CN110586952A - Room temperature preparation method of nano metal powder and conductive ink thereof - Google Patents
Room temperature preparation method of nano metal powder and conductive ink thereof Download PDFInfo
- Publication number
- CN110586952A CN110586952A CN201810651247.8A CN201810651247A CN110586952A CN 110586952 A CN110586952 A CN 110586952A CN 201810651247 A CN201810651247 A CN 201810651247A CN 110586952 A CN110586952 A CN 110586952A
- Authority
- CN
- China
- Prior art keywords
- deionized water
- solution
- conductive ink
- nano metal
- metal powder
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
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
- 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
- B22F1/0545—Dispersions or suspensions of 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
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a room temperature preparation method of nano metal powder and conductive ink thereof, wherein the room temperature preparation method of the nano metal powder comprises the following steps: and injecting the solution B into the solution A at room temperature under an ultrasonic state to obtain a mixed solution, adding a washing solvent into the mixed solution, washing by centrifuging, and obtaining a precipitate which is nano metal powder after washing. The preparation method of the conductive ink by using the nano metal powder comprises the following steps: compared with the prior art, the nano metal conductive ink has the advantages that the particle size of the nano metal powder prepared by the method is 5-20nm, the nano metal conductive ink has high oxidation resistance, the nano metal powder is not oxidized after being stored in the air for more than one year, and the large-scale production can be realized at room temperature; the conductive ink has high conductivity, the resistivity of an electronic device after infrared sintering in the air is only 2-8 times that of the traditional gold and silver wires or about 20 times that of copper wires, and the resistivity can be kept unchanged after the conductive ink is placed in the air for a long time.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a room temperature preparation method of nano metal powder and conductive ink thereof.
Background
The printed electronics technology refers to the preparation of large-area, flexible and low-cost electronic products or devices by printing various conductive inks on various substrates. Conductive inks can be used in a number of applications such as: electronic newspapers (EP), curved display screens, wireless intelligent identification electronic tags (RFID), Printed Circuit Boards (PCB), Thin Film Sensors (TFS), solar cell panels (TFSB), and the like. With the socioeconomic development trend of green production, energy conservation and emission reduction, the conductive ink must become a key material for sustainable development of the printing electronic technology and the electronic industry.
The conductive ink mainly comprises metal nanoparticles (gold, silver, copper or nickel and the like) or non-metal fillers (carbon materials and the like), thermosetting resin, benign solvent, some surfactants for improving the properties of the ink, a plasticizer, a defoaming agent and the like, and the preparation of the metal nanoparticles or the non-metal fillers with the conductive function is the key of the quality of the ink, and is the only source for the conductivity of the printed wires or the conductive patterns. Generally, since metal conductivity is higher than nonmetal conductivity, metal-based conductive inks are more conductive than nonmetal-based conductive inks.
At present, a lot of research reports of metal-based conductive ink exist, and companies such as the U.S. Flint ink company and the Korean ABC nanotechnology all develop marketable nano silver conductive ink, but the generation cost is high, the process is complex, and the large-scale application cannot be realized. In China, only colleges and universities, scientific research institutes and the like are researched, the preparation method is still in a starting stage, most reported preparation methods of silver nanoparticles need heating reaction at a certain temperature, for example, the low temperature reported by Chinese patent CN 102220045A still needs 20-70 ℃, the preparation method is complex, the preparation process or the solvent of the conductive ink has environmental pollution and the like, inert atmosphere protection is always needed for improving the oxidation resistance of the silver nanoparticles, after sintering at 50-150 ℃, the finally obtained resistivity is higher and close to 1000 microohm.cm, the actual application range is smaller, and large-scale production is difficult to realize. In order to make the prepared conductive pattern have higher conductivity (lower resistivity), sintering is generally required under the protection of 120-320 ℃ inert atmosphere, such as nitrogen, argon and the like, the operation process is complicated, and 100-200 ℃ is required even for low-temperature sintering (such as CN 101870832A). Therefore, the development and preparation of the nano metal powder and the conductive ink thereof which can be produced in batch at room temperature and have no pollution and high stability are necessary, and the nano metal conductive ink with high conductivity can be realized by low-power microwave sintering in the air is very necessary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a room-temperature preparation method of nano metal powder, and the invention also aims to provide a method for preparing conductive ink by using the nano metal powder;
another object of the present invention is to provide a use of the above conductive ink for increasing the resistivity of an electronic device.
The purpose of the invention is realized by the following technical scheme.
A room temperature preparation method of nano metal powder comprises the following steps:
1) injecting the solution B into the solution A at room temperature under an ultrasonic state to obtain a mixed solution, wherein the preparation method of the solution A and the solution B is as follows:
solution A: placing an organic protective agent and a reducing agent into deionized water, uniformly dissolving the organic protective agent and the reducing agent into the deionized water, and adjusting the pH value to 7.5-11 after the organic protective agent and the reducing agent are dissolved to obtain a solution A, wherein the organic protective agent is a nonionic surfactant and a cationic/anionic surfactant, and the molar ratio of the nonionic surfactant to the cationic/anionic surfactant is (0.1-2): 1;
in the technical scheme, the concentration of the organic protective agent in deionized water for dissolving the organic protective agent is 0.01-1.5 mol/L.
In the technical scheme, the concentration of the reducing agent in deionized water for dissolving the reducing agent is 0.04-0.6 mol/L.
In the technical scheme, the nonionic surfactant is polyvinylpyrrolidone, oleic acid, alkylolamide or fatty alcohol-polyoxyethylene ether.
In the above technical scheme, the cationic surfactant is 12, 14, 16, 18 alkyl trimethyl ammonium bromide, ammonium chloride, silicone oil or panthenol.
In the technical scheme, the anionic surfactant is sodium dodecyl benzene sulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate or sodium dodecyl sulfate.
In the above technical scheme, the reducing agent is a mixture of two or more of sodium hypophosphite, vitamin C (ascorbic acid), D-ascorbic acid and glucose.
In the technical scheme, the pH value is adjusted to 7.5-11 by adding alkaline substances, wherein the alkaline substances are concentrated ammonia water and/or sodium hydroxide.
Solution B: adding metal salt into deionized water, and uniformly dissolving the metal salt in the deionized water to obtain a solution B, wherein the metal salt is copper salt, gold salt or silver salt;
according to the amount of the substances, the ratio of the reducing agent to the organic protective agent to the metal salt is (4-20): (1-5): 1;
in the above technical scheme, the concentration of the metal salt in the deionized water in which the metal salt is dissolved is
0.01-1mol/L。
In the technical scheme, the silver salt is one or more of silver nitrate, silver nitrite, silver acetate, silver carbonate, silver phosphate and chitosan silver.
In the technical scheme, the copper salt is one or a mixture of more than one of copper sulfate pentahydrate, copper chloride and copper nitrate.
In the technical scheme, the gold salt is chloroauric acid and/or gold nitrate.
In the step 1), the operation method for uniformly dissolving the organic protective agent and the reducing agent in the deionized water comprises the following steps: continuously stirring for 3-30 minutes, and then carrying out ultrasonic treatment for 3-30 minutes.
In the step 1), the operation method for uniformly dissolving the metal salt in the deionized water comprises the following steps: continuously stirring for 3-30 minutes, and then carrying out ultrasonic treatment for 3-30 minutes.
2) And adding a washing solvent into the mixed solution, washing by centrifuging, and obtaining a precipitate which is nano metal powder after washing.
In the step 2), the ratio of the mixed solution to the washing solvent is 1 (2-5) in parts by volume.
In the step 2), the washing solvent is any one or a mixture of two of ethanol, acetone and deionized water.
The method for preparing the conductive ink by using the nano metal powder comprises the following steps: and ultrasonically dispersing the nano metal powder in a mixed solvent to obtain the nano metal conductive ink, wherein the viscosity of the mixed solvent is 8-10000cps, the nano metal powder accounts for 5-80% by mass percent, and the mixed solvent accounts for 20-95%.
In the technical scheme, the mixed solvent is a mixture of two or more of ethanol, ethylene glycol, glycerol, diethylene glycol, monomethyl ether, ethyl acetate, butyl acetate, methoxy-2-propanol acetate, butyl acetate, acrylic resin, a silane coupling agent and deionized water.
In the above technical scheme, the mixed solvent is, by mass percent: 0-30 wt% of ethanol, 5-30 wt% of ethylene glycol, 3-20 wt% of glycerol, 5-30 wt% of diethylene glycol, 5-20 wt% of monomethyl ether, 0-8 wt% of ethyl acetate, 0-5 wt% of butyl acetate, 0-20 wt% of methoxy-2-propanol acetate, 0-10 wt% of butyl acetate, 0-20 wt% of acrylic resin, 0-5 wt% of a silane coupling agent and the balance of deionized water.
The conductive ink is coated on a substrate of an electronic device, infrared sintering or furnace temperature sintering is carried out for 0-15 min, the resistivity of the obtained electronic device is 2-8 times that of pure metal (gold, silver or copper), wherein the infrared sintering power is 0-15W, and the furnace temperature sintering temperature is 25-100 ℃.
The coating method for coating the conductive ink on the substrate of the electronic device is ink jet, writing with an oil pen or brushing, and when the coating method is ink jet, the viscosity of the mixed solvent is 8-20 cps; when the coating method is oil pen writing, the viscosity of the mixed solvent is 20-1000 cps; when the coating method is brushing, the viscosity of the mixed solvent is 1000-10000 cps.
Compared with the prior art, the invention has the following beneficial effects:
1) the particle size of the nano metal powder prepared by the invention is 5-20nm, the nano metal powder has high oxidation resistance, and the nano metal powder is not oxidized after being stored in the air for more than one year, so that the large-scale production can be realized at room temperature;
2) the conductive ink prepared by the invention has high conductivity, the resistivity of an electronic device after infrared sintering in the air is only 2-8 times that of the traditional gold and silver wires or about 20 times that of a copper wire, and the resistivity can be kept unchanged after the conductive ink is placed in the air for a long time;
3) the conductive ink is suitable for preparing various printing electronic devices or functional parts thereof, has simple process and can realize large-scale production.
Drawings
Fig. 1 is an XRD pattern and TEM micrograph of the conductive ink prepared according to the present invention, wherein (a) is the XRD pattern of the initial and after 12 months of storage, (b) TEM micrograph of gold nanoparticles and conductive ink;
fig. 2 is an XRD pattern and TEM micrograph of the conductive ink prepared according to the present invention, wherein (a) is an XRD pattern of the initial and after 12 months of storage, (b) a TEM micrograph of silver nanoparticles and a conductive ink pattern;
FIG. 3 is an XRD pattern and TEM micrograph of a conductive ink prepared according to the present invention, wherein (a) is an XRD pattern of an initial and after 12 months of storage, (b) a TEM micrograph of copper nanoparticles and a conductive ink pattern;
FIG. 4 is a graph of resistivity as a function of sintering power for the resulting electronic device of example 7;
FIG. 5 is a graph showing the resistivity of the electronic device obtained in example 8 as a function of the number of times of spraying;
FIG. 6 shows the resistivity of the electronic device obtained in example 9 as a function of sintering time.
Detailed Description
In the following examples, solid drugs were purchased from Aladdin pharmaceuticals Ltd, purity was 99.9% analytical purity, the organic solvents were purchased from Tianjin Jiangtian science and technology Ltd, and the mass fraction of the solvents was greater than 99.7%, except that the solvents were prepared from deionized water laboratories.
The type of the ink-jet printer is hp1010, and the infrared heating lamp for infrared sintering is provided by Langpo optical and electrical technology, Inc. in Guangzhou, and the power is 0-100W.
The technical scheme of the invention is further explained by combining specific examples.
Example 1
A room temperature preparation method of nano metal powder (gold powder) comprises the following steps:
1) injecting the solution B into the solution A at room temperature of 20-25 ℃ under an ultrasonic state to obtain a mixed solution, wherein the preparation method of the solution A and the solution B comprises the following steps:
solution A: dissolving an organic protective agent and a reducing agent in deionized water, continuously stirring for 10 minutes, then carrying out ultrasonic treatment for 10 minutes to uniformly dissolve the organic protective agent and the reducing agent in the deionized water, and adding an alkaline substance to adjust the pH value to 8 after dissolving to obtain a solution A, wherein the alkaline substance is sodium hydroxide. The organic protective agent is nonionic surfactant and cationic surfactant, and the ratio of the nonionic surfactant to the cationic surfactant is 0.5: 1; the concentration of the organic protective agent in the deionized water for dissolving the organic protective agent is 0.05mol/L, and the concentration of the reducing agent in the deionized water for dissolving the reducing agent is 0.1 mol/L; the nonionic surfactant is polyvinylpyrrolidone; the cationic surfactant is 16 alkyl trimethyl ammonium bromide; the reducing agent is a mixture of sodium hypochlorite and glucose, and the mass part ratio of the sodium hypochlorite to the glucose is 2: 1.
solution B: adding a metal salt into deionized water, continuously stirring for 15 minutes, and then performing ultrasonic treatment for 15 minutes to uniformly dissolve the metal salt in the deionized water to obtain a solution B, wherein the metal salt is chloroauric acid, and the concentration of the metal salt in the deionized water in which the metal salt is dissolved is 0.01 mol/L.
The ratio of the reducing agent, the organic protective agent and the metal salt is 10: 5: 1;
2) and adding a washing solvent into the mixed solution, washing by centrifuging, and obtaining precipitate which is nano metal powder after washing, wherein the ratio of the mixed solution to the washing solvent is 1:3 in parts by volume, and the washing solvent is ethanol.
The prepared gold nanoparticles are shown in fig. 1(a), and it is confirmed that the obtained gold nanoparticles (nano metal powder) have good oxidation resistance, and the size of the gold particles is about 5-15nm as shown in a TEM micrograph of fig. 1 (b).
Example 2
A room temperature preparation method of nano metal powder (silver powder) for infrared sintering comprises the following steps:
1) injecting the solution B into the solution A at room temperature under an ultrasonic state to obtain a mixed solution, wherein the preparation method of the solution A and the solution B is as follows:
solution A: dissolving an organic protective agent and a reducing agent in deionized water, continuously stirring for 5 minutes, performing ultrasonic treatment for 5 minutes to uniformly dissolve the organic protective agent and the reducing agent in the deionized water, and adding an alkaline substance to adjust the pH value to 9 after dissolution to obtain a solution A, wherein the alkaline substance is concentrated ammonia water. The organic protective agent is nonionic surfactant and anionic surfactant, and the molar ratio of the nonionic surfactant to the anionic surfactant is 0.8: 1; the concentration of the organic protective agent in the deionized water for dissolving the organic protective agent is 0.08mol/L, and the concentration of the reducing agent in the deionized water for dissolving the reducing agent is 0.3 mol/L; the nonionic surfactant is oleic acid; the anionic surfactant is sodium dodecyl benzene sulfonate; the reducing agent is a mixture of vitamin C (ascorbic acid) and glucose, and the mass part ratio of the vitamin C (ascorbic acid) to the glucose is 2: 1.
solution B: adding metal salt into deionized water, continuously stirring for 5 minutes, and then performing ultrasonic treatment for 5 minutes to uniformly dissolve the metal salt in the deionized water to obtain a solution B, wherein the metal salt is silver nitrate, and the concentration of the metal salt in the deionized water in which the metal salt is dissolved is 0.05 mol/L.
The ratio of the reducing agent, the organic protective agent and the metal salt is 6: 1.6: 1;
2) and adding a washing solvent into the mixed solution, washing by centrifuging, and obtaining precipitate which is nano metal powder (silver nanoparticles) after washing, wherein the ratio of the mixed solution to the washing solvent is 1:4 in parts by volume, and the washing solvent is deionized water.
The prepared gold nanoparticles are shown in fig. 2(a), and it is confirmed that the obtained silver nanoparticles have good oxidation resistance. Meanwhile, TEM micrographs showed gold particles having a size of about 5 to 20nm, as shown in FIG. 2 (b).
Example 3
A room temperature preparation method of nano metal powder (copper powder) for infrared sintering comprises the following steps:
1) injecting the solution B into the solution A at room temperature under an ultrasonic state to obtain a mixed solution, wherein the preparation method of the solution A and the solution B is as follows:
solution A: dissolving an organic protective agent and a reducing agent in deionized water, continuously stirring for 8 minutes, then carrying out ultrasonic treatment for 8 minutes to uniformly dissolve the organic protective agent and the reducing agent in the deionized water, and adding an alkaline substance to adjust the pH value to 10.5 after dissolving to obtain a solution A, wherein the alkaline substance is sodium hydroxide. The organic protective agent is nonionic surfactant and cationic surfactant, and the molar ratio of the nonionic surfactant to the cationic surfactant is 1: 1; the concentration of the organic protective agent in the deionized water for dissolving the organic protective agent is 0.1mol/L, and the concentration of the reducing agent in the deionized water for dissolving the reducing agent is 0.5 mol/L; the nonionic surfactant is oleic acid; the cationic surfactant is 14 alkyl trimethyl ammonium chloride; the reducing agent is a mixture of D-ascorbic acid and sodium hypophosphite, and the mass fraction ratio of the D-ascorbic acid to the sodium hypophosphite is 2: 1.
Solution B: adding metal salt into deionized water, continuously stirring for 5 minutes, and then performing ultrasonic treatment for 5 minutes to uniformly dissolve the metal salt in the deionized water to obtain a solution B, wherein the metal salt is copper sulfate pentahydrate, and the concentration of the metal salt in the deionized water in which the metal salt is dissolved is 0.025 mol/L.
The ratio of the reducing agent, the organic protective agent and the metal salt is 20: 4: 1;
2) and adding a washing solvent into the mixed solution, washing by centrifuging, and obtaining precipitate which is nano metal powder after washing, wherein the ratio of the mixed solution to the washing solvent is 1:3.5 in parts by volume, and the washing solvent is acetone.
The prepared copper nanoparticles are shown in fig. 3(a), and it is confirmed that the obtained silver nanoparticles have good oxidation resistance. While the TEM micrograph of FIG. 3(b) shows gold particles of about 20-80nm in size.
Example 4
A method for preparing conductive ink using the nano metal powder (gold powder) of the above example 1, comprising the steps of: ultrasonically dispersing nano metal powder in a mixed solvent to obtain the nano metal conductive ink, wherein the nano metal powder accounts for 60% by mass, the mixed solvent accounts for 40% by mass, the viscosity of the mixed solvent is 2000cps, and the mixed solvent is as follows: 10 wt% of ethanol, 25 wt% of ethylene glycol, 10 wt% of glycerol, 15 wt% of diethylene glycol, 10 wt% of monomethyl ether, 5 wt% of ethyl acetate, 10 wt% of 2-methoxypropanol acetate, 10 wt% of acrylic resin and 5 wt% of a silane coupling agent.
The prepared nano silver conductive ink is shown in an inset of fig. 1(b), and shows that the obtained ink is purple,
example 5
The method for preparing the conductive ink using the nano metal powder of the above example 2 includes the steps of: ultrasonically dispersing nano metal powder in a mixed solvent to obtain the nano metal conductive ink, wherein the nano metal powder accounts for 20 percent by mass, the mixed solvent accounts for 80 percent by mass, the viscosity of the mixed solvent is 20cps, and the mixed solvent is as follows: 15 wt% of ethanol, 20 wt% of ethylene glycol, 13 wt% of glycerol, 25 wt% of diethylene glycol, 10 wt% of monomethyl ether, 10 wt% of acrylic resin, 5 wt% of a silane coupling agent and the balance of deionized water.
The prepared nano silver conductive ink is shown in an inset of fig. 2(b), and the obtained ink is dark yellow brown.
Example 6
A method for preparing conductive ink using the nano metal powder of the above example 3, comprising the steps of: ultrasonically dispersing nano metal powder in a mixed solvent to obtain the nano metal conductive ink, wherein the nano metal powder accounts for 60 percent, the mixed solvent accounts for 40 percent, the viscosity of the mixed solvent is 80cps, and the mixed solvent is as follows by mass percent: 8 wt% of ethanol, 20 wt% of ethylene glycol, 10 wt% of glycerol, 25 wt% of diethylene glycol, 10 wt% of monomethyl ether, 5 wt% of ethyl acetate, 10 wt% of 2-methoxypropanol acetate, 5 wt% of acrylic resin, 2 wt% of a silane coupling agent and the balance of deionized water.
The prepared nano-copper conductive ink is shown in an inset of fig. 3(b), and shows that the obtained ink is purple red.
Example 7
An electronic device was prepared using the conductive ink of example 4, the conductive ink was coated on a substrate of the electronic device by a brush coating method, and infrared sintering was performed for 6min at powers of 1, 3, 5, 8, 10, and 13W, respectively, wherein when the infrared sintering power was 10W, the conductive pattern length L was 5cm and the cross-sectional area S was 1 × 10, respectively, were measured-3cm2The resistivity p is 6.8 microohm cm, which is about 2.8 times the pure gold resistivity p is 2.40 microohm cm.
The resistivity test of fig. 4 shows that the resistivity of the gold conductive pattern gradually decreases as the sintering power increases, and that the resistivity becomes stable at 10 watts, and that ρ is about 6.8 microohm-cm.
Example 8
Electronic devices were prepared using the conductive ink of example 5, ink jet printing separately using a Hewlett packard 1010 printerPrinting 1, 3, 6 and 10 times to coat the conductive ink on a flexible photo paper substrate, sintering at 90 ℃ for 10min and the infrared sintering power is 4W, wherein after 10 times of ink-jet printing, the length L of the conductive pattern is 5cm, and the cross section S is 1 multiplied by 10-6cm2The resistivity p is calculated to be 8 microohm cm, which is about 5 times the pure silver resistivity p 1.58 microohm cm, from a resistivity calculation formula p is RS/L.
As shown in fig. 5, the resistivity was gradually decreased as the number of spraying was increased, and was stable at 10 times of spraying, and ρ was about 8 microohm · cm.
Example 9
Preparing an electronic device by using the conductive ink of example 6, coating the conductive ink on a substrate of the electronic device by using a pen-writing method, and infrared sintering for 1-15 min at a power of 5W, wherein when the conductive pattern is sintered for 12 minutes, the length L of the conductive pattern is 5cm, and the cross-sectional area S is 1 × 10-6cm2The resistivity p is calculated to be 13.6 microohm cm, which is about 5 times the pure copper resistivity p is 1.68 microohm cm, from a resistivity calculation formula p is RS/L.
Test resistivity as shown in fig. 6, the resistivity of the copper conductive pattern gradually decreased with the increase of the infrared sintering time, and the resistivity was stabilized at a time of sintering for 12 minutes, and was about ρ 13.6 microohm-cm.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A room temperature preparation method of nano metal powder is characterized by comprising the following steps:
1) injecting the solution B into the solution A at room temperature under an ultrasonic state to obtain a mixed solution, wherein the preparation method of the solution A and the solution B is as follows:
solution A: placing an organic protective agent and a reducing agent into deionized water, uniformly dissolving the organic protective agent and the reducing agent into the deionized water, and adjusting the pH value to 7.5-11 after the organic protective agent and the reducing agent are dissolved to obtain a solution A, wherein the organic protective agent is a nonionic surfactant and a cationic/anionic surfactant, and the molar ratio of the nonionic surfactant to the cationic/anionic surfactant is (0.1-2): 1;
solution B: adding metal salt into deionized water, and uniformly dissolving the metal salt in the deionized water to obtain a solution B, wherein the metal salt is copper salt, gold salt or silver salt;
according to the amount of the substances, the ratio of the reducing agent to the organic protective agent to the metal salt is (4-20): (1-5): 1;
2) and adding a washing solvent into the mixed solution, washing by centrifuging, and obtaining a precipitate which is nano metal powder after washing.
2. The room temperature preparation method of claim 1, wherein the concentration of the organic protective agent in deionized water in which the organic protective agent is dissolved is 0.01-1.5 mol/L;
the concentration of the reducing agent in deionized water for dissolving the reducing agent is 0.04-0.6 mol/L;
the nonionic surfactant is polyvinylpyrrolidone, oleic acid, alkylolamide or fatty alcohol-polyoxyethylene ether;
the cationic surfactant is 12/14/16/18 alkyl trimethyl ammonium bromide, ammonium chloride, silicone oil or panthenol;
the anionic surfactant is sodium dodecyl benzene sulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate or sodium dodecyl sulfate.
3. The room temperature preparation method according to claim 2, wherein the reducing agent is a mixture of two or more of sodium hypophosphite, vitamin C, D-ascorbic acid, and glucose;
the pH value is adjusted to 7.5-11 by adding alkaline substances, wherein the alkaline substances are concentrated ammonia water and/or sodium hydroxide.
4. The room temperature preparation method of claim 3, wherein the concentration of the metal salt in the deionized water in which the metal salt is dissolved is 0.01 to 1 mol/L;
the silver salt is one or more of silver nitrate, silver nitrite, silver acetate, silver carbonate, silver phosphate and chitosan silver;
the copper salt is one or a mixture of more than one of copper sulfate pentahydrate, copper chloride and copper nitrate; the gold salt is chloroauric acid and/or gold nitrate.
5. The room temperature preparation method of claim 4, wherein in the step 1), the operation method for uniformly dissolving the organic protective agent and the reducing agent in the deionized water comprises the following steps: continuously stirring for 3-30 minutes, and then carrying out ultrasonic treatment for 3-30 minutes;
in the step 1), the operation method for uniformly dissolving the metal salt in the deionized water comprises the following steps: continuously stirring for 3-30 minutes, and then carrying out ultrasonic treatment for 3-30 minutes;
in the step 2), the ratio of the mixed solution to the washing solvent is 1 (2-5) in parts by volume;
in the step 2), the washing solvent is any one or a mixture of two of ethanol, acetone and deionized water.
6. The method for preparing the conductive ink from the nano metal powder as claimed in claims 1 to 5, which is characterized by comprising the following steps: and ultrasonically dispersing the nano metal powder in a mixed solvent to obtain the nano metal conductive ink, wherein the viscosity of the mixed solvent is 8-10000cps, the nano metal powder accounts for 5-80% by mass percent, and the mixed solvent accounts for 20-95%.
7. The method according to claim 6, wherein the mixed solvent is a mixture of two or more of ethanol, ethylene glycol, glycerol, diethylene glycol, monomethyl ether, ethyl acetate, butyl acetate, methoxy-2 propanol acetate, butyl acetate, acrylic resin, a silane coupling agent, and deionized water.
8. The method according to claim 7, wherein the mixed solvent is, in mass percent: 0-30 wt% of ethanol, 5-30 wt% of ethylene glycol, 3-20 wt% of glycerol, 5-30 wt% of diethylene glycol, 5-20 wt% of monomethyl ether, 0-8 wt% of ethyl acetate, 0-5 wt% of butyl acetate, 0-20 wt% of methoxy-2-propanol acetate, 0-10 wt% of butyl acetate, 0-20 wt% of acrylic resin, 0-5 wt% of a silane coupling agent and the balance of deionized water.
9. The application of the conductive ink obtained by the method of claim 7 or 8 in improving the resistivity of an electronic device is to coat the conductive ink on a substrate of the electronic device, and perform infrared sintering or furnace temperature sintering for 0-15 min to obtain the electronic device with the resistivity 2-8 times that of a pure metal, wherein the infrared sintering power is 0-15W, and the furnace temperature sintering temperature is 25-100 ℃.
10. The use according to claim 9, wherein the conductive ink is applied on the substrate of the electronic device by an inkjet, a pen writing or a brush application method, and when the application method is the inkjet, the mixed solvent has a viscosity of 8 to 20 cps; when the coating method is oil pen writing, the viscosity of the mixed solvent is 20-1000 cps; when the coating method is brushing, the viscosity of the mixed solvent is 1000-10000 cps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810651247.8A CN110586952B (en) | 2018-06-22 | 2018-06-22 | Room temperature preparation method of nano metal powder and conductive ink thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810651247.8A CN110586952B (en) | 2018-06-22 | 2018-06-22 | Room temperature preparation method of nano metal powder and conductive ink thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110586952A true CN110586952A (en) | 2019-12-20 |
| CN110586952B CN110586952B (en) | 2022-06-24 |
Family
ID=68849313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810651247.8A Active CN110586952B (en) | 2018-06-22 | 2018-06-22 | Room temperature preparation method of nano metal powder and conductive ink thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110586952B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334129A (en) * | 2020-03-30 | 2020-06-26 | 善仁（浙江）新材料科技有限公司 | Preparation method of low-temperature sintered nano-silver conductive ink |
| CN111548194A (en) * | 2020-05-29 | 2020-08-18 | 南京凯泰化学科技有限公司 | Preparation method of printed circuit board |
| CN111618314A (en) * | 2020-05-15 | 2020-09-04 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
| CN112276108A (en) * | 2020-12-24 | 2021-01-29 | 西安宏星电子浆料科技股份有限公司 | Method for preparing silver powder by space confinement method |
| CN113308147A (en) * | 2021-06-07 | 2021-08-27 | 天津大学 | Bioabsorbable conductive ink, preparation method thereof and sintering method |
| CN114989472A (en) * | 2021-03-02 | 2022-09-02 | 天津理工大学 | Application of conductive ink in reducing resistivity of flexible polar plate after being bent for multiple times |
| CN115609000A (en) * | 2020-12-24 | 2023-01-17 | 赵伟 | Preparation method of high-dispersion nickel nano dispersion liquid |
| CN117844283A (en) * | 2024-01-02 | 2024-04-09 | 未来像素(南京)科技有限公司 | Composite catalyst ink and preparation method thereof, composite conductive film and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870832A (en) * | 2010-05-06 | 2010-10-27 | 复旦大学 | Method for preparing nano silver conductive ink |
| CN102120265A (en) * | 2010-01-07 | 2011-07-13 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
| CN102407344A (en) * | 2011-11-13 | 2012-04-11 | 西安科技大学 | Industrial production method of copper nanoparticle |
| CN102558954A (en) * | 2012-03-01 | 2012-07-11 | 复旦大学 | Preparation method for nano-copper ink applied to printed electronics |
| CN102816462A (en) * | 2012-08-13 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nano-silver particles coated with organic protection agent on surfaces |
| CN103087582A (en) * | 2013-01-25 | 2013-05-08 | 天津理工大学 | Preparation method of low-temperature sintering nano copper conductive ink |
| CN103101899A (en) * | 2011-11-15 | 2013-05-15 | 北京化工大学 | Preparation method of nano-material thin-film based on complex micelle system |
| CN103732701A (en) * | 2011-06-14 | 2014-04-16 | 拜耳技术服务有限公司 | Silver-containing aqueous ink formulation for producing electrically conductive structures, and ink jet printing method for producing such electrically conductive structures |
| CN104043839A (en) * | 2014-06-24 | 2014-09-17 | 天津大学 | Method for adopting isoniazide for preparing nanometer silver sol at room temperature |
| KR20150025596A (en) * | 2013-08-29 | 2015-03-11 | 주식회사 아모그린텍 | Apparatus for Manufacturing Metal Nano Particle and Method for Manufacturing Conductive Metal Nano Particle Ink using the Same |
| CN107661986A (en) * | 2017-08-03 | 2018-02-06 | 昆明贵金属研究所 | A kind of method for being prepared on a large scale the high sphericity super fine silver powder of high dispersive |
| CN108102464A (en) * | 2018-01-05 | 2018-06-01 | 华南理工大学 | It is a kind of can the water nano silver electrically conductive ink of room temperature sintering and its preparation and application |
-
2018
- 2018-06-22 CN CN201810651247.8A patent/CN110586952B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120265A (en) * | 2010-01-07 | 2011-07-13 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| CN101870832A (en) * | 2010-05-06 | 2010-10-27 | 复旦大学 | Method for preparing nano silver conductive ink |
| CN103732701A (en) * | 2011-06-14 | 2014-04-16 | 拜耳技术服务有限公司 | Silver-containing aqueous ink formulation for producing electrically conductive structures, and ink jet printing method for producing such electrically conductive structures |
| CN102407344A (en) * | 2011-11-13 | 2012-04-11 | 西安科技大学 | Industrial production method of copper nanoparticle |
| CN103101899A (en) * | 2011-11-15 | 2013-05-15 | 北京化工大学 | Preparation method of nano-material thin-film based on complex micelle system |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
| CN102558954A (en) * | 2012-03-01 | 2012-07-11 | 复旦大学 | Preparation method for nano-copper ink applied to printed electronics |
| CN102816462A (en) * | 2012-08-13 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nano-silver particles coated with organic protection agent on surfaces |
| CN103087582A (en) * | 2013-01-25 | 2013-05-08 | 天津理工大学 | Preparation method of low-temperature sintering nano copper conductive ink |
| KR20150025596A (en) * | 2013-08-29 | 2015-03-11 | 주식회사 아모그린텍 | Apparatus for Manufacturing Metal Nano Particle and Method for Manufacturing Conductive Metal Nano Particle Ink using the Same |
| CN104043839A (en) * | 2014-06-24 | 2014-09-17 | 天津大学 | Method for adopting isoniazide for preparing nanometer silver sol at room temperature |
| CN107661986A (en) * | 2017-08-03 | 2018-02-06 | 昆明贵金属研究所 | A kind of method for being prepared on a large scale the high sphericity super fine silver powder of high dispersive |
| CN108102464A (en) * | 2018-01-05 | 2018-06-01 | 华南理工大学 | It is a kind of can the water nano silver electrically conductive ink of room temperature sintering and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| 汪多仁: "《绿色发酵与生物化学品》", 31 August 2007, 北京：科学技术文献出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334129A (en) * | 2020-03-30 | 2020-06-26 | 善仁（浙江）新材料科技有限公司 | Preparation method of low-temperature sintered nano-silver conductive ink |
| CN111618314A (en) * | 2020-05-15 | 2020-09-04 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
| CN111618314B (en) * | 2020-05-15 | 2023-01-03 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
| CN111548194A (en) * | 2020-05-29 | 2020-08-18 | 南京凯泰化学科技有限公司 | Preparation method of printed circuit board |
| CN112276108A (en) * | 2020-12-24 | 2021-01-29 | 西安宏星电子浆料科技股份有限公司 | Method for preparing silver powder by space confinement method |
| CN112276108B (en) * | 2020-12-24 | 2021-04-13 | 西安宏星电子浆料科技股份有限公司 | Method for preparing silver powder by space confinement method |
| CN115609000A (en) * | 2020-12-24 | 2023-01-17 | 赵伟 | Preparation method of high-dispersion nickel nano dispersion liquid |
| CN114989472A (en) * | 2021-03-02 | 2022-09-02 | 天津理工大学 | Application of conductive ink in reducing resistivity of flexible polar plate after being bent for multiple times |
| CN114989472B (en) * | 2021-03-02 | 2023-04-14 | 天津理工大学 | Application of conductive ink in reducing resistivity of flexible polar plate after being bent for multiple times |
| CN113308147A (en) * | 2021-06-07 | 2021-08-27 | 天津大学 | Bioabsorbable conductive ink, preparation method thereof and sintering method |
| CN113308147B (en) * | 2021-06-07 | 2022-05-03 | 天津大学 | Bioabsorbable conductive ink, preparation method thereof and sintering method |
| CN117844283A (en) * | 2024-01-02 | 2024-04-09 | 未来像素(南京)科技有限公司 | Composite catalyst ink and preparation method thereof, composite conductive film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110586952B (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110586952B (en) | Room temperature preparation method of nano metal powder and conductive ink thereof | |
| CN103087582A (en) | Preparation method of low-temperature sintering nano copper conductive ink | |
| CN106981324B (en) | A kind of copper electrocondution slurry and its preparation method and application | |
| CN104505137A (en) | Conductive copper paste and preparation method and application thereof | |
| CN105733366B (en) | A kind of preparation method of ink jet printing nano silver conductive ink | |
| KR100713241B1 (en) | Method of manufacturing silver powder by chemical reduction | |
| KR102007306B1 (en) | Silver powder for sintered conductive paste | |
| CN104341860A (en) | Nanometer conductive ink and preparing method thereof | |
| CN102248177B (en) | Laser-induced method for preparing spherical silver powder | |
| CN109401440A (en) | A kind of solvent type conductive ink, preparation method and application | |
| TWI326297B (en) | Conductive ink composition and preparing method thereof | |
| CN111992736A (en) | Preparation method of silver nanoparticles | |
| CN102326211A (en) | Method for preparing metallic thin film | |
| Li et al. | Synthesis and characterization of silver–copper colloidal ink and its performance against electrical migration | |
| CN108326293B (en) | Method for producing silver-coated nickel powder | |
| CN104801709A (en) | Nickel-coated copper clad metal powder and preparation method and application thereof | |
| CN103619128A (en) | Preparing method of flexible circuit board based on ink-jet printing technique | |
| CN102558954A (en) | Preparation method for nano-copper ink applied to printed electronics | |
| CN107146652A (en) | A kind of copper electrocondution slurry and its production and use | |
| CN108250845A (en) | A kind of nanometer conductive ink and preparation method thereof | |
| CN102675963B (en) | Continuous preparing method of nanometer particle conductive ink | |
| CN111318688A (en) | Preparation method and application of aluminum-based conductive powder | |
| KR20140028208A (en) | Conductive metal ion ink composition, method of preparing the same and prerparing method of highly conductive metal pattern or film using the same | |
| CN106928775A (en) | A kind of low temperature sintering nano-copper conductive ink, preparation method and printing application | |
| KR20160117905A (en) | Composition for forming copper nanowire network by light sintering, method for preparing copper nanowire network, and transparent electrode including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |