WO2019192214A1 - Three-dimensional silver nanocomposite and manufacturing method thereof - Google Patents

Three-dimensional silver nanocomposite and manufacturing method thereof Download PDF

Info

Publication number
WO2019192214A1
WO2019192214A1 PCT/CN2018/122552 CN2018122552W WO2019192214A1 WO 2019192214 A1 WO2019192214 A1 WO 2019192214A1 CN 2018122552 W CN2018122552 W CN 2018122552W WO 2019192214 A1 WO2019192214 A1 WO 2019192214A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
solution
present
dimensional composite
nano silver
Prior art date
Application number
PCT/CN2018/122552
Other languages
French (fr)
Chinese (zh)
Inventor
黄翟
Original Assignee
太原氦舶新材料有限责任公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 太原氦舶新材料有限责任公司 filed Critical 太原氦舶新材料有限责任公司
Publication of WO2019192214A1 publication Critical patent/WO2019192214A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention relates to the field of nano silver technology, in particular to a three-dimensional composite nano silver and a preparation method thereof.
  • Nano-silver has the properties of conventional nanomaterials. As a precious metal nanomaterial, it also has good physical and chemical properties such as optics, electricity, and catalysis. It can be widely used in electronics, antibacterial materials, and catalysis.
  • the composite structure of nano-silver is a combination of nano-silver and other substances, which has wider significance in the application field.
  • the composite structure can make up for the shortcomings of nano-silver oxidized and easy to agglomerate.
  • the composite structure of nano-silver makes it widely used in the fields of catalysis and antibacterial.
  • the object of the present invention is to provide a method for preparing a three-dimensional composite nano-silver based on a physical process.
  • the invention provides a preparation method of three-dimensional composite nano silver, comprising:
  • the nanosilver is prepared into a three-dimensional composite nanosilver using a physical method.
  • the method for preparing the three-dimensional composite nano silver is specifically:
  • the nano silver solution is pretreated, centrifuged, ultrasonically dispersed and ground to obtain three-dimensional composite nano-silver.
  • the nano silver solution has a mass concentration of preferably 0.5 to 4%.
  • the nano silver in the nano silver solution has a particle diameter of 5 to 100 nm.
  • the solvent of the nano silver solution is one or more of an alcohol and water.
  • the pretreatment is:
  • the inorganic salt solution was mixed with the nano silver solution and allowed to stand.
  • the standing time is 24 to 48 hours.
  • the inorganic salt in the inorganic salt solution is a chlorate.
  • the chlorate salt is one or more of a perchlorate, a chlorate and a hydrochloride.
  • the invention provides a three-dimensional composite nano silver prepared by the method described in the above technical solution.
  • the invention provides a preparation method of three-dimensional composite nano silver, which comprises: preparing nano silver into three-dimensional composite nano silver by using a physical method.
  • the surface of the nano silver particles dispersed in the solution contains an organic protective agent to prevent sedimentation thereof.
  • the use of the chlorate in the present invention can destroy the surface protection, expose the surface of the metallic silver itself, and then perform centrifugation and ball milling.
  • the silver and silver surfaces are in contact with each other, and the electrical contact is good, so the electrical properties of the material are significantly improved.
  • the invention adopts a physical method to prepare three-dimensional composite nano silver, and the preparation method of the three-dimensional composite nano silver provided by the invention has the characteristics of high yield, low cost, environmental protection and high efficiency.
  • the invention uses the pure physical process to prepare the three-dimensional composite nano silver, is environmentally friendly and efficient, and the prepared three-dimensional composite nano silver has excellent electrical properties.
  • the invention provides a preparation method of three-dimensional composite nano silver, comprising:
  • the nanosilver is prepared into a three-dimensional composite nanosilver using a physical method.
  • the method for preparing the three-dimensional composite nano silver is specifically:
  • the nano silver solution is pretreated, centrifuged, ultrasonically dispersed and ground to obtain three-dimensional composite nano-silver.
  • the mass concentration of the nanosilver solution is preferably from 0.5 to 4%, more preferably from 1 to 3.5%, and most preferably from 1.5 to 3%.
  • the source of the nano silver solution in the present invention is not particularly limited, and can be prepared by a preparation method of a nano silver solution well known to those skilled in the art, and the nano silver solution can be directly reacted by a method well known to those skilled in the art.
  • the nano silver solution can be prepared by dissolving the nano silver in a solvent.
  • the preparation method of the nano silver solution is preferably:
  • the silver source solution and the protective agent solution are mixed, and then a reducing agent is added to carry out a reaction to obtain a nano silver solution.
  • the present invention is not particularly limited to the silver source, and a silver source for preparing nano silver, such as silver nitrate, which is well known to those skilled in the art, can be used.
  • the protective agent in the protective agent solution is preferably polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylsulfonate or sodium dodecylbenzenesulfonate.
  • gelatin polyvinyl alcohol, alkyl mercaptan, oleic acid, polyacrylic acid, sodium hexametaphosphate, polyethylene glycol, fatty alcohol polyoxyethylene ether, polyoxyethylene stearate, oleic acid amide, erucamide
  • polyacrylamide, sodium methylene dimethyl naphthalenesulfonate and ammonium polycarboxylate, more preferably polyvinylpyrrolidone is not particularly limited, and a reducing agent for preparing nano silver is well known to those skilled in the art.
  • the reducing agent is preferably an amine reducing agent, more preferably hydrazine hydrate or Ethylenediamine is most preferably ethylenediamine.
  • the temperature of the reaction is preferably from 150 to 250 ° C, more preferably from 170 to 200 ° C; and the reaction time is preferably from 8 to 12 hours, more preferably from 9 to 10 hours.
  • the particle size of the nanosilver in the nanosilver solution is preferably 5 to 100 nm, more preferably 10 to 80 nm, still more preferably 20 to 60 nm, and most preferably 30 to 50 nm.
  • the present invention has no particular limitation on the kind and source of the nano silver, and is prepared by a preparation method of nano silver well known to those skilled in the art or can be purchased from the market.
  • the nano silver prepared in the prior art is not easy to settle in a stable dispersion thereof, and the surface thereof generally has an organic protective agent.
  • the nano silver surface is provided with an organic protective agent, and the organic protection
  • the agent is preferably polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, gelatin, polyvinyl alcohol, alkyl mercaptan, oil Acid, polyacrylic acid, sodium hexametaphosphate, polyethylene glycol, fatty alcohol polyoxyethylene ether, polyoxyethylene stearate, oleic acid amide, erucamide, polyacrylamide, methylene dimethyl sulfene One or more of sodium and polycarboxylate ammonium salts, more preferably polyvinylpyrrolidone.
  • the preparation method of the nano silver is preferably:
  • the nano silver solution prepared by the method described in the above technical solution is centrifuged, and the precipitate after centrifugation is collected and dried to obtain nano silver. Since the method described in the above technical solution uses a protective agent solution in the process of preparing the nano silver solution, the obtained nano silver surface is provided with the above organic protective agent.
  • the solvent of the nanosilver solution is preferably one or more of an alcohol and water, more preferably an alcohol compound having 1 to 5 carbon atoms and one or more of water, most preferably ethanol.
  • an alcohol compound having 1 to 5 carbon atoms and one or more of water most preferably ethanol.
  • methanol, ethylene glycol, glycerol and water are preferably one or more of methanol, ethylene glycol, glycerol and water.
  • the pretreatment is preferably:
  • the inorganic salt solution was mixed with the nano silver solution and allowed to stand.
  • the standing time is preferably 24 to 48 hours, more preferably 30 to 40 hours, and most preferably 35 hours.
  • the standing temperature is preferably 20 to 30 ° C, more preferably 22 to 28 ° C, and most preferably 24 to 26 ° C.
  • the solvent in the inorganic salt solution is preferably one or more of a ketone compound, an alcohol compound and water, more preferably a ketone compound having 1 to 5 carbon atoms, and having a carbon number of One or more of the alcohol compound of 1 to 5 and water, and most preferably one or more of ethanol, methanol, ethylene glycol, glycerin, acetone, and water.
  • the mass concentration of the inorganic salt solution is preferably from 1 to 20%, more preferably from 5 to 15%, most preferably from 8 to 12%.
  • the inorganic salt is preferably a chlorate-containing salt, more preferably one or more of a perchlorate, a chlorate and a hydrochloride, most preferably sodium perchlorate, potassium perchlorate, One or more of sodium chloride and sodium chlorate.
  • the chlorate is capable of removing the organic protective agent on the surface of the nano silver particles, so that the contact between the silver nanoparticles is better during the subsequent physical treatment, so that the prepared three-dimensional composite nano silver has good conductivity. Sex.
  • the mass ratio of the nanosilver solution to the inorganic salt solution is preferably (10 to 20):1, more preferably (12 to 18):1, and most preferably (14 to 16):1.
  • all the steps of preparing the three-dimensional composite nanosilver are preferably carried out at room temperature, more preferably at 20 to 30 °C.
  • the rotational speed of the centrifugation is preferably 8,000 to 20,000 rpm, more preferably 10,000 to 16,000 rpm, and most preferably 12,000 to 14,000 rpm.
  • the centrifugation time is preferably from 1 to 15 hours, more preferably from 3 to 12 hours, and most preferably from 5 to 10 hours.
  • the ultrasonically dispersed reagent is preferably an alcohol compound, more preferably an alcohol compound having 1 to 5 carbon atoms, and most preferably ethanol.
  • the mass ratio of the reagent to the solid precipitate during the ultrasonic dispersion is preferably 1: (15 to 25), more preferably 1: (18 to 22), and most preferably 1:20.
  • the ultrasonic dispersion time is preferably from 20 to 40 minutes, more preferably from 25 to 35 minutes, and most preferably from 30 minutes.
  • the ultrasonication is preferably carried out after dispersion, and after drying, it is preferably subjected to ball milling.
  • the ball milling time is preferably from 2 to 10 hours, more preferably from 3 to 8 hours, and most preferably from 4 to 6 hours.
  • the three-dimensional composite nano silver prepared by the method provided by the invention has good electrical conductivity and catalytic property, and has application value in the fields of conduction and catalysis.
  • the invention adopts a physical method to prepare three-dimensional composite nano silver, and the preparation method of the three-dimensional composite nano silver provided by the invention has the characteristics of high yield, low cost, environmental protection and high efficiency.
  • the invention uses the pure physical process to prepare the three-dimensional composite nano silver, is environmentally friendly and efficient, and the prepared three-dimensional composite nano silver has excellent electrical properties.
  • nano silver used in the following examples of the present invention was prepared according to the following method:
  • the mixture was transferred to a hydrothermal reaction vessel, stirred and heated at 170 ° C in an oil bath, stirred for about 10 hours to carry out a reaction, and the pressure of the reaction was controlled to be 10 MPa.
  • the obtained reaction product was completely cooled and taken out to obtain a nanosilver solution.
  • nanosilver solution was centrifuged, and the precipitate obtained by centrifugation was collected and dried to obtain nanosilver having an average particle size of 40 nm.
  • a nano-silver solution having a mass concentration of 3% 100 mL of a nano-silver solution having a mass concentration of 3% was added to 5 mL of a sodium perchlorate solution having a mass concentration of 2%, and the solution was uniformly mixed and allowed to stand for 10 hours; the solvent in the nano-silver solution was water.
  • the solvent in the sodium perchlorate solution is water;
  • the three-dimensional composite nano silver prepared by the first embodiment of the invention is prepared into a silver paste, and the specific method is as follows:
  • the conductive properties of the silver paste prepared in Example 1 of the present invention were tested by a four-probe square resistance tester. The test results showed that the conductive silver paste prepared in Example 1 of the present invention had a square resistance of 20 m ⁇ .
  • a nano-silver solution having a mass concentration of 5% 100 mL of a nano-silver solution having a mass concentration of 5% was added to 10 mL of a 1% sodium chlorate solution, and the solution was mixed and stirred uniformly for 10 hours; the solvent in the nano-silver solution was water.
  • the solvent in the sodium chlorate solution is water;
  • Example 2 of the present invention was prepared into a silver paste according to the method of Example 1.
  • Example 2 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Example 2 of the present invention was 42 m ⁇ .
  • Example 3 of the present invention was prepared into a silver paste according to the method of Example 1.
  • Example 3 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Example 3 of the present invention was 25 m ⁇ .
  • the silver paste was prepared according to the method of Example 1, and the difference from Example 1 was that the three-dimensional composite nano-silver in Example 1 was replaced with silver powder having an average particle size of 10 ⁇ m, and the amount of silver powder was compared with the three-dimensional composite nanometer in Example 1.
  • the amount of silver used is the same.
  • the silver paste prepared in Comparative Example 1 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Comparative Example 1 of the present invention was 68 m ⁇ .
  • the silver paste was prepared according to the method of Example 1. The difference from Example 1 was that the three-dimensional composite nano-silver in Example 1 was replaced with a nano-silver powder having an average particle size of 40 nm, and the amount of the nano-silver powder was compared with the three-dimensional composite nanometer in Example 1. The amount of silver used is the same.
  • the silver paste prepared in Comparative Example 2 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Comparative Example 2 of the present invention was 123 m ⁇ .
  • the three-dimensional composite nanosilver was prepared according to the method described in Example 1, and was different from Example 1 in that no sodium perchlorate solution was added.
  • the three-dimensional composite nanosilver prepared in Comparative Example 3 of the present invention was prepared into a silver paste according to the method of Example 1.
  • the silver paste prepared in Comparative Example 3 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Comparative Example 3 of the present invention was 164 m ⁇ .
  • the present invention provides a method for preparing a three-dimensional composite nano-silver, comprising: preparing a nano-silver into a three-dimensional composite nano-silver using a physical method.
  • the invention adopts a physical method to prepare three-dimensional composite nano silver, and the preparation method of the three-dimensional composite nano silver provided by the invention has the characteristics of high yield, low cost, environmental protection and high efficiency.
  • the invention uses the pure physical process to prepare the three-dimensional composite nano silver, is environmentally friendly and efficient, and the prepared three-dimensional composite nano silver has excellent electrical properties.

Abstract

A manufacturing method of a three-dimensional silver nanocomposite, employing a physical method to manufacture a three-dimensional silver nanocomposite from nano silver, and specifically comprising: performing centrifugation, ultrasonic dispersion and grinding on a pre-processed nano silver solution. Further provided is a three-dimensional silver nanocomposite manufactured by the above manufacturing method. The manufacturing method of a three-dimensional silver nanocomposite has high yields and low costs, is eco-friendly and highly efficient, and produces a three-dimensional silver nanocomposite having excellent electrical properties.

Description

一种三维复合纳米银及其制备方法Three-dimensional composite nano silver and preparation method thereof
本申请要求于2018年4月4日提交中国专利局、申请号为201810298295.3、发明名称为“一种三维复合纳米银及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。The present application claims priority to Chinese Patent Application No. 201810298295.3, entitled "A Three-Dimensional Composite Nanosilver and Its Preparation Method", filed on April 4, 2018, the entire contents of which are incorporated herein by reference. In this application.
技术领域Technical field
本发明涉及纳米银技术领域，尤其涉及到一种三维复合纳米银及其制备方法。The invention relates to the field of nano silver technology, in particular to a three-dimensional composite nano silver and a preparation method thereof.
背景技术Background technique
纳米银具有常规纳米材料的性质，作为贵金属纳米材料，还具有良好的光学、电学、催化等奇特的物理化学性能，可以广泛应用于电子、抗菌材料、催化等领域。Nano-silver has the properties of conventional nanomaterials. As a precious metal nanomaterial, it also has good physical and chemical properties such as optics, electricity, and catalysis. It can be widely used in electronics, antibacterial materials, and catalysis.
纳米银的复合结构，是将纳米银与其他物质复合在一起，在应用领域具有更广泛的意义，复合结构可以弥补纳米银易氧化，易团聚的缺点。纳米银的复合结构，使其在催化、抗菌领域应用广泛。The composite structure of nano-silver is a combination of nano-silver and other substances, which has wider significance in the application field. The composite structure can make up for the shortcomings of nano-silver oxidized and easy to agglomerate. The composite structure of nano-silver makes it widely used in the fields of catalysis and antibacterial.
但是，现有技术在制备纳米银复合结构时往往采用化学与物理结合的方法，制备工艺复杂。However, the prior art often adopts a combination of chemical and physical methods in preparing a nano-silver composite structure, and the preparation process is complicated.
发明内容Summary of the invention
有鉴于此，本发明的目的在于提供一种基于物理过程的工艺简单的三维复合纳米银的制备方法。In view of this, the object of the present invention is to provide a method for preparing a three-dimensional composite nano-silver based on a physical process.
本发明提供了一种三维复合纳米银的制备方法，包括：The invention provides a preparation method of three-dimensional composite nano silver, comprising:
使用物理方法将纳米银制备成三维复合纳米银。The nanosilver is prepared into a three-dimensional composite nanosilver using a physical method.
优选的，所述三维复合纳米银的制备方法具体为：Preferably, the method for preparing the three-dimensional composite nano silver is specifically:
将纳米银溶液预处理后进行离心、超声分散和研磨，得到三维复合纳米银。The nano silver solution is pretreated, centrifuged, ultrasonically dispersed and ground to obtain three-dimensional composite nano-silver.
优选的，所述纳米银溶液的质量浓度优选为0.5～4％。Preferably, the nano silver solution has a mass concentration of preferably 0.5 to 4%.
优选的，所述纳米银溶液中纳米银的粒径为5～100nm。Preferably, the nano silver in the nano silver solution has a particle diameter of 5 to 100 nm.
优选的，所述纳米银溶液的溶剂为醇和水中的一种或几种。Preferably, the solvent of the nano silver solution is one or more of an alcohol and water.
优选的，所述预处理为：Preferably, the pretreatment is:
将无机盐溶液与纳米银溶液混合后静置。The inorganic salt solution was mixed with the nano silver solution and allowed to stand.
优选的，所述静置的时间为24～48小时。Preferably, the standing time is 24 to 48 hours.
优选的，所述无机盐溶液中的无机盐为含氯酸盐。Preferably, the inorganic salt in the inorganic salt solution is a chlorate.
优选的，所述含氯酸盐为高氯酸盐、氯酸盐和盐酸盐中的一种或几种。Preferably, the chlorate salt is one or more of a perchlorate, a chlorate and a hydrochloride.
本发明提供了一种上述技术方案所述的方法制备得到的三维复合纳米银。The invention provides a three-dimensional composite nano silver prepared by the method described in the above technical solution.
本发明提供了一种三维复合纳米银的制备方法，包括：使用物理方法将纳米银制备成三维复合纳米银。在本发明中，分散在溶液中的纳米银颗粒表面含有有机保护剂，避免其沉降，本发明采用含氯酸盐可以破坏其表面保护，使金属银本身的表面暴露出来，在后续离心，球磨等物理过程中，银与银表面相接触，其电接触较好，因此材料的电性能有显著提高。本发明使用物理的方法制备得到三维复合纳米银，本发明提供的三维复合纳米银的制备方法具有产率高、成本低、环保和高效等特点。本发明使用纯物理过程制备三维复合纳米银，环保高效，而且制备得到的三维复合纳米银电学性能优异。The invention provides a preparation method of three-dimensional composite nano silver, which comprises: preparing nano silver into three-dimensional composite nano silver by using a physical method. In the present invention, the surface of the nano silver particles dispersed in the solution contains an organic protective agent to prevent sedimentation thereof. The use of the chlorate in the present invention can destroy the surface protection, expose the surface of the metallic silver itself, and then perform centrifugation and ball milling. In the physical process, the silver and silver surfaces are in contact with each other, and the electrical contact is good, so the electrical properties of the material are significantly improved. The invention adopts a physical method to prepare three-dimensional composite nano silver, and the preparation method of the three-dimensional composite nano silver provided by the invention has the characteristics of high yield, low cost, environmental protection and high efficiency. The invention uses the pure physical process to prepare the three-dimensional composite nano silver, is environmentally friendly and efficient, and the prepared three-dimensional composite nano silver has excellent electrical properties.
具体实施方式detailed description
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described below. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
本发明提供了一种三维复合纳米银的制备方法，包括：The invention provides a preparation method of three-dimensional composite nano silver, comprising:
使用物理方法将纳米银制备成三维复合纳米银。The nanosilver is prepared into a three-dimensional composite nanosilver using a physical method.
在本发明中，所述三维复合纳米银的制备方法具体为：In the present invention, the method for preparing the three-dimensional composite nano silver is specifically:
将纳米银溶液预处理后进行离心、超声分散和研磨，得到三维复合纳米银。The nano silver solution is pretreated, centrifuged, ultrasonically dispersed and ground to obtain three-dimensional composite nano-silver.
在本发明中，所述纳米银溶液的质量浓度优选为0.5～4％，更优选为 1～3.5％，最优选为1.5～3％。本发明对所述纳米银溶液的来源没有特殊的限制，采用本领域技术人员熟知的纳米银溶液的制备方法进行制备即可，可采用本领域技术人员熟知的方法直接反应制备纳米银溶液，也可将纳米银溶解在溶剂中配制得到纳米银溶液。In the present invention, the mass concentration of the nanosilver solution is preferably from 0.5 to 4%, more preferably from 1 to 3.5%, and most preferably from 1.5 to 3%. The source of the nano silver solution in the present invention is not particularly limited, and can be prepared by a preparation method of a nano silver solution well known to those skilled in the art, and the nano silver solution can be directly reacted by a method well known to those skilled in the art. The nano silver solution can be prepared by dissolving the nano silver in a solvent.
在本发明中，所述纳米银溶液的制备方法优选为：In the present invention, the preparation method of the nano silver solution is preferably:
将银源溶液和保护剂溶液混合后加入还原剂进行反应，得到纳米银溶液。The silver source solution and the protective agent solution are mixed, and then a reducing agent is added to carry out a reaction to obtain a nano silver solution.
本发明对所述银源没有特殊的限制，采用本领域技术人员熟知的制备纳米银的银源即可，如硝酸银。在本发明中，所述保护剂溶液中的保护剂优选为聚乙烯吡络烷酮、十六烷基三甲基溴化铵、十二烷基磺酸钠、十二烷基苯磺酸钠、明胶、聚乙烯醇、烷基硫醇、油酸、聚丙烯酸、六偏磷酸钠、聚乙二醇、脂肪醇聚氧乙烯醚、硬脂酸聚氧乙烯酯、油酸酰胺、芥酸酰胺、聚丙烯酰胺、亚甲基双甲基萘磺酸钠和聚羧酸铵盐中的一种或几种，更优选为聚乙烯吡络烷酮。本发明对所述还原剂没有特殊的限制，采用本领域技术人员熟知的制备纳米银的还原剂即可，在本发明中，所述还原剂优选为胺类还原剂，更优选为水合肼或乙二胺，最优选为乙二胺。在本发明中，所述反应的温度优选为150～250℃，更优选为170～200℃；所述反应的时间优选为8～12小时，更优选为9～10小时。The present invention is not particularly limited to the silver source, and a silver source for preparing nano silver, such as silver nitrate, which is well known to those skilled in the art, can be used. In the present invention, the protective agent in the protective agent solution is preferably polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylsulfonate or sodium dodecylbenzenesulfonate. , gelatin, polyvinyl alcohol, alkyl mercaptan, oleic acid, polyacrylic acid, sodium hexametaphosphate, polyethylene glycol, fatty alcohol polyoxyethylene ether, polyoxyethylene stearate, oleic acid amide, erucamide One or more of polyacrylamide, sodium methylene dimethyl naphthalenesulfonate and ammonium polycarboxylate, more preferably polyvinylpyrrolidone. The reducing agent is not particularly limited, and a reducing agent for preparing nano silver is well known to those skilled in the art. In the present invention, the reducing agent is preferably an amine reducing agent, more preferably hydrazine hydrate or Ethylenediamine is most preferably ethylenediamine. In the present invention, the temperature of the reaction is preferably from 150 to 250 ° C, more preferably from 170 to 200 ° C; and the reaction time is preferably from 8 to 12 hours, more preferably from 9 to 10 hours.
在本发明中，所述纳米银溶液中纳米银的粒径优选为5～100nm，更优选为10～80nm，更优选为20～60nm，最优选为30～50nm。本发明对所述纳米银的种类和来源没有特殊的限制，采用本领域技术人员熟知的纳米银的制备方法制备得到或者由市场购买即可。现有技术中所制备的纳米银为使其稳定的分散在溶液中不易沉降，其表面一般带有有机保护剂，在本发明中，所述纳米银表面带有有机保护剂，所述有机保护剂优选为聚乙烯吡络烷酮、十六烷基三甲基溴化铵、十二烷基磺酸钠、十二烷基苯磺酸钠、明胶、聚乙烯醇、烷基硫醇、油酸、聚丙烯酸、六偏磷酸钠、聚乙二醇、脂肪醇聚氧乙烯醚、硬脂酸聚氧乙烯酯、油酸酰胺、芥酸酰胺、聚丙烯酰胺、亚甲基双甲基萘磺酸钠和聚羧酸铵盐中的一种或几种，更优选为聚乙烯吡络烷酮。在本发明中，所述纳米银的制备方法优选为：In the present invention, the particle size of the nanosilver in the nanosilver solution is preferably 5 to 100 nm, more preferably 10 to 80 nm, still more preferably 20 to 60 nm, and most preferably 30 to 50 nm. The present invention has no particular limitation on the kind and source of the nano silver, and is prepared by a preparation method of nano silver well known to those skilled in the art or can be purchased from the market. The nano silver prepared in the prior art is not easy to settle in a stable dispersion thereof, and the surface thereof generally has an organic protective agent. In the present invention, the nano silver surface is provided with an organic protective agent, and the organic protection The agent is preferably polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, gelatin, polyvinyl alcohol, alkyl mercaptan, oil Acid, polyacrylic acid, sodium hexametaphosphate, polyethylene glycol, fatty alcohol polyoxyethylene ether, polyoxyethylene stearate, oleic acid amide, erucamide, polyacrylamide, methylene dimethyl sulfene One or more of sodium and polycarboxylate ammonium salts, more preferably polyvinylpyrrolidone. In the present invention, the preparation method of the nano silver is preferably:
将上述技术方案所述的方法制备得到的纳米银溶液进行离心分离，收集离心后的沉淀进行干燥，得到纳米银。由于上述技术方案所述的方法在制备纳米银溶液过程中采用了保护剂溶液使获得的纳米银表面带有上述有机保护剂。The nano silver solution prepared by the method described in the above technical solution is centrifuged, and the precipitate after centrifugation is collected and dried to obtain nano silver. Since the method described in the above technical solution uses a protective agent solution in the process of preparing the nano silver solution, the obtained nano silver surface is provided with the above organic protective agent.
在本发明中，所述纳米银溶液的溶剂优选为醇和水中的一种或几种，更优选为碳原子数为1～5的醇类化合物和水中的一种或几种，最优选为乙醇、甲醇、乙二醇、丙三醇和水中的一种或几种。In the present invention, the solvent of the nanosilver solution is preferably one or more of an alcohol and water, more preferably an alcohol compound having 1 to 5 carbon atoms and one or more of water, most preferably ethanol. One or more of methanol, ethylene glycol, glycerol and water.
在本发明中，所述预处理优选为：In the present invention, the pretreatment is preferably:
将无机盐溶液与纳米银溶液混合后静置。The inorganic salt solution was mixed with the nano silver solution and allowed to stand.
在本发明中，优选在搅拌的条件下进行混合。In the present invention, it is preferred to carry out the mixing under stirring.
在本发明中，所述静置的时间优选为24～48小时，更优选为30～40小时，最优选为35小时。In the present invention, the standing time is preferably 24 to 48 hours, more preferably 30 to 40 hours, and most preferably 35 hours.
在本发明中，所述静置的温度优选为20～30℃，更优选为22～28℃，最优选为24～26℃。In the present invention, the standing temperature is preferably 20 to 30 ° C, more preferably 22 to 28 ° C, and most preferably 24 to 26 ° C.
在本发明中，所述无机盐溶液中的溶剂优选为酮类化合物、醇类化合物和水中的一种或几种，更优选为碳原子数为1～5的酮类化合物、碳原子数为1～5的醇类化合物和水中的一种或几种，最优选为乙醇、甲醇、乙二醇、丙三醇、丙酮和水中的一种或几种。In the present invention, the solvent in the inorganic salt solution is preferably one or more of a ketone compound, an alcohol compound and water, more preferably a ketone compound having 1 to 5 carbon atoms, and having a carbon number of One or more of the alcohol compound of 1 to 5 and water, and most preferably one or more of ethanol, methanol, ethylene glycol, glycerin, acetone, and water.
在本发明中，所述无机盐溶液的质量浓度优选为1～20％，更优选为5～15％，最优选为8～12％。In the present invention, the mass concentration of the inorganic salt solution is preferably from 1 to 20%, more preferably from 5 to 15%, most preferably from 8 to 12%.
在本发明中，所述无机盐优选为含氯酸盐，更优选为高氯酸盐、氯酸盐和盐酸盐中的一种或几种，最优选为高氯酸钠、高氯酸钾、氯化钠和氯酸钠中的一种或几种。在本发明中，所述含氯酸盐能够除去纳米银颗粒表面的有机保护剂，使后续物理处理过程中，银纳米颗粒间接触更好，从而使制备得到的三维复合纳米银具有良好的导电性。In the present invention, the inorganic salt is preferably a chlorate-containing salt, more preferably one or more of a perchlorate, a chlorate and a hydrochloride, most preferably sodium perchlorate, potassium perchlorate, One or more of sodium chloride and sodium chlorate. In the present invention, the chlorate is capable of removing the organic protective agent on the surface of the nano silver particles, so that the contact between the silver nanoparticles is better during the subsequent physical treatment, so that the prepared three-dimensional composite nano silver has good conductivity. Sex.
在本发明中，所述纳米银溶液和无机盐溶液的质量比优选为(10～20)：1，更优选为(12～18)：1，最优选为(14～16)：1。In the present invention, the mass ratio of the nanosilver solution to the inorganic salt solution is preferably (10 to 20):1, more preferably (12 to 18):1, and most preferably (14 to 16):1.
在本发明中，所述制备三维复合纳米银的所有操作步骤优选在室温下进行，更优选在20～30℃下进行。In the present invention, all the steps of preparing the three-dimensional composite nanosilver are preferably carried out at room temperature, more preferably at 20 to 30 °C.
在本发明中，所述离心的转速优选为8000～20000转/分钟，更优选为10000～16000转/分钟，最优选为12000～14000转/分钟。在本发明中，所述离心的时间优选为1～15小时，更优选为3～12小时，最优选为5～10小时。In the present invention, the rotational speed of the centrifugation is preferably 8,000 to 20,000 rpm, more preferably 10,000 to 16,000 rpm, and most preferably 12,000 to 14,000 rpm. In the present invention, the centrifugation time is preferably from 1 to 15 hours, more preferably from 3 to 12 hours, and most preferably from 5 to 10 hours.
在本发明中，所述离心完成后优选取出固体沉淀进行超声分散。In the present invention, after the completion of the centrifugation, it is preferred to take out a solid precipitate for ultrasonic dispersion.
在本发明中，所述超声分散的试剂优选为醇类化合物，更优选为碳原子数为1～5的醇类化合物，最优选为乙醇。In the present invention, the ultrasonically dispersed reagent is preferably an alcohol compound, more preferably an alcohol compound having 1 to 5 carbon atoms, and most preferably ethanol.
在本发明中，所述超声分散过程中试剂和固体沉淀的质量比优选为1：(15～25)，更优选为1：(18～22)，最优选为1:20。In the present invention, the mass ratio of the reagent to the solid precipitate during the ultrasonic dispersion is preferably 1: (15 to 25), more preferably 1: (18 to 22), and most preferably 1:20.
在本发明中，所述超声分散的时间优选为20～40分钟，更优选为25～35分钟，最优选为30分钟。In the present invention, the ultrasonic dispersion time is preferably from 20 to 40 minutes, more preferably from 25 to 35 minutes, and most preferably from 30 minutes.
在本发明中，所述超声分散后优选进行干燥，干燥后优选进行球磨。In the present invention, the ultrasonication is preferably carried out after dispersion, and after drying, it is preferably subjected to ball milling.
在本发明中，所述球磨的时间优选为2～10小时，更优选为3～8小时，最优选为4～6小时。In the present invention, the ball milling time is preferably from 2 to 10 hours, more preferably from 3 to 8 hours, and most preferably from 4 to 6 hours.
本发明提供的方法制备得到的三维复合纳米银具有良好的导电性和催化性，在导电及催化等领域具有应用价值。The three-dimensional composite nano silver prepared by the method provided by the invention has good electrical conductivity and catalytic property, and has application value in the fields of conduction and catalysis.
本发明使用物理的方法制备得到三维复合纳米银，本发明提供的三维复合纳米银的制备方法具有产率高、成本低、环保和高效等特点。本发明使用纯物理过程制备三维复合纳米银，环保高效，而且制备得到的三维复合纳米银电学性能优异。The invention adopts a physical method to prepare three-dimensional composite nano silver, and the preparation method of the three-dimensional composite nano silver provided by the invention has the characteristics of high yield, low cost, environmental protection and high efficiency. The invention uses the pure physical process to prepare the three-dimensional composite nano silver, is environmentally friendly and efficient, and the prepared three-dimensional composite nano silver has excellent electrical properties.
本发明以下实施例所采用的纳米银为按照下述方法制备得到的：The nano silver used in the following examples of the present invention was prepared according to the following method:
配置100mL，质量浓度为27％的硝酸银水溶液；加入200mL质量浓度为25％的聚乙烯吡络烷酮乙醇溶液，将溶液混合搅拌均匀；将30mL的乙二胺加入到混合液中搅拌，将搅拌物转移至水热反应釜中，在油浴中搅拌加热170℃，搅拌10h左右进行反应，控制反应的压力为10MPa，将得到的反应产物完全冷却后取出，得到纳米银溶液。Dispensing 100 mL of a silver nitrate aqueous solution having a mass concentration of 27%; adding 200 mL of a 25% by weight solution of polyvinylpyrrolidone in ethanol, mixing and stirring the solution uniformly; adding 30 mL of ethylenediamine to the mixture and stirring The mixture was transferred to a hydrothermal reaction vessel, stirred and heated at 170 ° C in an oil bath, stirred for about 10 hours to carry out a reaction, and the pressure of the reaction was controlled to be 10 MPa. The obtained reaction product was completely cooled and taken out to obtain a nanosilver solution.
将上述纳米银溶液进行离心分离，收集离心分离得到的沉淀进行干燥，得到平均粒度为40nm的纳米银。The above nanosilver solution was centrifuged, and the precipitate obtained by centrifugation was collected and dried to obtain nanosilver having an average particle size of 40 nm.
实施例1Example 1
将100mL的质量浓度为3％的纳米银溶液，加入5mL质量浓度为2％的高氯酸钠溶液中，将溶液混合搅拌均匀、静置10小时；所述纳米银溶液中的溶剂为水，所述高氯酸钠溶液中的溶剂为水；100 mL of a nano-silver solution having a mass concentration of 3% was added to 5 mL of a sodium perchlorate solution having a mass concentration of 2%, and the solution was uniformly mixed and allowed to stand for 10 hours; the solvent in the nano-silver solution was water. The solvent in the sodium perchlorate solution is water;
将静置后的溶液在12000转/分钟的转速下，离心1小时，取出固体，加入10mL的乙醇，超声30分钟，干燥后，球磨3小时，得到三维复合纳米银。The solution after standing was centrifuged at 12,000 rpm for 1 hour, the solid was taken out, 10 mL of ethanol was added, ultrasonication was carried out for 30 minutes, and after drying, it was ball-milled for 3 hours to obtain three-dimensional composite nano silver.
将本发明实施例1制备得到的三维复合纳米银制备成银浆，具体方法为：The three-dimensional composite nano silver prepared by the first embodiment of the invention is prepared into a silver paste, and the specific method is as follows:
将对甲苯磺酸3g、醛酮树脂10g、松油醇40mL、钛酸酯偶联剂2g和5g本发明实施例1制备的三维复合纳米银均匀混合，得到银浆。3 g of p-toluenesulfonic acid, 10 g of aldehyde ketone resin, 40 mL of terpineol, 2 g of titanate coupling agent, and 5 g of the three-dimensional composite nanosilver prepared in Example 1 of the present invention were uniformly mixed to obtain a silver paste.
采用四探针方阻测试仪测试本发明实施例1制备得到的银浆的导电性能，检测结果为，本发明实施例1制备得到的导电银浆的方阻为20mΩ。The conductive properties of the silver paste prepared in Example 1 of the present invention were tested by a four-probe square resistance tester. The test results showed that the conductive silver paste prepared in Example 1 of the present invention had a square resistance of 20 mΩ.
实施例2Example 2
将100mL、质量浓度为5％的纳米银溶液，加入10mL质量浓度为1％的氯酸钠溶液中，将溶液混合搅拌均匀、静置10小时；所述纳米银溶液中的溶剂为水，所述氯酸钠溶液中的溶剂为水；100 mL of a nano-silver solution having a mass concentration of 5% was added to 10 mL of a 1% sodium chlorate solution, and the solution was mixed and stirred uniformly for 10 hours; the solvent in the nano-silver solution was water. The solvent in the sodium chlorate solution is water;
将静置后的溶液在12000转/分钟的转速下，离心3小时，取出固体，加入10mL的乙醇，超声30分钟，干燥后，球磨2小时，得到三维复合纳米银。The solution after standing was centrifuged at 12,000 rpm for 3 hours, the solid was taken out, 10 mL of ethanol was added, ultrasonication was carried out for 30 minutes, and after drying, ball milling was carried out for 2 hours to obtain three-dimensional composite nano silver.
按照实施例1的方法将本发明实施例2制备得到的三维复合纳米银制备成银浆。The three-dimensional composite nano silver prepared in Example 2 of the present invention was prepared into a silver paste according to the method of Example 1.
按照实施例1的方法对本发明实施例2制备得到银浆进行导电性检测，检测结果为，本发明实施例2制备的导电银浆的方阻为42mΩ。The silver paste prepared in Example 2 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Example 2 of the present invention was 42 mΩ.
实施例3Example 3
将100mL、质量浓度为10％的纳米银溶液，加入20mL质量浓度为2％的含氯酸盐溶液中，所述含氯酸盐为摩尔比为1:1的氯化钠和高氯酸钠，将溶液混合搅拌均匀、静置10小时；所述纳米银溶液中的溶剂为水，所述含氯酸盐溶液中的溶剂为水；100 mL of a 10% by mass nano silver solution was added to 20 mL of a 2% by weight chlorate solution, the chlorate was 1:1 molar ratio of sodium chloride and sodium perchlorate. The solution is uniformly stirred and allowed to stand for 10 hours; the solvent in the nano silver solution is water, and the solvent in the chlorate solution is water;
将静置后的溶液在12000转/分钟的转速下，离心5小时，取出固体， 加入10mL的乙醇，超声30分钟，干燥后，球磨2小时，得到三维复合纳米银。The solution after standing was centrifuged at 12,000 rpm for 5 hours, the solid was taken out, 10 mL of ethanol was added, ultrasonication was carried out for 30 minutes, and after drying, it was ball-milled for 2 hours to obtain three-dimensional composite nano silver.
按照实施例1的方法将本发明实施例3制备得到的三维复合纳米银制备成银浆。The three-dimensional composite nano silver prepared in Example 3 of the present invention was prepared into a silver paste according to the method of Example 1.
按照实施例1的方法对本发明实施例3制备得到银浆进行导电性检测，检测结果为，本发明实施例3制备的导电银浆的方阻为25mΩ。The silver paste prepared in Example 3 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Example 3 of the present invention was 25 mΩ.
比较例1Comparative example 1
按照实施例1的方法制备得到银浆，与实施例1的区别在于，将实施例1中的三维复合纳米银替换为平均粒度为10微米的银粉，银粉的用量与实施例1中三维复合纳米银的用量相同。The silver paste was prepared according to the method of Example 1, and the difference from Example 1 was that the three-dimensional composite nano-silver in Example 1 was replaced with silver powder having an average particle size of 10 μm, and the amount of silver powder was compared with the three-dimensional composite nanometer in Example 1. The amount of silver used is the same.
按照实施例1的方法对本发明比较例1制备得到银浆进行导电性检测，检测结果为，本发明比较例1制备的导电银浆的方阻为68mΩ。The silver paste prepared in Comparative Example 1 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Comparative Example 1 of the present invention was 68 mΩ.
比较例2Comparative example 2
按照实施例1的方法制备得到银浆，与实施例1的区别在于，将实施例1中的三维复合纳米银替换为平均粒度为40nm纳米银粉，纳米银粉的用量与实施例1中三维复合纳米银的用量相同。The silver paste was prepared according to the method of Example 1. The difference from Example 1 was that the three-dimensional composite nano-silver in Example 1 was replaced with a nano-silver powder having an average particle size of 40 nm, and the amount of the nano-silver powder was compared with the three-dimensional composite nanometer in Example 1. The amount of silver used is the same.
按照实施例1的方法对本发明比较例2制备得到银浆进行导电性检测，检测结果为，本发明比较例2制备的导电银浆的方阻为123mΩ。The silver paste prepared in Comparative Example 2 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Comparative Example 2 of the present invention was 123 mΩ.
比较例3Comparative example 3
按照实施例1所述的方法制备得到三维复合纳米银，与实施例1的区别在于，不加入高氯酸钠溶液。The three-dimensional composite nanosilver was prepared according to the method described in Example 1, and was different from Example 1 in that no sodium perchlorate solution was added.
按照实施例1的方法将本发明比较例3制备得到的三维复合纳米银制备成银浆。The three-dimensional composite nanosilver prepared in Comparative Example 3 of the present invention was prepared into a silver paste according to the method of Example 1.
按照实施例1的方法对本发明比较例3制备得到银浆进行导电性检测，检测结果为，本发明比较例3制备的导电银浆的方阻为164mΩ。The silver paste prepared in Comparative Example 3 of the present invention was subjected to conductivity measurement according to the method of Example 1. As a result, the square resistance of the conductive silver paste prepared in Comparative Example 3 of the present invention was 164 mΩ.
由以上实施例可知，本发明提供了一种三维复合纳米银的制备方法，包括：使用物理方法将纳米银制备成三维复合纳米银。本发明使用物理的方法制备得到三维复合纳米银，本发明提供的三维复合纳米银的制备方法具有产率高、成本低、环保和高效等特点。本发明使用纯物理过程 制备三维复合纳米银，环保高效，而且制备得到的三维复合纳米银电学性能优异。It can be seen from the above embodiments that the present invention provides a method for preparing a three-dimensional composite nano-silver, comprising: preparing a nano-silver into a three-dimensional composite nano-silver using a physical method. The invention adopts a physical method to prepare three-dimensional composite nano silver, and the preparation method of the three-dimensional composite nano silver provided by the invention has the characteristics of high yield, low cost, environmental protection and high efficiency. The invention uses the pure physical process to prepare the three-dimensional composite nano silver, is environmentally friendly and efficient, and the prepared three-dimensional composite nano silver has excellent electrical properties.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It should be considered as the scope of protection of the present invention.

Claims (10)

  1. 一种三维复合纳米银的制备方法，包括：A method for preparing three-dimensional composite nano-silver, comprising:
    使用物理方法将纳米银制备成三维复合纳米银。The nanosilver is prepared into a three-dimensional composite nanosilver using a physical method.
  2. 根据权利要求1所述的方法，其特征在于，所述三维复合纳米银的制备方法具体为：The method according to claim 1, wherein the method for preparing the three-dimensional composite nano-silver is specifically:
    将纳米银溶液预处理后进行离心、超声分散和研磨，得到三维复合纳米银。The nano silver solution is pretreated, centrifuged, ultrasonically dispersed and ground to obtain three-dimensional composite nano-silver.
  3. 根据权利要求2所述的方法，其特征在于，所述纳米银溶液的质量浓度为0.5～4％。The method according to claim 2, wherein the nanosilver solution has a mass concentration of 0.5 to 4%.
  4. 根据权利要求2所述的方法，其特征在于，所述纳米银溶液中纳米银的粒径为5～100nm。The method according to claim 2, wherein the nano silver in the nano silver solution has a particle diameter of 5 to 100 nm.
  5. 根据权利要求2所述的方法，其特征在于，所述纳米银溶液的溶剂为醇和水中的一种或几种。The method according to claim 2, wherein the solvent of the nanosilver solution is one or more of an alcohol and water.
  6. 根据权利要求2所述的方法，其特征在于，所述预处理为：The method of claim 2 wherein said preprocessing is:
    将无机盐溶液与纳米银溶液混合后静置。The inorganic salt solution was mixed with the nano silver solution and allowed to stand.
  7. 根据权利要求6所述的方法，其特征在于，所述静置的时间为24～48小时。The method according to claim 6, wherein the standing time is 24 to 48 hours.
  8. 根据权利要求6所述的方法，其特征在于，所述无机盐溶液中的无机盐为含氯酸盐。The method according to claim 6, wherein the inorganic salt in the inorganic salt solution is a chlorate-containing salt.
  9. 根据权利要求8所述的方法，其特征在于，所述含氯酸盐为高氯酸盐、氯酸盐和盐酸盐中的一种或几种。The method of claim 8 wherein said chlorate is one or more of a perchlorate, a chlorate and a hydrochloride.
  10. 一种权利要求1所述的方法制备得到的三维复合纳米银。A three-dimensional composite nanosilver prepared by the method of claim 1.
PCT/CN2018/122552 2018-04-04 2018-12-21 Three-dimensional silver nanocomposite and manufacturing method thereof WO2019192214A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810298295.3A CN108500255B (en) 2018-04-04 2018-04-04 A kind of three-dimensional composite nano silver and preparation method thereof
CN201810298295.3 2018-04-04

Publications (1)

Publication Number Publication Date
WO2019192214A1 true WO2019192214A1 (en) 2019-10-10

Family

ID=63380563

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/122552 WO2019192214A1 (en) 2018-04-04 2018-12-21 Three-dimensional silver nanocomposite and manufacturing method thereof

Country Status (2)

Country Link
CN (1) CN108500255B (en)
WO (1) WO2019192214A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108500255B (en) * 2018-04-04 2019-08-02 太原氦舶新材料有限责任公司 A kind of three-dimensional composite nano silver and preparation method thereof
CN113102746A (en) * 2021-04-08 2021-07-13 瑞安铭恩科技有限公司 Frog egg-shaped nano Ag antibacterial material and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103223488A (en) * 2013-05-08 2013-07-31 宁波大学 Preparation method for silver-coated silicon dioxide composite microsphere particles
EP2333024B1 (en) * 2009-12-10 2014-08-13 Riso Kagaku Corporation Electrically conductive emulsion ink and method for producing electrically conductive thin film using the same
CN104162681A (en) * 2014-07-30 2014-11-26 青岛科技大学 Preparation method for silver-zinc oxide nano-composite structure
CN104668574A (en) * 2014-11-26 2015-06-03 侯善敬 Nano Ag powder preparation method
CN106735290A (en) * 2016-11-30 2017-05-31 华南理工大学 Nano Silver prepared by a kind of utilization reducing sugar low-temperature reduction and preparation method thereof and the application in electrically conductive ink
JP2017157633A (en) * 2016-02-29 2017-09-07 出光興産株式会社 Composition, method for manufacturing the same, metal nano material composition, method for manufacturing conducting circuit, and electronic device
CN108500255A (en) * 2018-04-04 2018-09-07 太原氦舶新材料有限责任公司 A kind of three-dimensional composite nano silver and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103341634B (en) * 2013-06-24 2015-04-08 上海理工大学 Method for preparing ZnO/Ag nanometer composite materials in room temperature
CN103785852B (en) * 2014-01-25 2016-08-17 华南理工大学 A kind of nanometer silver-nano micro crystal cellulose complex and preparation method and application
TWI593634B (en) * 2015-12-15 2017-08-01 國家中山科學研究院 A process to synthesize silver nano particles
CN106493389A (en) * 2016-11-28 2017-03-15 上海无线电设备研究所 A kind of preparation method of composite-grain diameter nano silver paste

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2333024B1 (en) * 2009-12-10 2014-08-13 Riso Kagaku Corporation Electrically conductive emulsion ink and method for producing electrically conductive thin film using the same
CN103223488A (en) * 2013-05-08 2013-07-31 宁波大学 Preparation method for silver-coated silicon dioxide composite microsphere particles
CN104162681A (en) * 2014-07-30 2014-11-26 青岛科技大学 Preparation method for silver-zinc oxide nano-composite structure
CN104668574A (en) * 2014-11-26 2015-06-03 侯善敬 Nano Ag powder preparation method
JP2017157633A (en) * 2016-02-29 2017-09-07 出光興産株式会社 Composition, method for manufacturing the same, metal nano material composition, method for manufacturing conducting circuit, and electronic device
CN106735290A (en) * 2016-11-30 2017-05-31 华南理工大学 Nano Silver prepared by a kind of utilization reducing sugar low-temperature reduction and preparation method thereof and the application in electrically conductive ink
CN108500255A (en) * 2018-04-04 2018-09-07 太原氦舶新材料有限责任公司 A kind of three-dimensional composite nano silver and preparation method thereof

Also Published As

Publication number Publication date
CN108500255B (en) 2019-08-02
CN108500255A (en) 2018-09-07

Similar Documents

Publication Publication Date Title
CN103787328B (en) A kind of preparation method of modified graphene
TWI543931B (en) Preparation method of graphene and dispersed composition of graphene
Barkade et al. Ultrasound assisted miniemulsion polymerization for preparation of polypyrrole–zinc oxide (PPy/ZnO) functional latex for liquefied petroleum gas sensing
WO2018107795A1 (en) Method for exfoliating hexagonal boron nitride (h-bn) by means of ball milling
CN103614098B (en) A kind of functionalization graphene doping epoxide resin conductive adhesive and preparation method thereof
Saterlie et al. Surfactant effects on dispersion characteristics of copper-based nanofluids: A dynamic light scattering study
WO2019192214A1 (en) Three-dimensional silver nanocomposite and manufacturing method thereof
CN102728852B (en) Preparation method of oxide or meta-coated nickel ultrafine powder
Cauchy et al. Synthesis of highly conductive, uniformly silver-coated carbon nanofibers by electroless deposition
US20190143286A1 (en) Two-Dimensional Nanomaterial Dispersant, Preparation Method of Two-Dimensional Nanomaterial by Liquid Phase Exfoliation, and Use Thereof
Zhao et al. Natural amino acids: high-efficiency intercalants for graphene exfoliation
CN103725046A (en) Graphene dispersion liquid and preparation method thereof
CN101306468A (en) Preparation method of conductive silver composite nano particles coated by polypyrrole
CN105945302A (en) Preparation method for antioxidant copper nanopowder
CN102371358A (en) Aqueous-phase preparation method for re-dispersible nano-copper particles
CN108659457B (en) Boron nitride coated sulfonated graphene-epoxy resin composite material and preparation method thereof
JP2016195103A (en) Composite conductive particle and method for producing the same, and conductive resin
CN104830248B (en) A kind of high-termal conductivity heat-conducting glue and preparation method thereof
Xu et al. Preparation, morphology, and properties of conducting polyaniline‐grafted multiwalled carbon nanotubes/epoxy composites
CN104538600A (en) AgNPs/MoS2 functional composite material and preparation method thereof
KR20130043458A (en) Nanocomposite comprising titanium oxide/metal nanoparticles/carbon nanostructures, and the preparing the nanocomposite, and dssc electrode using the nanocomposite
Ye et al. Alumina-coated Cu@ reduced graphene oxide microspheres as enhanced antioxidative and electrically insulating fillers for thermal interface materials with high thermal conductivity
Dhiaa et al. Study the thermal properties of PVP/CuNPs composite prepared by different concentrations
CN101508934A (en) Electrorheological liquid preparation method for core-shell particle/composite base liquid
CN103084582A (en) Preparation method for atomic scale precious metal nanoparticle stable colloidal suspension

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18913969

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18913969

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC