is provided with an accommodating groove;
the control power panel is positioned in the accommodating groove of the electrode group bracket base;
the waterproof glue is poured into the accommodating groove and solidified, and then the control power panel is sealed in the accommodating groove;
the fixing screw fixes the anode sheet and the cathode sheet on the outer surface of the electrode group bracket seat;
a first avoidance groove for avoiding the negative conductive screw is arranged on the anode sheet; a second avoidance groove for avoiding the positive conductive screw is arranged on the cathode plate;
when the first electrode connection structure is adopted, one end of the negative conductive screw sequentially penetrates through the first cathode sheet, the first avoidance groove of the anode sheet, the second cathode sheet and the electrode group support seat and then is connected with the negative end on the control power panel; one end of the positive conductive screw sequentially penetrates through the second avoidance groove of the first cathode sheet, the anode sheet, the second avoidance groove of the second cathode sheet and the electrode group bracket seat and then is connected with the positive end on the control power panel;
when the second electrode connection structure is adopted, one end of the positive conductive screw sequentially penetrates through the first positive plate, the second avoidance groove of the negative plate, the second positive plate and the electrode group bracket seat and then is connected with the positive end on the control power panel; one end of the negative conductive screw sequentially penetrates through the first avoidance groove of the first anode strip, the cathode strip, the first avoidance groove of the second anode strip and the electrode group bracket seat and then is connected with the negative end on the control power panel.
Furthermore, the joint of the cathode sheet and the fixing screw and the joint of the anode sheet and the fixing screw are respectively provided with a spacing-limited insulating gasket for insulating and separating the anode sheet and the cathode sheet;
sealing rings for preventing liquid from entering the accommodating groove are arranged between the positive and negative conductive screws and the electrode group support seat respectively;
when the first electric connection structure is adopted, a conductive spacing sheet is further sleeved on the negative conductive screw positioned at the first avoidance groove of the anode sheet;
when the second electric connection structure is adopted, the positive electrode conductive screw at the second avoiding groove of the cathode plate is also sleeved with a conductive spacing plate.
Furthermore, the electrode group bracket base is integrally provided with two electrode connecting column holes which penetrate through the accommodating groove and are communicated with the outside and a fixing screw column hole which is isolated from the accommodating groove and is used for connecting a fixing screw;
the electrode group support base is also provided with an assembly hole, so that the electrode group support base is convenient to fix and install.
Compared with the prior art, the electrode for electrolyzing ozone adopts the nano tin dioxide modified by the perfluorosulfonic acid as O absorbed by the anode in electrolysis2The atomic retention makes the catalyst obtain high-efficiency reaction in the catalytic process to generate O3Increase O3The precipitation rate of the tin oxide is improved in the heat treatment process of the nanometer tin dioxide modified by the perfluorosulfonic acid, and the problem of heavy metal pollution of water caused by replacement of tin dioxide metal ions and water solubility is also avoided in the electrolysis process in water; the metal oxides such as ruthenium, iridium and the like in the catalytic coating of the electrode for generating ozone improve the conductivity of the electrode for generating ozone, thereby improving the electrolysis efficiency;
ozone water directly generated in tap water by an electrode for electrolytic ozone is used for killing bacteria, mold, microorganism, chlorine-resistant bacteria, sporophyte, pathogenic protozoa and the like by ozone water with very strong bactericidal power;
in the preparation method, the heat treatment method of the electrode catalyst coating can improve the associativity of the catalytic coating and the matrix member and also improve the density of the catalytic coating;
the electrolytic ozone water module device can be placed in tap water to supply power to the electrolytic ozone water module to generate ozone water from water in the container without adding a meson film in the electrolytic electrode assembly or adding liquid medicine or additives in the water; when in use, objects needing sterilization can be put into the container for sterilization and disinfection, no residual pollutants are left on the sterilized and disinfected objects, and electrolyzed ozone water can be taken out of the container for use; the electrolytic ozone water module device provides convenience for the design of household and sanitary cleaning products.
Drawings
Fig. 1 is a schematic diagram of an electrical operation of the present invention.
Fig. 2 is another electrical schematic of the present invention.
Fig. 3 is an angle perspective view of the electrolytic ozonated water module device according to the present invention.
Figure 4 is another perspective view of the electrolytic ozonated water module device in accordance with the present invention.
FIG. 5 is a perspective view of the ozonated water module apparatus of the present invention with the control power board removed.
Fig. 6 is an exploded view of an electrolytic ozonated water module apparatus according to the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and examples.
The working principle of the invention is as follows:
in the general knowledge of water electrolysis, H is known when water is electrolyzed2Will be generated at the cathode and O at the anode, as described by the following half-reaction:
cathode reaction 2H2O+2e→H2+20H-E0＝0.0V；
Anodic reaction 2H2O→O2+4H++4e E0＝1.23V；
Ozone generation is described as a higher potential anodic reaction:
3H2O→O3+6H++6e E0＝1.6V
in order to improve the efficiency of ozone generation, a high oxygen overvoltage material is required on the anode, and the electrolysis electrode serving as the anode is composed of a conductive substrate made of, for example, titanium and an electrode catalyst formed on the surface of the conductive substrate, and the electrode catalyst on the surface layer of the conductive substrate of the anode serves to improve the ozone generation efficiency during electrolysis in water.
Example 1
An electrode for electrolyzing ozone, comprising a substrate member, a catalytic coating layer formed by coating electrode catalyst material on the substrate member, characterized in that:
the base component is made of inert conductive material; the inert conductive material comprises titanium-plated niobium;
the components in the catalytic coating comprise organic metal compounds and metal oxides; the organic metal compound is nanometer stannic oxide modified by perfluorosulfonic acid; the metal oxide at least comprises iridium metal oxide and ruthenium metal oxide;
the proportion of the dielectric formed by high-temperature 500 ℃ thermal decomposition in the components of the catalytic coating in the surface area of the coating member is more than 81%.
In this example, the catalytic coating layer contains ruthenium oxide and iridium oxide, and the conductivity of the electrode for electrolyzing ozone is improved, thereby improving the electrolysis efficiency.
The electrode for electrolyzing ozone used as an anode in the embodiment contains the nanometer tin dioxide modified by the perfluorosulfonic acid, and the problem of heavy metal pollution of water caused by replacement of tin dioxide metal ions and water solubility is avoided in the electrolysis process in water; increasing O in electrolysis by using nano tin dioxide modified by perfluorosulfonic acid2The atomic retention makes the catalyst obtain high-efficiency reaction in the catalytic process to generate O3Increase O3The precipitation rate of (2).
Example 2
A preparation method of the electrode is characterized by adopting the following method:
(1) preparing perfluorosulfonic acid modified nano tin dioxide organic metal compound: weighing 100g of perfluorosulfonic acid resin and 32g of pretreated nano tin dioxide; putting the ingredients into 320ml of solvent, dissolving the ingredients in a high-pressure reaction kettle at constant temperature and constant pressure, wherein the temperature of the reaction kettle is 180-260 ℃, the pressure of the reaction kettle is 4.5-9 MPa, the stirring speed is set to be 1500-2800 r/min, and closing the reaction kettle after reacting for 5-8 hours; cooling to room temperature and room pressure to obtain a primary solution of the perfluorosulfonic acid modified nano tin dioxide for later use; the pretreated nano tin dioxide is prepared by cleaning the surface of nano tin dioxide by using hydrogen and then drying the nano tin dioxide to improve the surface affinity of the nano tin dioxide; the solvent is prepared by mixing the following solvent raw materials in volume ratio: 36-65% of water: 26-55% of n-propanol: 9% of methanol;
(2) weighing 72 wt% of perfluorosulfonic acid modified nano tin dioxide, 18 wt% of manganese monoxide, 2 wt% of tetrabutyl titanate, 3 wt% of ruthenium trichloride and 5 wt% of iridium oxide hydrate as raw materials of the catalytic coating;
(3) putting the raw materials into a container, and stirring for 1 hour at the rotating speed of 500-900 rpm by a magnetic stirrer at the environmental temperature of 23-26 ℃ to form an electrode catalyst coating; the coating in this case is by brushing or spraying or dipping;
(4) coating the electrode catalyst coating on the surface of a substrate member, drying at 100-140 ℃ for 5-10 minutes, and then performing heat treatment in an atmosphere furnace at 260-650 ℃ for 15-20 minutes;
(5) and (4) repeating the step (4) for 20-30 times to prepare a catalytic surface layer with density on the surface of the substrate member to form the electrode for electrolyzing ozone. The heat treatment can improve the bonding property of the catalytic coating and the base member and also improve the density of the catalytic coating.
In the embodiment, the nanometer tin dioxide modified by the perfluorosulfonic acid improves the deposition rate of tin oxide in the heat treatment process.
The invention adopts the metal oxide generated by thermal decomposition of manganese-containing oxide, ruthenium-containing chloride and iridium oxide hydrate to improve the conductivity of the electrode for electrolyzing ozone, thereby improving the electrolysis efficiency.
The tetrabutyl titanate (C16H3604Ti) is used for catalysis and crosslinking in the heat treatment process after the coating of the electrode catalyst coating, so that the adhesion of the catalyst coating and a base member can be improved, the density of organic metal compounds, metal oxides and the like in the catalytic coating is improved, the conductivity of the electrode for electrolyzing ozone can be improved, and the electrolysis efficiency is improved.
Example 3
Referring to fig. 1 to 6, the present embodiment is an electrolytic ozonated water module apparatus, which is characterized in that it employs either one of the following two electrode connection structures:
a first electrode connection structure including 1 anode 1, 2 cathode 2, 1 anode conductor 3, and 1 cathode conductor 4; one end of the conductor 3 for the anode is connected with the positive electrode of the power supply, and the other end of the conductor 3 for the anode is connected with the anode 1; one end of the conductor 4 for the cathode is connected with the negative pole of the power supply, and the other end of the conductor 4 for the cathode is connected with 2 cathodes 2 in parallel;
a second electrode connection structure including 1 cathode 2, 2 anodes 1, 1 anode conductor 3, and 1 cathode conductor 4; one end of the conductor 4 for the cathode is connected with the negative pole of the power supply, and the other end of the conductor 4 for the cathode is connected with the cathode 2; one end of the conductor 3 for the anode is connected with the positive pole of the power supply, and the other end of the conductor 3 for the anode is connected with 2 anodes 1 in parallel;
the anode adopts the electrode for electrolyzing ozone prepared by the preparation method of the electrode in the embodiment 2; the cathode 2 can be made of 316L stainless steel, and can also be made of inert oxidation-resistant conductive materials, such as titanium-plated niobium, titanium-plated platinum and the like.
The anode 1 adopts a pore-shaped or net-shaped anode sheet; the cathode 2 adopts a pore-shaped or mesh-shaped cathode sheet; the conductor 3 for the anode adopts a positive conductive screw; the conductor 4 for the cathode is a negative conductive screw.
Further, the method also comprises the following steps:
the electrode group bracket base 5 is provided with an accommodating groove 5-1;
the control power panel 6 is positioned in the accommodating groove 5-1 of the electrode group bracket seat 5 and is used for connecting a power line and carrying out related control;
waterproof glue, after pouring the waterproof glue into the holding tank 5-1 to solidify, the control power panel 6 is sealed in the holding tank 5-1;
the fixing screw 7 fixes the anode sheet and the cathode sheet on the outer surface of the electrode group bracket seat 5; in this example, 2 fixing screws are adopted; the fixing screw is made of an insulating material;
a first avoidance groove 1-1 for avoiding the negative conductive screw is arranged on the anode sheet; a second avoidance groove 2-1 for avoiding the positive conductive screw is arranged on the cathode plate;
when the first electrode connection structure is adopted, one end of the negative electrode conductive screw penetrates through the first cathode sheet, the first avoidance groove 1-1 of the anode sheet, the conductive spacing limit sheet 8, the second cathode sheet and the electrode group support base 5 in sequence and then is connected with the negative end on the control power panel 6, and the negative end is locked by a nut; one end of the positive conductive screw sequentially penetrates through the second avoidance groove 2-1 of the first cathode sheet, the anode sheet, the second avoidance groove 2-1 of the second cathode sheet and the electrode group support seat 5 to be connected with the positive end on the control power panel 6 and is locked by a nut;
when the second electrode connection structure is adopted, one end of the positive conductive screw sequentially penetrates through the first anode sheet, the second avoidance groove of the cathode sheet, the conductive spacing distance limiting sheet 8, the second anode sheet and the electrode group support base 5 to be connected with the positive end on the control power panel 6 and is locked by the nut; one end of the negative conductive screw sequentially penetrates through the first avoidance groove of the first anode sheet, the cathode sheet, the first avoidance groove of the second anode sheet and the electrode group bracket seat 5 to be connected with the negative end on the control power panel 6 and locked by a nut.
Furthermore, the joint of the cathode sheet and the fixing screw 7 and the joint of the anode sheet and the fixing screw 7 are respectively provided with a spacing-limited insulating gasket 9 for insulating and separating the anode sheet and the cathode sheet, wherein the cross section of the spacing-limited insulating gasket is T-shaped in the embodiment; referring to fig. 2, when the first electrode connection structure is adopted, the distance between the anode sheet and the first cathode sheet is 0.2 MM to 2.0 MM; the distance between the anode sheet and the second cathode sheet is 0.2-1.0 MM; a medium ion membrane is not required to be added between the cathode and the anode;
and sealing rings 10 for preventing liquid from entering the accommodating groove 5-1 are respectively arranged between the positive and negative conductive screws and the electrode group support seat 5.
Furthermore, the electrode group bracket seat 5 is integrally provided with two electrode connecting column holes 5-2 which penetrate through the accommodating groove 5-1 and are connected with the outside and a fixing screw column hole 5-3 which is isolated from the accommodating groove 5-1 and is used for connecting a limiting screw 7; the electrode group bracket base 5 is also provided with an assembly hole 5-4 so as to be conveniently and fixedly arranged at a specific place.
During the use, electrolysis ozone water module device can drop into the aquatic, and positive, negative electrode piece need submergence in the aquatic, can directly produce the ozone bubble that the bactericidal power is very strong, active oxygen group and hydroxyl (hydroxyl group) etc. in the aquatic electrolysis when switching on the power, and the ozone bubble of little shape can be high-efficient evenly to be merged in the aquatic, has improved the ozone content in aqueous, is used for killing bacterium and mould, microorganism and chlorine-resistant fungus or sporophyte, sick protozoan etc. more effectively.
The electrolytic ozone water module device can be used for one or more ozone water modules, can be determined according to the requirements of the ozone water generation amount, can generate ozone water only by using household tap water, and is flexible and convenient to use.
Every electrolytic ozone water module device adopts a control power supply board, if a plurality of electrolytic ozone water modules are used in the basin simultaneously, every electrolytic ozone water module all has the control power supply board control of oneself, can not receive the interference of different voltages, the different electric current power consumptions of different electrolytic ozone water modules, can design the quantity of electrolytic ozone water module according to the demand of different ozone water, and application that in use can be very nimble. Therefore, the phenomena of voltage robbery and current robbery in the use process of a plurality of electrolytic ozone water modules are avoided, if the voltage-limiting and current-limiting control of a single electrolytic ozone water module is not performed, the plurality of electrolytic ozone water modules share one power supply, the voltage and the current of each electrolytic ozone water module are different easily in the use process, and if the voltage-limiting and current-limiting control of the single electrolytic ozone water module is not performed, one electrolytic ozone water module is over-high in power generation and is easily damaged.
The electrolytic ozone water module device can be used on household cleaning, sterilizing and disinfecting equipment, such as vegetable and fruit cleaning, residual pesticide degradation generators, sterilizing and disinfecting water machine equipment and the like, and provides convenience for the design of household and life sanitary cleaning products.
Claims (10)
1. An electrode for electrolyzing ozone, comprising a substrate member, a catalytic coating layer formed by coating electrode catalyst material on the substrate member, characterized in that:
the base component is made of inert conductive material; the inert conductive material comprises titanium-plated niobium;
the components in the catalytic coating comprise organic metal compounds and metal oxides; the organic metal compound is nanometer stannic oxide modified by perfluorosulfonic acid; the metal oxide at least comprises iridium metal oxide and ruthenium metal oxide;
the proportion of dielectric formed by high-temperature 500 ℃ thermal decomposition in the components of the catalytic coating in the surface area of the coating member is more than 81 percent;
the method for preparing the perfluorosulfonic acid modified nano tin dioxide comprises the following steps: weighing perfluorinated sulfonic acid resin and pretreated nano tin dioxide; putting the ingredients into a solvent, dissolving the ingredients in a high-pressure reaction kettle at constant temperature and constant pressure, wherein the temperature of the reaction kettle is 180-260 ℃, the pressure of the reaction kettle is 4.5-9 MPa, the stirring speed is set to be 1500-2800 r/min, and closing the reaction kettle after reacting for 5-8 hours; cooling to room temperature and room pressure to obtain a primary solution of the perfluorosulfonic acid modified nano tin dioxide for later use; the perfluorinated sulfonic acid resin: nano tin dioxide: the solvent adopts the following mixture ratio: 100 g: 32 g: 320 ml; the solvent is prepared by mixing the following solvent raw materials in volume ratio: 36% -65% of water: 26% -55% of n-propanol: 9% methanol.
2. A method for preparing the electrode of claim 1, comprising the steps of:
(1) weighing 72-82% by mass of perfluorosulfonic acid modified nano tin dioxide, 13-18% by mass of manganese-containing oxide, 0.5-2% by mass of titanium-containing catalytic cross-linking agent, 1.5-3% by mass of ruthenium-containing chloride and 3-5% by mass of iridium oxide hydrate as raw materials of a catalytic coating;
(2) putting the raw materials into a container, and stirring for 1 hour at the rotating speed of 500-900 rpm by a magnetic stirrer at the environmental temperature of 23-26 ℃ to form an electrode catalyst coating;
(3) coating the electrode catalyst coating on the surface of a substrate member, drying at 100-140 ℃ for 5-10 minutes, and then performing heat treatment in an atmosphere furnace at 260-650 ℃ for 15-20 minutes;
(4) and (4) repeating the step (4) for 20-30 times to prepare a catalytic coating with density on the surface of the substrate member to form the electrode for electrolyzing ozone.
3. The method of preparing an electrode according to claim 2, wherein:
the manganese-containing oxide comprises any one of manganese monoxide, manganese nitrate and manganese chloride;
the titanium-containing catalytic cross-linking agent comprises any one of tetrabutyl titanate, titanium tetrachloride and titanium trichloride hydrochloric acid solution;
the ruthenium-containing chloride comprises any one of ruthenium trichloride and ruthenium dodecacarbonyl;
the iridium oxide hydrate includes any one of iridium oxide dihydrate, ammonium chloroiridate and chloroiridate.
4. The method of preparing an electrode according to claim 2, wherein: the pretreated nano tin dioxide is prepared by cleaning the surface of the nano tin dioxide by using hydrogen and then drying the nano tin dioxide to improve the surface affinity of the nano tin dioxide.
5. The method of preparing an electrode according to claim 2, wherein: the step (4) of applying the electrode catalyst coating on the surface of the base member is a method of brushing or spraying or dipping.
6. An electrolytic ozone water module device, characterized in that it adopts any one of the following two electrode connection structures:
a first electrode connection structure comprising 1 anode (1), 2 cathode (2), 1 anode conductor (3), and 1 cathode conductor (4); one end of the conductor (3) for the anode is connected with the positive electrode of the power supply, and the other end of the conductor (3) for the anode is connected with the anode (1); one end of the conductor (4) for the cathode is connected with the negative pole of the power supply, and the other end of the conductor (4) for the cathode is connected with 2 cathodes (2) in parallel;
a second electrode connection structure comprising 1 cathode (2), 2 anodes (1), 1 anode conductor (3), and 1 cathode conductor (4); one end of the conductor (4) for the cathode is connected with the negative pole of the power supply, and the other end of the conductor (4) for the cathode is connected with the cathode (2); one end of the conductor (3) for the anode is connected with the positive electrode of the power supply, and the other end of the conductor (3) for the anode is connected with 2 anodes (1) in parallel;
the anode is an electrode for electrolyzing ozone prepared by the preparation method of the electrode as claimed in any one of claims 2 to 5; the cathode (2) is made of stainless steel or inert oxidation-resistant conductive materials, and the inert oxidation-resistant conductive materials comprise titanium-plated niobium and titanium-plated platinum.
7. The electrolytic ozonated water module apparatus according to claim 6, wherein the anode (1) is a perforated sheet-shaped or a mesh sheet-shaped anode sheet; the cathode (2) adopts a pore-shaped or mesh-shaped cathode sheet; the conductor (3) for the anode adopts a positive conductive screw; the conductor (4) for the cathode adopts a cathode conductive screw.
8. The ozonated water module apparatus according to claim 7, further comprising:
the electrode group bracket base (5) is provided with an accommodating groove (5-1);
the control power panel (6) is positioned in the accommodating groove (5-1) of the electrode group bracket base (5);
waterproof glue, after the waterproof glue is poured into the accommodating groove (5-1) to be solidified, the control power panel (6) is sealed in the accommodating groove (5-1);
the fixing screw (7) fixes the anode sheet and the cathode sheet on the outer surface of the electrode group bracket seat (5);
a first avoidance groove (1-1) for avoiding the negative conductive screw is arranged on the anode sheet; a second avoidance groove (2-1) for avoiding the positive conductive screw is arranged on the cathode plate;
when the first electrode connection structure is adopted, one end of the negative conductive screw sequentially penetrates through the first cathode sheet, the first avoidance groove (1-1) of the anode sheet, the second cathode sheet and the electrode group support seat (5) and then is connected with the negative end on the control power panel (6); one end of the positive conductive screw sequentially penetrates through the second avoidance groove (2-1) of the first cathode sheet, the anode sheet, the second avoidance groove (2-1) of the second cathode sheet and the electrode group support seat (5) and then is connected with the positive end on the control power panel (6);
when the second electrode connection structure is adopted, one end of the positive conductive screw sequentially penetrates through the first anode strip, the second avoidance groove of the cathode strip, the second anode strip and the electrode group bracket seat (5) and then is connected with the positive end on the control power panel (6); one end of the negative conductive screw sequentially penetrates through the first avoidance groove of the first anode sheet, the cathode sheet, the first avoidance groove of the second anode sheet and the electrode group bracket seat (5) and then is connected with the negative end on the control power panel (6).
9. The ozonated water module apparatus according to claim 8, wherein,
the joint of the cathode sheet and the fixing screw (7) and the joint of the anode sheet and the fixing screw (7) are respectively provided with a spacing-limited insulating gasket (9) for insulating and separating the anode sheet and the cathode sheet;
sealing rings (10) for preventing liquid from entering the accommodating groove (5-1) are respectively arranged between the positive and negative conductive screws and the electrode group support seat (5);
when the first electric connection structure is adopted, a conductive spacing sheet (8) is further sleeved on the negative conductive screw positioned at the first avoidance groove (1-1) of the anode sheet;
when the second electric connection structure is adopted, the positive conductive screw at the second avoidance groove (2-1) of the cathode plate is also sleeved with a conductive spacing plate (8).
10. The ozonated water module apparatus according to claim 9, wherein,
the electrode group bracket seat (5) is integrally provided with two electrode connecting column holes (5-2) which penetrate through the accommodating groove (5-1) and are connected with the outside and fixing screw column holes (5-3) which are isolated from the accommodating groove (5-1) and are used for connecting fixing screws (7);
the electrode group support base (5) is also provided with an assembly hole (5-4) which is convenient for fixed installation.
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| KR20210036724A (en) * | 2019-09-26 | 2021-04-05 | 주식회사 엘지화학 | Electrode for Electrolysis |
| CN113388855A (en) * | 2020-03-11 | 2021-09-14 | 上海喜运环保科技有限公司 | Improved method and structure of ozone mouth wash instant generation device |
| TWI747462B (en) * | 2020-08-26 | 2021-11-21 | 百特環保科技股份有限公司 | Electrolytic ozone water generator composed of coated titanium anode |
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| CN1751140B (en) * | 2003-02-14 | 2011-02-02 | 克拉里宗有限公司 | Device for and method of generating ozone |
| CN108034960A (en) * | 2017-12-29 | 2018-05-15 | 唐锋机电科技（深圳）有限公司 | Ozone generation system and portable ozone generator |
| CN108754533B (en) * | 2018-05-25 | 2020-11-17 | 西安交通大学 | Preparation method of long-life high-activity doped tin oxide electrode for electrolyzing aquatic ozone |
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