WO2021022762A1 - 阳极及其制备方法和应用、臭氧(超氧)发生系统和洗牙器 - Google Patents

阳极及其制备方法和应用、臭氧(超氧)发生系统和洗牙器 Download PDF

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WO2021022762A1
WO2021022762A1 PCT/CN2019/126857 CN2019126857W WO2021022762A1 WO 2021022762 A1 WO2021022762 A1 WO 2021022762A1 CN 2019126857 W CN2019126857 W CN 2019126857W WO 2021022762 A1 WO2021022762 A1 WO 2021022762A1
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anode
precursor
titanium
ozone
nickel
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PCT/CN2019/126857
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English (en)
French (fr)
Inventor
张青
刘小文
王刚
刘信全
李进峰
周刚
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深圳市耐菲尔医疗器械科技有限公司
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Publication of WO2021022762A1 publication Critical patent/WO2021022762A1/zh

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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
    • C25B11/04—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C17/00—Devices for cleaning, polishing, rinsing or drying teeth, teeth cavities or prostheses; Saliva removers; Dental appliances for receiving spittle
    • A61C17/02—Rinsing or air-blowing devices, e.g. using fluid jets or comprising liquid medication
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • 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
    • C25B11/04—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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/026—Treating water for medical or cosmetic purposes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C02F2201/782—Ozone generators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to the technical field of ozone generation, in particular to an anode used in the process of electrolyzing aquatic ozone production, a preparation method and application thereof, an ozone generation system and a tooth cleaner.
  • ozone water to rinse teeth or carry out oral care can quickly and effectively kill virus bacteria and harmful microorganisms such as tuberculosis, Escherichia coli, gonorrhoeae, typhoid bacillus, etc. in the teeth and oral cavity.
  • the electrolysis of aquatic ozone technology has the advantages of low voltage and no harmful by-products. Its principle is to use DC voltage to electrolyze water and generate ozone at the anode.
  • the disadvantage of this method is that it is difficult to controllably generate an appropriate content of ozone. When using this technology to generate ozone water to rinse teeth, it cannot maintain a stable sterilization effect.
  • the anode used in a process of electrolyzing aquatic ozone production.
  • the anode includes a titanium substrate and a composite oxide layer attached to the surface of the titanium substrate.
  • the material of the composite oxide layer includes a metal oxide.
  • the metal elements in include tin, ruthenium, manganese, titanium and nickel.
  • the molar ratio of tin, ruthenium, manganese, titanium and nickel is (200 ⁇ 500): (2.5-20):1:(1.5-7): (5 ⁇ 15).
  • the molar ratio of the tin, ruthenium, manganese, titanium and nickel is (300-400): (5-15): 1: (3-5): (8-12).
  • a method for preparing an anode used in the process of electrolyzing aquatic ozone production comprising the following steps:
  • the molar ratio of the precursor of, the precursor of titanium and the precursor of nickel is (200 ⁇ 500):(2.5 ⁇ 20):1:(1.5 ⁇ 7):(5 ⁇ 15);
  • the mixed solution is coated on a titanium substrate and then fired to obtain an anode.
  • the titanium substrate before the mixed solution is coated on the titanium substrate, the titanium substrate is pretreated and then placed in an etching solution for etching.
  • the pretreatment includes sandblasting.
  • the etching solution is selected from at least one of oxalic acid solution and hydrochloric acid solution.
  • the etching conditions include: a temperature of 70°C to 90°C, and a time of 20 minutes to 40 minutes.
  • the molar ratio of the tin precursor, the ruthenium precursor, the manganese precursor, the titanium precursor, and the nickel precursor in terms of metal elements is (300-400): (5 ⁇ 15): 1: (3 ⁇ 5): (8 ⁇ 12).
  • the mixed solution is coated on the titanium substrate and then dried, and then the baking is performed; the drying conditions include: a temperature of 90°C to 130°C, and a time of 5min to 10min .
  • the firing conditions include: a temperature of 380°C to 600°C, and a time of 1h to 3h.
  • the step of coating the mixed solution on the titanium substrate and then firing is repeated 3 to 5 times.
  • the conditions of the ozone production process from aquatic electrolysis include: the voltage does not exceed 24V, and the constant current density does not exceed 20mA/cm 2 .
  • An ozone generation system is also provided, which includes the above-mentioned anode.
  • tooth cleaner including the ozone generating system described above.
  • the anode has a special composite oxide layer, and the anode can be used in the process of electrolyzing aquatic ozone to stably output ozone water with an ozone concentration of 0.1 mg/L to 0.6 mg/L.
  • the anode used in the process of electrolyzing aquatic ozone, includes a titanium substrate and a composite oxide layer attached to the surface of the titanium substrate.
  • the titanium substrate may be a titanium-based material of any shape, such as a titanium plate or a titanium rod, and preferably a titanium plate.
  • the titanium substrate can be made of a titanium alloy with a titanium content of more than 98%.
  • the titanium substrate may have at least one surface, and the composite oxide layer may be attached to one surface of the titanium substrate, or may be attached to multiple surfaces of the titanium substrate.
  • the material of the composite oxide layer includes metal oxides.
  • the metal elements in the metal oxide include tin, ruthenium, manganese, titanium and nickel, that is, the material of the composite oxide layer includes tin oxide, ruthenium oxide, and manganese oxide. Substances, titanium oxide and nickel oxide.
  • the molar ratio of tin, ruthenium, manganese, titanium and nickel is (200-500): (2.5-20): 1: (1.5-7): (5-15).
  • the molar ratio of tin, ruthenium, manganese, titanium and nickel is (300 to 400): (5 to 15): 1: (3 to 5): (8 to 12):.
  • the anode has a special composite oxide layer, and the anode can be used in the process of electrolyzing aquatic ozone to stably output ozone water with an ozone concentration of 0.1 mg/L to 0.6 mg/L.
  • the method includes the following steps:
  • the pretreatment may include sandblasting.
  • Sandblasting can increase the roughness of the surface of the titanium substrate, which is beneficial to improve the adhesion of the composite oxide layer on the surface of the titanium substrate.
  • the blasting material used in the sandblasting treatment can be, for example, silicon carbide or quartz sand.
  • the etching solution can be selected from at least one of oxalic acid solution and hydrochloric acid solution. Further, the concentration of the oxalic acid solution may be 20% by weight to 50% by weight, and the concentration of the hydrochloric acid solution may be 10% by weight to 30%.
  • the etching conditions may include: a temperature of 70°C to 90°C, and a time of 20 minutes to 40 minutes. The etching is beneficial to further improve the adhesion of the composite oxide layer on the surface of the titanium substrate. After etching, pure water can be used to clean the etching solution remaining on the surface of the titanium substrate to obtain an etched titanium substrate.
  • S3 Obtain a mixed solution containing a precursor of tin, a precursor of ruthenium, a precursor of manganese, a precursor of titanium, and a precursor of nickel.
  • the molar ratio of tin precursors, ruthenium precursors, manganese precursors, titanium precursors and nickel precursors in terms of metal elements are (200 ⁇ 500): (2.5 ⁇ 20):1:( 1.5 to 7): (5 to 15), preferably (300 to 400): (5 to 15): 1: (3 to 5): (8 to 12).
  • the precursor of tin is a compound containing tin, for example, it may be at least one selected from tin chloride and tin oxalate.
  • the precursor of ruthenium is a compound containing ruthenium, such as ruthenium chloride.
  • the precursor of manganese is a compound containing manganese, such as manganese chloride.
  • the precursor of titanium is a compound containing titanium, such as butyl titanate.
  • the precursor of nickel is a compound containing nickel, for example, it can be selected from at least one of nickel chloride and nickel acetate.
  • the tin precursor, ruthenium precursor, manganese precursor, titanium precursor, and nickel precursor are dissolved in the solvent according to the above-mentioned ratio to obtain a mixed solution.
  • the solvent may be selected from at least one of ethanol, isopropanol and n-butanol, for example.
  • the amount of solvent can be adjusted within a wide range.
  • the weight ratio of the total weight of the precursor of ruthenium, the precursor of manganese, the precursor of titanium, the precursor of nickel and the precursor of tin to the weight of the solvent can be 1:( 5 ⁇ 20).
  • the drying conditions may include: a temperature of 90°C to 130°C, and a time of 5min to 10min.
  • the baking conditions include: the temperature is 380°C ⁇ 600°C, and the time is 1h ⁇ 3h.
  • the mixed solution is coated on the etched titanium substrate and dried, and then the step of firing can be repeated 3 to 5 times, which is beneficial to increase the amount of metal oxide deposited on the surface of the titanium substrate.
  • the temperature of the last calcination can be higher than the calcination temperature of the previous several times.
  • the temperature of the first 4 calcinations can be 380°C ⁇ 450°C
  • the temperature of the fifth calcination can be It is 500°C ⁇ 600°C.
  • the above anode can be used in the electrolysis of aquatic ozone process, especially the electrolysis of aquatic ozone process under low pressure.
  • the conditions of the ozone production process of electrolyzed aquatic water include: the voltage does not exceed 24V, and the constant current density does not exceed 20mA/cm 2 . Further, the voltage may be 12V-24V, and the constant current density may be 5mA/cm 2 -20mA/cm 2 .
  • the above anode is particularly suitable for preparing ozone generating systems in dental scalers. Under the conditions of providing water, DC power and constant current, ozone water with suitable and stable ozone concentration can be produced anytime and anywhere, at any water flow rate. Realize safe ozone water output.
  • the ozone generating system prepared by using the above anode can be used in any dental scaler on the market, and has significant advantages such as long service life, low cost, no pollution, simple manufacturing, and convenient carrying.
  • a dental scaler includes an ozone generating system including the above-mentioned anode.
  • the ozone generation system also includes conventional structures in the field, such as a cathode, a container that contains the anode and the cathode, and a power supply unit.
  • the cathode and anode can be arranged opposite to each other.
  • the vertical distance between the cathode and the anode should not exceed 5mm.
  • the ozone generation system can be used as an independent component or standard part, which can be located between the water tank and the water pump of the dental scaler, or between the water pump and the nozzle, or inside the nozzle assembly.
  • the ozone generating system When the ozone generating system is connected to a constant current power source, with a certain flow of water quickly passing through the ozone generating system, it can stably output ozone water with an ozone concentration of 0.1 mg/L to 0.6 mg/L at the anode.
  • the ozone water can clean the teeth gums in all directions, not only can achieve the purpose of fast cleaning, but also can directly sterilize and disinfect, remove bad breath, and achieve the dual effects of purifying the oral cavity and protecting the health of the gums.
  • the tooth cleaner described above has no toxic substances remaining in the process of use, and no additives are required. It is safe to use and is an environmentally friendly and healthy low-cost product.
  • the titanium substrate used in the examples is a titanium plate TA1, and other reagents are all commercially available products.
  • the titanium plate was subjected to sandblasting treatment, and then placed in an oxalic acid solution with a concentration of 20% by weight to be etched at 80°C for 30 minutes, and then removed and cleaned with pure water.
  • Dissolve tin chloride, ruthenium chloride, manganese chloride, butyl titanate and nickel chloride in ethanol to obtain a mixed solution, where Sn: Ru: Mn: Ti: Ni (molar ratio) 320:12: 1:4:10, the weight ratio of the total weight of tin chloride, ruthenium chloride, manganese chloride, butyl titanate and nickel chloride to ethanol is 1:5.
  • the mixture was coated on the surface of the titanium plate, dried at 120°C for 10 minutes, and then calcined at 450°C for 1 hour. Repeated coating, drying and firing under the above conditions 4 times, the last time the firing temperature was increased to 600° C. and fired for 3 hours to obtain the anode prepared in this example.
  • the anodes prepared in Examples 1 to 5 and Comparative Example 1 were assembled into an ozone generation system and tested for ozone generation.
  • the container has a water inlet and a water outlet, and is connected to a constant current power supply.
  • the upper limit voltage is 20V
  • the constant current density is 15mA/cm 2 .
  • Tap water was injected from the water inlet at a flow rate of 15L/hr, and the real-time concentration of ozone water was tested at the water outlet. The ozone concentration was recorded every 0.5h and listed in Table 1.
  • the anode of the present invention can stably output ozone water with an ozone concentration of 0.1 mg/L to 0.6 mg/L in the process of electrolyzing aquatic ozone production.

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  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract

本发明涉及一种用于电解水产臭氧工艺的阳极及其制备方法和应用、臭氧发生系统和洗牙器。该阳极包括钛基材和附着在所述钛基材表面的复合氧化物层，所述复合氧化物层的材料包括金属氧化物，所述金属氧化物中的金属元素包括锡、钌、锰、钛和镍，所述锡、钌、锰、钛和镍的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)：(5～15)。本发明的阳极具有特殊的复合氧化物层，用于电解水产臭氧工艺中能够稳定可控地输出臭氧浓度在0.1mg/L～0.6mg/L的臭氧水。

Description

阳极及其制备方法和应用、臭氧(超氧)发生系统和洗牙器 技术领域
本发明涉及臭氧发生技术领域，特别是涉及一种用于电解水产臭氧工艺的阳极及其制备方法和应用、臭氧发生系统和洗牙器。
背景技术
采用臭氧水冲洗牙齿或进行口腔护理，能快速有效的杀灭牙齿部位及口腔内的结核菌、大肠杆菌、淋菌、伤寒杆菌等病毒细菌及有害微生物。电解水产臭氧技术具有低电压、无有害副产物等优点，其原理是利用直流电压电解水，在阳极生成臭氧。但该方法的缺点是难以可控地生成适宜含量的臭氧，在利用该技术生成臭氧水冲洗牙齿时，无法维持稳定的杀菌效果。
发明内容
基于此，有必要提供一种用于电解水产臭氧工艺并且能够稳定地产生适宜含量臭氧的阳极。
一种用于电解水产臭氧工艺的阳极，该阳极包括钛基材和附着在所述钛基材表面的复合氧化物层，所述复合氧化物层的材料包括金属氧化物，所述金属氧化物中的金属元素包括锡、钌、锰、钛和镍，所述锡、钌、锰、钛和镍的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)：(5～15)。
在其中一个实施例中，所述锡、钌、锰、钛和镍的摩尔比为(300～400)：(5～15)：1：(3～5)：(8～12)。
一种用于电解水产臭氧工艺的阳极的制备方法，该方法包括以下步骤：
获取含有锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的混合液；其中，以金属元素计的所述锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)：(5～15)；
将所述混合液涂覆在钛基材上，然后焙烧，得到阳极。
在其中一个实施例中，在将所述混合液涂覆在钛基材上之前，先对钛基材进行预处理，然后置于刻蚀液中进行刻蚀。
在其中一个实施例中，所述预处理包括喷砂处理。
在其中一个实施例中，所述刻蚀液选自草酸溶液和盐酸溶液中的至少一种。
在其中一个实施例中，所述刻蚀的条件包括：温度为70℃～90℃，时间为20min～40min。
在其中一个实施例中，以金属元素计的所述锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的摩尔比为(300～400)：(5～15)：1：(3～5)：(8～12)。
在其中一个实施例中，将所述混合液涂覆在钛基材上后进行干燥，然后再进行所述焙烧；所述干燥的条件包括：温度为90℃～130℃，时间为5min～10min。
在其中一个实施例中，所述焙烧的条件包括：温度为380℃～600℃，时间为1h～3h。
在其中一个实施例中，将所述混合液涂覆在钛基材上然后焙烧的步骤重复进行3～5次。
还提供上述阳极在电解水产臭氧工艺中的应用。
在其中一个实施例中，所述电解水产臭氧工艺的条件包括：电压不超过24V， 恒流电流密度不超过20mA/cm 2。
还提供一种臭氧发生系统，包括上述阳极。
还提供一种洗牙器，包括上述臭氧发生系统。
上述阳极具有特殊的复合氧化物层，将该阳极用于电解水产臭氧工艺中能够稳定地输出臭氧浓度在0.1mg/L～0.6mg/L的臭氧水。
具体实施方式
为了便于理解本发明，下面将具体实施方式对本发明进行更全面的描述。具体实施方式给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
一实施方式的用于电解水产臭氧工艺的阳极，该阳极包括钛基材和附着在钛基材表面的复合氧化物层。
其中，钛基材可以为任意形状的钛基材料，例如钛板或钛棒等，优选为钛板。钛基材可以由钛合金制成，其钛含量在98％以上。
其中，钛基材可以具有至少一个表面，复合氧化物层可以附着在钛基材的一个表面上，也可以附着在钛基材的多个表面上。复合氧化物层的材料包括金属氧化物，金属氧化物中的金属元素包括锡、钌、锰、钛和镍，即复合氧化物层的材料包括锡的氧化物、钌的氧化物、锰的氧化物、钛的氧化物和镍的氧化物。其中锡、钌、锰、钛和镍的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)： (5～15)。优选情况下，锡、钌、锰、钛和镍的摩尔比为(300～400)：(5～15)：1：(3～5)：(8～12)：。
上述阳极具有特殊的复合氧化物层，将该阳极用于电解水产臭氧工艺中能够稳定地输出臭氧浓度在0.1mg/L～0.6mg/L的臭氧水。
一实施方式的上述阳极的制备方法，该方法包括以下步骤：
S1：对钛基材进行预处理，得到预处理后的钛基材。
其中，预处理可以包括喷砂处理。通过喷砂处理可以使钛基材表面的粗糙度增大，有利于提高复合氧化物层在钛基材表面的附着力。喷砂处理所采用的喷料例如可以为金刚砂或石英砂等。
S2：将预处理后的钛基材置于刻蚀液中进行刻蚀，得到刻蚀后的钛基材。
其中，刻蚀液可以选自草酸溶液和盐酸溶液中的至少一种。进一步地，草酸溶液的浓度可以为20重量％～50重量％，盐酸溶液的浓度可以为10重量％～30％。刻蚀的条件可以包括：温度为70℃～90℃，时间为20min～40min。通过刻蚀有利于进一步提高复合氧化物层在钛基材表面的附着力。刻蚀后，可以采用纯水将钛基材表面残留的刻蚀液清洗干净，得到刻蚀后的钛基材。
S3：获取含有锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的混合液。
其中，以金属元素计的锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)：(5～15)，优选为(300～400)：(5～15)：1：(3～5)：(8～12)。
其中，锡的前驱物为含有锡的化合物，例如可以选自氯化锡和草酸锡中的至少一种。钌的前驱物为含有钌的化合物，例如可以为氯化钌。锰的前驱物为含有锰的化合物，例如可以为氯化锰。钛的前驱物为含有钛的化合物，例如可 以为钛酸丁酯。镍的前驱物为含有镍的化合物，例如可以选自氯化镍和醋酸镍中的至少一种。
按上述配比将锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物溶于溶剂中，即可得到混合液。其中，溶剂例如可以选自乙醇、异丙醇和正丁醇中的至少一种。溶剂的用量可以在很大范围内调整，例如，钌的前驱物、锰的前驱物、钛的前驱物、镍的前驱物和锡的前驱物的总重量与溶剂的重量比可以为1：(5～20)。
S4：将混合液涂覆于刻蚀后的钛基材上并干燥，然后焙烧，得到用于电解水产臭氧工艺的阳极。
其中，干燥的条件可以包括：温度为90℃～130℃，时间为5min～10min。焙烧的条件包括：温度为380℃～600℃，时间为1h～3h。
进一步地，将混合液涂覆于刻蚀后的钛基材上并干燥，然后焙烧的步骤可以重复进行3～5次，这样有利于提高金属氧化物在钛基材表面的沉积量。这时，最后一次焙烧的温度可以较前几次的焙烧温度高，例如，当重复进行5次该步骤时，前4次焙烧的温度可以为380℃～450℃，第5次焙烧的温度可以为500℃～600℃。
上述阳极可以用于电解水产臭氧工艺，尤其是低压下的电解水产臭氧工艺。在一个实施例中，该电解水产臭氧工艺的条件包括：电压不超过24V，恒流电流密度不超过20mA/cm 2。进一步地，电压可以为12V～24V，恒流电流密度可以为5mA/cm 2～20mA/cm 2。
上述阳极特别适用于制备洗牙器中的臭氧发生系统，在提供水以及直流电源和恒定电流的条件下，即可随时随地制造具有适宜且稳定臭氧浓度的臭氧水，在任意水流量下均可实现安全的臭氧水输出。采用上述阳极制备的臭氧发生系 统可用于市面上任意洗牙器中，具备使用寿命长、成本低、无污染、制造简单、方便携带等显著优点。
一实施方式的洗牙器，包括臭氧发生系统，该臭氧发生系统包括上述阳极。此外，该臭氧发生系统还包括本领域的常规结构，例如阴极、容纳阳极和阴极的容器、供电单元等。阴极与阳极可以相对设置，为了达到较好的电解水产臭氧效果，阴极与阳极之间的垂直距离不超过5mm。臭氧发生系统可作为一个独立的组件或标准零件，可位于洗牙器的水箱与水泵之间，或者水泵与喷嘴之间，又或者喷嘴组件内部。将该臭氧发生系统接入恒流电源时，随着一定流量的水快速通过臭氧发生系统，能够在阳极稳定地输出臭氧浓度在0.1mg/L～0.6mg/L的臭氧水。该臭氧水可对牙齿牙床全方位进行清洁，既可达到快速洁净的目的，同时又可直接杀菌消毒，去除口臭，实现净化口腔和保护牙床健康的双重效能。上述洗牙器在使用过程中无任何有毒物质残存也无需任何添加剂，使用安全，是环保健康的低成本产品。
以下通过实施例进一步说明本发明，但不用于限制本发明。
实施例中所用的钛基材为钛板TA1，其它试剂均为商购产品。
实施例1
对钛板进行喷砂处理，然后置于浓度为20重量％的草酸溶液中在80℃下进行刻蚀30min，取出用纯水清洗干净。将氯化锡、氯化钌、氯化锰、钛酸丁酯和氯化镍溶于乙醇中，得到混合液，其中，Sn：Ru：Mn：Ti：Ni(摩尔比)＝320：12：1：4：10，氯化锡、氯化钌、氯化锰、钛酸丁酯和氯化镍的总重量与乙醇的重量比为1：5。将该混合液涂覆于钛板表面，在120℃烘干10min，然后在450℃下焙烧1h。再重复涂覆并在上述条件下烘干、焙烧4次，最后一次将焙烧温度提高为600℃并焙烧3h，得到本实施例制备的阳极。
实施例2
本实施例的阳极的制备步骤与实施例1大致相同，区别在于，混合液中，Sn：Ru：Mn：Ti：Ni(摩尔比)＝400：15：1：5：12。
实施例3
本实施例的阳极的制备步骤与实施例1大致相同，区别在于，混合液中，Sn：Ru：Mn：Ti：Ni(摩尔比)＝300：5：1：3：8。
实施例4
本实施例的阳极的制备步骤与实施例1大致相同，区别在于，混合液中，Sn：Ru：Mn：Ti：Ni(摩尔比)＝200：2.5：1：1.5：5。
实施例5
本实施例的阳极的制备步骤与实施例1大致相同，区别在于，混合液中，Sn：Ru：Mn：Ti：Ni(摩尔比)＝500：20：1：7：15。
对比例1
本对比例的阳极的制备步骤与实施例1大致相同，区别在于，混合液中不含钛酸丁酯，Sn：Ru：Mn：Ni(摩尔比)＝500：20：1：15。
测试例
将实施例1～5和对比例1制备的阳极组装为臭氧发生系统并进行臭氧发生测试。
将阳极与阴极置于一容器内，阳极与阴极之间距离为2mm，该容器具有入水口和出水口，接入恒流电源，上限电压为20V，恒流电流密度为15mA/cm 2，并由入水口以15L/hr的水流速度注入自来水，在出水口处测试臭氧水的实时浓度，每隔0.5h记录臭氧浓度列于表1。
表1
Figure PCTCN2019126857-appb-000001
由表1可见，将本发明的阳极用于电解水产臭氧工艺中能够稳定地输出臭氧浓度在0.1mg/L～0.6mg/L的臭氧水。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种用于电解水产臭氧工艺的阳极，其特征在于，该阳极包括钛基材和附着在所述钛基材表面的复合氧化物层，所述复合氧化物层的材料包括金属氧化物，所述金属氧化物中的金属元素包括锡、钌、锰、钛和镍，所述锡、钌、锰、钛和镍的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)：(5～15)。
  2. 根据权利要求1所述的阳极，其特征在于，所述锡、钌、锰、钛和镍的摩尔比为(300～400)：(5～15)：1：(3～5)：(8～12)。
  3. 一种用于电解水产臭氧工艺的阳极的制备方法，其特征在于，该方法包括以下步骤：
    获取含有锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的混合液；其中，以金属元素计的所述锡的前驱物、钌的前驱物、锰的前驱物、钛的前驱物和镍的前驱物的摩尔比为(200～500)：(2.5～20)：1：(1.5～7)：(5～15)；
    将所述混合液涂覆在钛基材上，然后焙烧，得到阳极。
  4. 根据权利要求3所述的方法，其特征在于，在将所述混合液涂覆在钛基材上之前，先对钛基材进行预处理，然后置于刻蚀液中进行刻蚀。
  5. 根据权利要求4所述的方法，其特征在于，所述预处理包括喷砂处理；及/或，
    所述刻蚀液选自草酸溶液和盐酸溶液中的至少一种；及/或，所述刻蚀的条件包括：温度为70℃～90℃，时间为20min～40min。
  6. 根据权利要求3所述的方法，其特征在于，将所述混合液涂覆在钛基材上后进行干燥，然后再进行所述焙烧；所述干燥的条件包括：温度为90℃～130℃，时间为5min～10min；及/或，
    所述焙烧的条件包括：温度为380℃～600℃，时间为1h～3h。
  7. 根据权利要求3所述的方法，其特征在于，将所述混合液涂覆在钛基材上然后焙烧的步骤重复进行3～5次。
  8. 权利要求1或2所述的阳极或者由权利要求3～7任意一项所述的方法制备得到的阳极在电解水产臭氧工艺中的应用，其特征在于，所述电解水产臭氧工艺的条件包括：电压不超过24V，恒流电流密度不超过20mA/cm 2。
  9. 一种臭氧发生系统，其特征在于，包括权利要求1或2所述的阳极或者权利要求3～7任意一项所述的方法制备得到的阳极。
  10. 一种洗牙器，其特征在于，包括权利要求9所述的臭氧发生系统。
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CN112921354B (zh) * 2021-01-25 2022-07-01 深圳市飞猫电器有限公司 一种阳极及其制备方法和应用、臭氧发生系统和食品净化器
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1751140A (zh) * 2003-02-14 2006-03-22 弗西蒂技术有限公司 产生臭氧的装置和方法
TW200932956A (en) * 2008-01-31 2009-08-01 Gainia Intellectual Asset Services Inc Configurable ozone generators
CN101608317A (zh) * 2008-06-19 2009-12-23 冠亚智财股份有限公司 臭氧产生器
CN105002517A (zh) * 2015-07-01 2015-10-28 苏州聪歌新能源科技有限公司 一种臭氧生成电极及其阳极的生产工艺和臭氧产生器
CN108456894A (zh) * 2018-02-02 2018-08-28 苏州庚泽新材料科技有限公司 一种新型的阳极材料及其制备方法、电解产生臭氧的装置
CN109602512A (zh) * 2019-01-24 2019-04-12 深圳市耐菲尔医疗器械科技有限公司 一种能够提供多种水源的冲牙器
CN110055548A (zh) * 2019-04-18 2019-07-26 周起文 电解臭氧用电极及其制备方法及电解臭氧水模组装置
CN110408949A (zh) * 2019-08-07 2019-11-05 深圳市耐菲尔医疗器械科技有限公司 阳极及其制备方法和应用、臭氧发生系统和洗牙器

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1620582B1 (en) * 2003-05-07 2016-12-21 De Nora Tech, Inc. Smooth surface morphology anode coatings
JP2005230707A (ja) * 2004-02-20 2005-09-02 Mitsubishi Heavy Ind Ltd 電気化学反応方法及び該装置
JP2006097122A (ja) * 2004-08-31 2006-04-13 Sanyo Electric Co Ltd 電解用電極及び電解用電極の製造方法
CN1900368B (zh) * 2006-06-30 2010-05-12 福州大学 高铈含量的含钌涂层钛阳极及其制备方法
JP6200508B2 (ja) * 2012-09-11 2017-09-20 アメリカン イーグル インストラメンツ インコーポレイテッドＡｍｅｒｉｃａｎ Ｅａｇｌｅ Ｉｎｓｔｒｕｍｅｎｔｓ， Ｉｎｃ． 放電洗浄器装置および方法
DE102013202144A1 (de) * 2013-02-08 2014-08-14 Bayer Materialscience Ag Elektrokatalysator, Elektrodenbeschichtung und Elektrode zur Herstellung von Chlor
US10329172B2 (en) * 2014-09-10 2019-06-25 Yan Tang & Ruizhi Feng Electrode, preparation method therefor, and uses thereof
JP7058152B2 (ja) * 2017-03-22 2022-04-21 旭化成株式会社 電解用電極
CN108754533B (zh) 2018-05-25 2020-11-17 西安交通大学 一种长寿命高活性电解水产臭氧的掺杂氧化锡电极的制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1751140A (zh) * 2003-02-14 2006-03-22 弗西蒂技术有限公司 产生臭氧的装置和方法
TW200932956A (en) * 2008-01-31 2009-08-01 Gainia Intellectual Asset Services Inc Configurable ozone generators
CN101608317A (zh) * 2008-06-19 2009-12-23 冠亚智财股份有限公司 臭氧产生器
CN105002517A (zh) * 2015-07-01 2015-10-28 苏州聪歌新能源科技有限公司 一种臭氧生成电极及其阳极的生产工艺和臭氧产生器
CN108456894A (zh) * 2018-02-02 2018-08-28 苏州庚泽新材料科技有限公司 一种新型的阳极材料及其制备方法、电解产生臭氧的装置
CN109602512A (zh) * 2019-01-24 2019-04-12 深圳市耐菲尔医疗器械科技有限公司 一种能够提供多种水源的冲牙器
CN110055548A (zh) * 2019-04-18 2019-07-26 周起文 电解臭氧用电极及其制备方法及电解臭氧水模组装置
CN110408949A (zh) * 2019-08-07 2019-11-05 深圳市耐菲尔医疗器械科技有限公司 阳极及其制备方法和应用、臭氧发生系统和洗牙器

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