WO2023173627A1 - Poudre d'argent sphérique et procédé de préparation associé, et pâte conductrice - Google Patents

Poudre d'argent sphérique et procédé de préparation associé, et pâte conductrice Download PDF

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WO2023173627A1
WO2023173627A1 PCT/CN2022/103623 CN2022103623W WO2023173627A1 WO 2023173627 A1 WO2023173627 A1 WO 2023173627A1 CN 2022103623 W CN2022103623 W CN 2022103623W WO 2023173627 A1 WO2023173627 A1 WO 2023173627A1
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silver
organic
colloid
silver powder
solution
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PCT/CN2022/103623
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Chinese (zh)
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夏孝天
廖云红
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江苏连银新材料有限公司
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Publication of WO2023173627A1 publication Critical patent/WO2023173627A1/fr

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • This application relates to the technical field of new electronic materials. Specifically, this application relates to a spherical silver powder and its preparation method and conductive paste.
  • the commonly used technical solutions are generally: using silver nitrate or its complex as a silver precursor, and reducing it by adding a certain reducing agent to obtain silver powder.
  • the reducing agent used generally uses vitamin C, and a large amount of dispersing agent is used.
  • Polyvinylpyrrolidone (PVP) is used.
  • the production cost of silver powder produced by the above-mentioned process technology is high, wastewater treatment is extremely difficult, and it is also very difficult to control performance indicators such as morphology, particle size, and microstructure, and it is highly uncontrollable.
  • the main defects of silver powder products prepared under currently common techniques are:
  • a high-vibration spherical silver powder is widely used in front-side silver paste in the photovoltaic industry in China.
  • the amount of dispersant PVP is as high as 22% to 50% of the silver powder output, and this cost accounts for about 20% to 30% of the material cost.
  • PVP which is used in large quantities, all enters the wastewater after completing the dispersion of the silver powder production process.
  • high-concentration PVP wastewater has extremely high viscosity. If the evaporation rate is too high, it will completely block the system and cause system paralysis. For the sake of system safety, the current evaporation rate can only be set to 80%, and the other 20%. % of the evaporated concentrated residue must be processed through the incineration system.
  • the wastewater treatment cost per kilogram of silver powder is generally around 30 yuan.
  • microstructure of silver powder affects the activity of silver powder and directly affects the sintering performance of silver paste.
  • the lack of diversification of silver powder has seriously restricted the applicable window of silver powder and cannot meet the needs of different silver paste systems for silver powder activity at different sintering temperatures.
  • this application aims to provide a preparation method of spherical silver powder. During the reduction stage of silver powder, , using an organic silver colloid as a reduction aid, successfully prepared spherical silver powder with stable performance.
  • This application also provides a spherical silver powder prepared by the above method and a conductive paste containing the spherical silver powder.
  • a method for preparing spherical silver powder characterized in that it includes the following steps:
  • Reduction reaction reduction reaction of inorganic silver salt, reducing agent, organic silver colloid and dispersion containing dispersant
  • Coating silver powder Add coating agent to the solution after the reduction reaction to obtain spherical silver powder.
  • the oxidizing liquid, the reducing liquid and the organic silver colloidal dispersion are mixed to cause a reduction reaction.
  • a reducing agent and organic silver colloid are added to the dispersion liquid, and then an oxidizing liquid is added to cause a reduction reaction.
  • the organic silver colloid particles are silver dipyridine nitrate particles, silver tetrapyridine nitrate particles, silver dipyridine sulfate particles, silver tetrapyridine sulfate particles, silver citrate particles or silver oxalate particles, preferably nitric acid.
  • the viscosity of the organic silver colloid is maintained at 5 to 30 Pa ⁇ s, preferably 10 to 20 Pa ⁇ s;
  • the prepared organic silver colloid is stored in a container, wherein the part in contact with the air is the upper surface of the organic silver colloid, and the part in contact with the bottom of the container is the bottom of the organic silver colloid, within at least 10 days after storage At any time, the absolute value of the viscosity change rate of the bottom of the organic silver colloid relative to the upper surface of the organic silver colloid is less than 10%;
  • the absolute value of the viscosity change rate of the organic silver colloid at the same position is less than 10%
  • the specific gravity of the organic silver colloid is 1.0-1.3g/mL;
  • the mass of the organic silver colloid is 0.01% to 0.5% of the mass of silver ions in the inorganic silver salt, preferably 0.1% to 0.5%;
  • the content of the stabilizer in the organic silver colloid is 20-150g/L, preferably 40-130g/L;
  • the stabilizer is a non-ionic polymer compound, preferably the stabilizer is selected from one, two or three types of gelatin, gum arabic and polyvinylpyrrolidone, and more preferably the stabilizer is polyethylene. Pyrrolidone.
  • the dispersant is a non-ionic polymer compound, preferably the dispersant is selected from polyvinylpyrrolidone, gelatin or gum arabic.
  • the dispersing agent is polyvinylpyrrolidone.
  • the concentration of silver ions in the oxidation solution is 0.2 to 2 mol/L.
  • reducing agent is selected from one, two or three types of vitamin C, formaldehyde and hydrazine hydrate;
  • the molar ratio of the reducing agent to the silver in the inorganic silver salt is 0.43 to 3:1.
  • the coating agent is selected from any one of stearic acid, sodium stearate or palmitic acid;
  • the coating agent is added to the solution after the reduction reaction, stirred for 1 to 1.5 hours, and allowed to stand for separation;
  • the coating agent is added to the solution after the reduction reaction, stirred at 200 to 500 rpm, and allowed to stand for separation.
  • the mass of the coating agent is 0.5% to 1.5% of the mass of silver ions in the inorganic silver salt, preferably 0.5% to 1%.
  • a spherical silver powder characterized in that the D50 of the silver powder is 0.5-2.0 ⁇ m, and the specific surface area of the silver powder is 0.2-1.0 m 2 /g;
  • the D10 of the silver powder is 0.6-1.2 ⁇ m;
  • the D90 of the silver powder is 1.5-2.5 ⁇ m;
  • the D100 of the silver powder is 2.2-4.5 ⁇ m;
  • the tap density of the silver powder is 5.5-6.6g/cm 3 ;
  • the silver powder has a burning loss of 0.2% to 0.9% at 540°C.
  • a spherical silver powder prepared by the preparation method described in any one of items 1 to 11.
  • a conductive paste characterized in that it contains spherical silver powder prepared by the preparation method according to any one of items 1 to 11 or spherical silver powder according to item 12.
  • the preparation method of this application uses an organic silver colloid as a reduction aid in the reduction reaction stage of silver powder to prepare a low-cost and high-performance spherical silver powder, which successfully solves the following problems:
  • Stabilizing the dosage of organic silver colloid keeps the silver powder stable in key indicators such as particle size distribution and specific surface area;
  • the microstructure of silver powder can be affected.
  • Figures 1A and 1B are respectively 6.8mm ⁇ 1.50k and 6.8mm ⁇ 10.0k scanning electron microscope images of the silver powder (L1-6) in Example 1 of the present application.
  • Figures 2A and 2B are respectively 5.7mm ⁇ 5.00k and 5.7mm ⁇ 10.0k scanning electron microscope images of the silver powder (L1-2) in Example 2 of the present application.
  • this application provides a method for preparing spherical silver powder, which includes the following steps:
  • Reduction reaction reduction reaction of inorganic silver salt, reducing agent, organic silver colloid and dispersion containing dispersant
  • Coating silver powder Add coating agent to the solution after the reduction reaction to obtain spherical silver powder.
  • the preparation method of spherical silver powder of the present application causes a reduction reaction between organic silver salt, reducing agent, and reduction aid organic silver colloid and a dispersion liquid containing a dispersant, so that the silver powder is reduced and precipitated, thereby obtaining microscopic and macroscopic silver powder with high efficiency and low cost.
  • Silver powder with highly controllable and stable properties.
  • the reduction reaction step includes:
  • the oxidizing liquid, the reducing liquid and the organic silver colloidal dispersion are mixed to cause a reduction reaction.
  • the preparation method of the present application adds organic silver colloidal dispersion liquid to the reaction kettle, and then adds the oxidizing liquid and the reducing liquid in order to cause a reduction reaction.
  • the order of the oxidizing liquid and the reducing liquid is not limited.
  • the preparation method of the present application adds organic silver colloidal dispersion liquid and reducing liquid to the reaction kettle, mixes them evenly, and then adds the oxidizing liquid to cause a reduction reaction.
  • the preparation method of the present application adds the organic silver colloidal dispersion liquid and the oxidizing liquid to the reaction kettle, mixes them evenly, and then adds the reducing liquid to cause a reduction reaction.
  • the reduction reaction step includes:
  • a reducing agent and organic silver colloid are added to the dispersion liquid, and then an oxidizing liquid is added to cause a reduction reaction.
  • the silver ion concentration in the oxidation solution is 0.2 ⁇ 2mol/L, for example, it can be 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, etc.
  • the volume of the reducing liquid is 0.3 to 1 times the volume of the oxidizing liquid, for example, it can be 0.3 times, 0.4 times, 0.5 times, 0.6 times, 0.7 times, 0.8 times, 0.9 times, 1 times, etc.
  • the preparation method of the present application involves mixing the oxidizing liquid, the reducing liquid and the organic silver colloid dispersion to undergo a reduction reaction, or adding a reducing agent and organic silver colloid to the dispersion.
  • the speed of adding the oxidizing solution is 25-50L/min, for example, it can be 25L/min, 27L/min, 30L/min, 32L/min, 35L/min, 38L/min, 40L/min , 43L/min, 45L/min, 48L/min, 50L/min, etc.
  • the grain growth mechanism of the silver powder reduction reaction is as follows: crystal nuclei are formed first, and the crystal nuclei grow in a specific direction due to the influence of the reaction environment. As the reaction time passes, the grown crystal nuclei will gradually agglomerate between particles. The feeding speed is fast, the reaction time is shortened, and the probability of grain agglomeration is greatly reduced, so the dispersion is improved.
  • the reduction reaction step includes:
  • the preparation method of the present application involves mixing the oxidizing liquid, the reducing liquid and the organic silver colloid dispersion to undergo a reduction reaction, or adding silver salt and organic silver colloid to the dispersion.
  • the speed of adding the reducing solution is 25 ⁇ 50L/min, for example, it can be 25L/min, 27L/min, 30L/min, 32L/min, 35L/min, 38L/min, 40L/min , 43L/min, 45L/min, 48L/min, 50L/min, etc.
  • the feeding speed is fast, the reaction time is shortened, and the probability of grain agglomeration is greatly reduced, so the dispersion is improved.
  • the organic silver colloid contains organic silver colloid particles and a stabilizer, wherein the silver content in the organic silver colloid is 0.01 to 0.2 mol/L, preferably 0.01 to 0.05 mol. /L, for example, it can be 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L , 0.1mol/L, 0.12mol/L, 0.14mol/L, 0.16mol/L, 0.18mol/L, 0.2mol/L, etc.
  • the method for measuring the silver content in the organic silver colloid of this application is:
  • step (3) Accurately weigh the sample weight W2 in step (2) (accurate to 0.001g);
  • the organic silver colloidal particles are silver dipyridine nitrate particles, silver tetrapyridine nitrate particles, silver dipyridine sulfate particles, silver tetrapyridine sulfate particles, citric acid
  • Silver particles or silver oxalate particles are preferably silver dipyridine nitrate particles, silver tetrapyridine nitrate particles, silver dipyridine sulfate particles or silver tetrapyridine sulfate particles, and more preferably silver dipyridine nitrate particles or tetrapyridine nitrate particles.
  • the organic silver colloid particles formed by the complexation of two or four molecules of pyridine groups with one silver ion can make the organic silver colloid more stable.
  • the organic silver colloid is prepared at any time within at least 10 days, preferably at least 15 days, more preferably at least 20 days, using a rotational viscometer at 25°C,
  • the viscosity measured at 10 rpm is 5 to 30 Pa ⁇ s, preferably 10 to 20 Pa ⁇ s, for example, it can be 5 Pa ⁇ s, 8 Pa ⁇ s, 10 Pa ⁇ s, 12 Pa ⁇ s, 15 Pa ⁇ s, 18 Pa ⁇ s, 20 Pa ⁇ s , 23Pa ⁇ s, 25Pa ⁇ s, 27Pa ⁇ s, 30Pa ⁇ s, etc.
  • at least 10 days can be, for example, 10 days, 15 days, 20 days, 25 days, 30 days, etc.
  • the specific gravity of the organic silver colloid obtained by the preparation method of the present application is 1.0-1.3g/mL, for example, it can be 1.0g/mL, 1.05g/mL, 1.1g/mL, 1.15g/mL, 1.2g/mL, 1.25g/mL, 1.3g/mL, etc.
  • the viscosity of the organic silver colloid is maintained at 5 to 30 Pa ⁇ s for at least 10 days, preferably at least 15 days, and more preferably at least 20 days after preparation, preferably 10 to 30 Pa ⁇ s. 20 Pa ⁇ s; the prepared organic silver colloid is stored in a container, where the part in contact with the air is the upper surface of the organic silver colloid, and the part in contact with the bottom of the container is the bottom of the organic silver colloid.
  • the absolute value of the viscosity change rate of the bottom of the organic silver colloid relative to the upper surface of the organic silver colloid is less than 10%, for example, it can be 9.8%, 9.5%, 9%, 8.5%, 8%, 7.5%, 7%, 6.5%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5% , 1%, 0.5%, 0%, etc., the smaller the value, the more stable the organic silver colloid is, wherein at least 10 days can be, for example, 10 days, 15 days, 20 days, 25 days, 30 days, etc.
  • the viscosity of the organic silver colloid is maintained at 5 to 30 Pa ⁇ s, preferably 10 to 20 Pa within 10 days, preferably at least 15 days, and more preferably at least 20 days after preparation.
  • the prepared organic silver colloid is stored in a container, wherein the part in contact with the air is the upper surface of the organic silver colloid, and the part in contact with the bottom of the container is the bottom of the organic silver colloid, within at least 10 days after storage , preferably within at least 15 days, more preferably at any time within at least 20 days, the absolute value of the viscosity change rate of the bottom of the organic silver colloid relative to the upper surface of the organic silver colloid is less than 10%, for example, it can be 9.8%, 9.5 %, 9%, 8.5%, 8%, 7.5%, 7%, 6.5%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.5%, 0%, etc., at least 10 days can be, for example, 10 days, 15 days, 20 days, 25 days, 30 days, etc., preferably at least 15 days, more preferably at least 20 days; the organic silver colloid After storage for at least 10 days, preferably
  • the mass of the organic silver colloid is 0.01% to 0.5% of the mass of silver ions in the inorganic silver salt, preferably 0.1% to 0.5%, for example, it can be 0.01% , 0.02%, 0.03%, 0.04%, 0.05%, 0.12%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, etc.
  • the organic silver colloid also contains a stabilizer, and the organic silver colloid particles are evenly dispersed in the microscopic colloidal structure constructed by the stabilizer. Due to the protection of the microscopic colloidal structure, the organic silver colloid is protected. The agglomeration between silver colloid particles plays a very good blocking role and effectively prevents organic silver from losing activity due to oxidation when exposed to air, thereby preparing highly stable organic silver colloid.
  • the content of the stabilizer is 20 to 150g/L, preferably 40 to 130g/L.
  • the stabilizer is a non-ionic polymer compound, and preferably the stabilizer is selected from the group consisting of gelatin, gum arabic and polyvinylpyrrolidone. One kind, two kinds or three kinds, more preferably the stabilizer is polyvinylpyrrolidone.
  • the dispersant is a non-ionic polymer compound.
  • the dispersant is selected from one, two or three types of polyvinylpyrrolidone, gelatin or gum arabic. , more preferably the dispersant is polyvinylpyrrolidone.
  • the inorganic silver salt used in the reduction reaction is a silver salt solution or silver salt crystal.
  • the inorganic silver salt is silver nitrate.
  • Silver nitrate is the most water-soluble inorganic salt with low cost, sufficient market supply and stable performance.
  • the preparation method of the present application uses a reducing agent to reduce and precipitate silver.
  • a reducing agent one or more of vitamin C, formaldehyde, hydrazine hydrate, amine compounds and glucose can be selected.
  • the reducing agent is selected from one, two or three types of vitamin C, formaldehyde and hydrazine hydrate.
  • silver powder with stable particle size distribution can be obtained.
  • the molar ratio of silver in the reducing agent and the inorganic silver salt is 0.43 to 3:1, for example, it can be 0.43:1, 0.45:1, 1:1, 1.5:1, 2: 1, 2.5:1, 3:1, etc.
  • the coating agent is attached to the surface of the silver powder.
  • the coating agent has two functions: it provides a guarantee for the stability of the dispersion performance of the silver powder product during storage; This ensures that the organic components in the slurry, including solvents, carriers, etc., form a whole quickly and uniformly.
  • the coating agent is not particularly limited. For example, it can be any one of stearic acid, sodium stearate or palmitic acid. kind.
  • a coating agent is added to the solution after the reduction reaction, stirred, left to stand for layering, and spherical silver powder is obtained after solid-liquid separation.
  • the above-mentioned stirring speed is 200-500 rpm, and the stirring time is 1-1.5 h, etc.
  • the mass of the dispersant does not exceed 10% of the mass of silver ions in the inorganic silver salt, and is preferably 2% to 8% of the mass of silver ions in the inorganic silver salt.
  • the mass of the dispersant is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
  • the mass of silver ions in the silver salt is 0.5% to 1.5%, preferably 0.5% to 1.0%, for example, it can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.
  • the preparation method of the present application is to add each reaction liquid, such as: oxidizing liquid, reducing liquid, organic silver colloid dispersion liquid, the liquid obtained by adding reducing agent and organic silver colloid to the dispersion liquid, or to the dispersion liquid.
  • the temperature of the liquid obtained after adding inorganic silver salt and organic silver colloid is controlled at 15-40°C for later use. For example, it can be 15°C, 18°C, 20°C, 23°C, 25°C, 28°C, 30°C, 33°C. °C, 35°C, 37°C, 40°C, etc.
  • the water is deionized water.
  • the preparation method of the present application may also include a cleaning step of silver powder. Since the silver powder obtained through the above-mentioned reduction reaction and silver powder coating contains impurities, cleaning is required.
  • a cleaning solvent used for the above-mentioned cleaning pure water is preferred.
  • the above-mentioned recovery and cleaning methods are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include decantation and press filtration.
  • the preparation method of the present application may also include a step of drying the silver powder.
  • the silver powder obtained after solid-liquid separation or the cleaned silver powder contains moisture and needs to be removed before use.
  • vacuum drying is preferred.
  • the drying temperature is preferably 100°C or lower.
  • the present application also provides a spherical silver powder
  • the D50 of the silver powder is 0.2-2.0 ⁇ m, preferably 0.9-1.6 ⁇ m, for example, it can be 0.2 ⁇ m, 0.4 ⁇ m, 0.6 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1.0 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.5 ⁇ m, 1.7 ⁇ m, 1.9 ⁇ m, 2.0 ⁇ m, etc.
  • the specific surface area of the silver powder is 0.2 to 1.0 m 2 /g, preferably 0.3 to 0.7 m 2 /g, and more It is preferably 0.25 to 0.4m 2 /g, for example, it can be 0.2m 2 /g, 0.25m 2 /g, 0.3m 2 /g, 0.35m 2 /g, 0.4m 2 / g, 0.45m 2 / g, 0.5 m 2 /g, 0.6m 2 /g
  • the spherical shape in this application refers to a silver powder whose particle shape is spherical or approximately spherical when observed under a scanning electron microscope (SEM), and the sphericity of 100 particles is 1.5 or less.
  • the sphericity refers to the silver powder obtained through the SEM photo. When observing particles, the ratio of the longest diameter to the shortest diameter.
  • the measurement method of D50 is the cumulative 50% particle size in the volume-based particle size distribution measured by a laser diffraction particle size distribution measuring method.
  • the specific surface area of the silver powder in this application is the BET specific surface area.
  • the measurement method is: BET static method, and the measurement equipment is: Japanese Horiba 9603SA.
  • the specific surface area is too high, such as higher than 1.0m 2 /g, the viscosity of the prepared slurry will increase sharply, which will have a fatal impact on the printing performance of the slurry.
  • the specific surface area is too low, such as higher than 0.2m 2 /g, the viscosity of the prepared slurry will be very low, the printing line shape of the slurry cannot be maintained, and collapse will occur, seriously affecting the electrical properties of the slurry.
  • the D10 of the silver powder of the present application is 0.6-1.2 ⁇ m, for example, it can be 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1.0 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, etc.
  • D10 in this application means that 10% of particles have a particle size smaller than this value.
  • the D90 of the silver powder of the present application is 1.5-2.5 ⁇ m, for example, it can be 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.9 ⁇ m, 2.2 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, etc.
  • D90 in this application means that 90% of particles have a particle size smaller than this value.
  • the D100 of the silver powder of the present application is 2.2-4.5 ⁇ m, for example, it can be 2.5 ⁇ m, 2.8 ⁇ m, 3.0 ⁇ m, 3.3 ⁇ m, 3.5 ⁇ m, 3.9 ⁇ m, etc.
  • D100 in this application means that 100% of particles have a particle size smaller than this value.
  • the determination methods of D10, D90 and D100 in this application are the same as the determination method of D50.
  • the prepared silver paste will easily block the screen during printing and will be difficult to burn through during sintering, causing electrical performance problems. If the particle size distribution of the silver powder is too small, it will be difficult to disperse and easy to form agglomerates when preparing the silver paste. It is easy to block the screen during printing, and the silver paste is easy to burn out when sintering, causing electrical performance problems. In addition, it is preferable to use a silver powder with a narrow peak width of the particle size distribution and a uniform particle size with little variation.
  • the tap density of the silver powder of the present application is 5.5-6.6g/cm 3 , preferably 6.1-6.6g/cm 3 , for example, it can be 5.5g/cm 3 , 5.6g/cm 3 , 5.7 g/cm 3 , 5.8g/cm 3 , 6.0g/cm 3 , 6.1g/cm 3 , 6.2g/cm 3 , 6.3g/cm 3 , 6.5g/cm 3 , 6.6g/cm 3 etc.
  • Tap density refers to the mass per unit volume measured after the powder in the container is tapped under specified conditions.
  • the tap density of the prepared silver paste will be high, making it difficult to increase the silver content of the silver paste, making it difficult to achieve the purpose of improving electrical properties by increasing the silver content.
  • the tap density of silver powder in this application was measured with reference to GB/T 5162-2006.
  • the burning loss of the silver powder of the present application at 540°C is 0.2% to 0.9%, preferably 0.25% to 0.6%, for example, it can be 0.2%, 0.25%, 0.3%, 0.35%, 0.4% , 0.45%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc.
  • Burning loss refers to: after burning at 540°C for 2 hours, the organic coating agent is completely decomposed. At this time, the measured weight loss of the silver powder (i.e., the burning loss value) is the content of the organic coating agent.
  • the preparation method of the organic silver colloid of the present application includes the following steps:
  • Preparing a silver precursor solution dissolving the inorganic silver salt solid in water to obtain the silver precursor solution;
  • Preparing an organic complexing solution diluting the organic complexing agent with water to obtain the organic complexing solution;
  • Preparing organic silver colloid Mix the stabilizer solution, organic complex solution and silver precursor solution to cause a complexing reaction to obtain the organic silver colloid.
  • the preparation method of organic silver colloids in this application uses organic groups to complex with silver ions, and at the same time, stabilizers are used in the synthesis environment, so that the organic silver colloid particles generated by the complexation reaction are evenly dispersed in the microscopic colloidal structure constructed by the stabilizer. , due to the protection of the microscopic colloidal structure, it plays a good blocking role in the agglomeration of organic silver compound powders, and effectively prevents the loss of activity of organic silver due to oxidation due to exposure to air, thus preparing highly stable organic Silver colloid.
  • the organic complexing agent is selected from one of pyridine, citric acid and its salts, oxalic acid and its salts, preferably pyridine.
  • Pyridine is an organic compound, a six-membered heterocyclic compound containing a nitrogen heteroatom, which can be regarded as a CH in the benzene molecule replaced by N.
  • the chemical properties of this type of heterocyclic compounds are as follows: electrophilic substitution reaction is difficult, nucleophilic substitution reaction is easy, oxidation reaction is difficult, and reduction reaction is easy.
  • the stability is greatly improved in common application scenarios, especially in storage environments.
  • a pyridine group is introduced into the anionic part of the organic silver compound, and the pyridine group is used to complex with silver ions, thereby obtaining an organic silver colloid with higher stability.
  • the concentration of the organic complexing agent in the organic complex solution is 0.1 to 1 mol/L, preferably It is 0.2 ⁇ 0.6mol/L, for example, it can be 0.1mol/L, 0.12mol/L, 0.15mol/L, 0.17mol/L, 0.2mol/L, 0.22mol/L, 0.24mol/L, 0.26mol/L , 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L, etc., to control the concentration of organic complexing agent in the organic complexing solution within this range, organic silver colloids with better stability can be obtained.
  • the organic complexing agent is pyridine
  • the coordination number between silver and pyridine groups can be better controlled, and silver bipyridine has the best stability.
  • the inorganic silver salt in the preparation method of the organic silver colloid of the present application, is silver nitrate or silver sulfate, preferably silver nitrate.
  • Silver nitrate is the most water-soluble inorganic salt with low cost, sufficient market supply and stable performance, so that an organic silver colloid with good stability can finally be obtained.
  • the concentration of silver ions in the silver precursor solution is 0.05 ⁇ 0.5mol/L, preferably 0.08 ⁇ 0.3mol /L, for example, it can be 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L , 0.5mol/L, etc. If the concentration of silver ions is too high, it is easy to produce precipitates with coarse particle sizes during the complexation process, which affects the activity and stability of the colloid. If the concentration is too low, the amount of colloid used in the actual application process will increase. By controlling the concentration of silver ions in the silver precursor solution within this range, the prepared organic silver colloid can have higher activity, better stability and a smaller dosage.
  • the stabilizer in the preparation method of organic silver colloid of the present application, is a non-ionic polymer compound, which dissolves in the aqueous phase and builds a stable colloidal structure, for example, it can be selected from gelatin One, two or three of gum arabic and polyvinylpyrrolidone (PVP). Because PVP has high water solubility, it is more preferred that the stabilizer is polyvinylpyrrolidone.
  • PVP polyvinylpyrrolidone
  • the stabilizer concentration in the stabilizer solution is 50-150g/L, preferably 50-135g/L, for example, it can be 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 133g/L, 135g/L, 140g/L, 150g/L, etc., put into the dosage solution
  • concentration of the stabilizer is controlled within the above range, so that the prepared organic silver colloid has better stability and a smaller dosage.
  • the viscosity of the stabilizer solution measured at 25°C and 10 rpm using a rotational viscometer is 10 to 30 Pa.
  • ⁇ s preferably 18 to 30 Pa ⁇ s, more preferably 20 to 25 Pa ⁇ s, for example, 10 Pa ⁇ s, 12 Pa ⁇ s, 14 Pa ⁇ s, 15 Pa ⁇ s, 18 Pa ⁇ s, 20 Pa ⁇ s, 22 Pa ⁇ s , 24Pa ⁇ s, 25Pa ⁇ s, 28Pa ⁇ s, 30Pa ⁇ s, etc., control the viscosity of the stabilizer solution within this range, so that the viscosity of the finally prepared organic silver colloid is controlled at 5-30Pa ⁇ s, and the viscosity is more stable and uniform , the organic silver colloidal particles generated by the complexation reaction are more evenly dispersed in the stabilizer.
  • the molar ratio of the organic complexing agent to the silver in the inorganic silver salt solid is 2 to 4:1, for example, it can be 2:1, 2.2 :1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, etc., in this application, by controlling the organic complexation
  • the molar ratio of the agent to the silver in the inorganic silver salt solid is such that an excess of organic complexing agent is added to ensure that the inorganic silver salt is fully complexed.
  • the mass of the stabilizer is 20 to 50 times the solid mass of the inorganic silver salt, preferably 30 to 45 times, for example, it can be 20 times, 22 times, 24 times, 26 times, 28 times, 30 times, 32 times , 34 times, 36 times, 38 times, 40 times, 42 times, 44 times, 46 times, 48 times, 50 times, etc., which can ensure that the organic silver colloid is fully wrapped.
  • the stabilizer solution and the organic complex solution are mixed, and then the silver precursor solution is slowly added , a complexation reaction occurs, and the organic silver colloid is obtained; or, the stabilizer solution and the silver precursor solution are mixed, and then the organic complexation solution is slowly added, and a complexation reaction occurs, and the organic silver colloid is obtained. colloid.
  • the speed of slowly adding the silver precursor solution or slowly adding the organic complex solution is 0.01 ⁇ 1L/min, preferably 0.05 ⁇ 0.5L /min, for example, it can be 0.01L/min, 0.05L/min, 0.1L/min, 0.2L/min, 0.3L/min, 0.4L/min, 0.5L/min, 0.6L/min, 0.7L/min , 0.8L/min, 0.9L/min, 1L/min, etc.
  • controlling the slow addition speed can make the complexation reaction more thorough; after the complexation reaction, vacuum treatment is performed, preferably under low-speed stirring. , the organic silver colloid is obtained, and the vacuum treatment can fully remove the air mixed in the organic silver colloid during the preparation process to further ensure the stability of the organic silver colloid.
  • the steps of preparing the silver precursor solution, the step of preparing the organic complex solution, the step of preparing the stabilizer solution, and the step of preparing the organic silver colloid are all performed at 10 to 30°C.
  • the temperature may be 10°C, 12°C, 14°C, 16°C, 18°C, 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, etc.; the water is deionized water.
  • the present application also provides a spherical silver powder prepared by any of the aforementioned preparation methods.
  • the present application also provides a conductive paste containing any of the aforementioned spherical silver powders or spherical silver powders prepared by any of the aforementioned preparation methods.
  • the conductive slurry further includes glass powder, organic solvent and carrier.
  • Silver nitrate solid Purity: ⁇ 99.8%, Tongbai, Henan;
  • PVP pharmaceutical grade, BASF
  • Organic silver colloid homemade in the laboratory.
  • Preparation of organic silver colloid Mix the stabilizer solution and the organic complex solution in a stirring tank. After stirring evenly, add the silver precursor solution. The adding time is 2 hours. The temperature is controlled to 15°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 1 hour, seal the stirring tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain uniform color dipyridine silver nitrate organic silver colloid or dipyridine silver nitrate organic silver colloid mixed with tetrapyridine silver nitrate.
  • Preparation of organic silver colloid Mix the stabilizer solution and silver precursor solution in a stirring tank. After stirring evenly, add the organic complex solution. The adding time is 3 hours. The temperature is controlled to 20°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 2 hours, seal the stirring tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain uniform color dipyridine silver nitrate organic silver colloid or dipyridine silver nitrate organic silver colloid mixed with tetrapyridine silver nitrate.
  • Preparation of organic silver colloid Mix the stabilizer solution and silver precursor solution in a stirring tank. After stirring evenly, add the organic complex solution. The adding time is 3 hours. The temperature is controlled to 20°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 2 hours, seal the stirring tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain uniform color dipyridine silver nitrate organic silver colloid or dipyridine silver nitrate organic silver colloid mixed with tetrapyridine silver nitrate.
  • the stabilizer solution is prepared: add 1000g of gelatin in the mixing tank, add deionized water, stir and dissolve into a clear and transparent solution, and obtain 20L of stabilizer solution.
  • the stabilizer solution is measured using a rotational viscometer at 25°C and 10rpm. The viscosity is 30Pa ⁇ s;
  • Preparation of organic silver colloid Mix the stabilizer solution and silver precursor solution in a stirring tank. After stirring evenly, add the organic complex solution. The adding time is 3 hours. The temperature is controlled to 20°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 2 hours, seal the stirring tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain uniform color dipyridine silver nitrate organic silver colloid or dipyridine silver nitrate organic silver colloid mixed with tetrapyridine silver nitrate.
  • Silver precursor solution Add 48g of solid silver nitrate into the batching tank, add deionized water, stir and dissolve into a clear and transparent solution, and obtain 1.5L of silver precursor solution;
  • Organic complex solution add 110g citric acid crystals into the batching tank, dilute with deionized water, stir evenly to form a clear and transparent solution, and obtain 1.5L organic complex solution;
  • Preparation of organic silver colloid Mix the organic complex solution and the stabilizer solution in a stirring tank. After stirring evenly, add the silver precursor solution. The adding time is 2 hours. The temperature is controlled to 15°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 1 hour, seal the mixing tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain organic silver colloid with uniform color.
  • Preparation of organic silver colloid Mix the stabilizer solution and the organic complex solution in a stirring tank. After stirring evenly, add the silver precursor solution. The adding time is 2 hours. The temperature is controlled to 15°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 1 hour, seal the stirring tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain uniform color dipyridine silver nitrate organic silver colloid or dipyridine silver nitrate organic silver colloid mixed with tetrapyridine silver nitrate.
  • Preparation of organic silver colloid Mix the stabilizer solution and the organic complex solution in a stirring tank. After stirring evenly, add the silver precursor solution. The adding time is 2 hours. The temperature is controlled to 15°C. After the reaction is completed, stir at a low speed of 20 rpm and let stand. Leave for 1 hour, seal the stirring tank, and perform vacuum treatment with low-speed stirring at 20 rpm to obtain uniform color dipyridine silver nitrate organic silver colloid or dipyridine silver nitrate organic silver colloid mixed with tetrapyridine silver nitrate.
  • the evaluation method of organic silver colloid activity is as follows: apply organic silver colloid products to the silver nitrate reduction system. When obtaining silver powder particles of the same particle size, the smaller the amount of colloid used, the higher the activity.
  • the evaluation standard for the stability of organic silver colloid is: according to the degree of satisfaction of the continuity of silver powder production, at any time within 10 days after the preparation of the organic silver colloid, the bottom of the organic silver colloid relative to the upper surface of the organic silver colloid The absolute value of the viscosity change rate is required to be less than 10%. After the organic silver colloid is stored for 10 days, the absolute value of the viscosity change rate of the organic silver colloid at the same location is required to be less than 10%.
  • Examples 1-1 to 1-4 and 1-7 can all obtain organic silver colloids with better performance
  • Example 5 settled after being stored for 10 days, and the activity also decreased significantly;
  • Examples 1-1 to 1-4 are higher than Examples 1-6 and 1-7;
  • Example 1-1 and Example 1-2 are better than Example 1-3 and Example 1-4, and Examples 1-3 and 1-4 are better than Examples 1-6 and 1 -7, Embodiments 1-6 and 1-7 are better than Embodiment 1-5.
  • Example 1-1 The organic silver colloid prepared in Example 1-1 was used to prepare the spherical silver powder of Examples 2-1 to 2-7.
  • Reduction reaction Open the stirrer of the reaction kettle, use a metering pump to add the prepared oxidizing liquid and reducing liquid to the reactor in sequence according to the set flow rate and order.
  • the adding speed of the oxidizing liquid and reducing liquid is 50L/ min, the stirring speed is controlled to 200rpm;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for stratification. , the stirring speed is 400rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • reaction bottom solution add 2kg of PVP into a 1000L reaction kettle, add 450L of deionized water, add 20kg of vitamin C after dissolving, stir and dissolve; finally add 50g of organic silver colloid, stir evenly, and heat to 30°C for later use;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for separation. layer, the stirring speed is 400 rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • reaction bottom solution add 2kg of PVP to a 1000L reaction kettle, add 450L of deionized water, add 40kg of silver nitrate after dissolution, stir and dissolve; finally add 50g of organic silver colloid, stir evenly and adjust with ammonia water Adjust pH to 7 ⁇ 8, heat to 30°C and set aside;
  • Reduction reaction Open the stirrer of the reaction kettle, use a metering pump to add the prepared reducing liquid into the reaction kettle according to the set flow rate, the adding speed of the reducing liquid is 50L/min, and the stirring speed is 200rpm;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for separation. layer, the stirring speed is 400 rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • Reduction reaction Open the stirrer of the reaction kettle, use a metering pump to add the prepared oxidizing liquid and reducing liquid to the reactor in sequence according to the set flow rate and order.
  • the adding speed of the oxidizing liquid and reducing liquid is 50L/ min, the stirring speed is controlled to 200rpm;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for stratification. , the stirring speed is 400rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • Reduction reaction Open the stirrer of the reaction kettle, use a metering pump to add the prepared oxidizing liquid and reducing liquid to the reactor in sequence according to the set flow rate and order.
  • the adding speed of the oxidizing liquid and reducing liquid is 50L/ min, the stirring speed is controlled to 200rpm;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for stratification. , the stirring speed is 400rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • Reduction reaction Open the stirrer of the reaction kettle, use a metering pump to add the prepared oxidizing liquid and reducing liquid to the reactor in sequence according to the set flow rate and order.
  • the adding speed of the oxidizing liquid and reducing liquid is 50L/ min, the stirring speed is controlled to 200rpm;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for stratification. , the stirring speed is 400rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • Reduction reaction Open the stirrer of the reaction kettle, use a metering pump to add the prepared oxidizing liquid and reducing liquid to the reactor in sequence according to the set flow rate and order.
  • the adding speed of the oxidizing liquid and reducing liquid is 50L/ min, the stirring speed is controlled to 200rpm;
  • Silver powder coating After the reduction reaction is completed, add sodium stearate into the reaction kettle in an amount of 0.5% to 1.5% of the mass of silver ions in the initial silver nitrate. Stir at high speed for 1 to 1.5 hours and then let stand for stratification. , the stirring speed is 400rpm; after solid-liquid separation, spherical silver powders with various particle size ranges are obtained.
  • the performance of silver powder is mainly reflected in its applicability. Silver powder with better performance often has stronger applicability and shows good performance under different customer systems.
  • the difference is less than 4 ⁇ m, especially less than 3 ⁇ m, the silver powder particle size distribution width is narrow; conversely, when the difference is greater than 4 ⁇ m, especially greater than 5 ⁇ m, the silver powder particle size distribution width is large.
  • the specific surface area and tap density are related to the printing performance of the prepared silver paste. A suitable specific surface area and a higher tap density provide guarantee for the printing performance of the silver paste. In addition, a higher tap density also ensures the printing performance of the silver paste. Linear shape and higher electrical performance are guaranteed.
  • the appropriate burning loss value at 540°C ensures the dispersion and stability of the prepared slurry.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

Procédé de préparation de poudre d'argent sphérique comprenant : la réalisation d'une réaction de réduction : la réalisation d'une réaction de réduction sur un sel d'argent inorganique, un agent réducteur, un colloïde d'argent organique et un liquide de dispersion comprenant un agent de dispersion ; et l'enveloppement de poudre d'argent : l'ajout d'un agent d'enveloppement dans la solution soumise à la réaction de réduction de manière à obtenir une poudre d'argent sphérique. L'invention concerne également de la poudre d'argent, le D50 de la poudre d'argent étant de 0,5 à 2,0 µm, et la surface spécifique de la poudre d'argent étant de 0,2-1,0 m2/g. L'invention concerne en outre une pâte conductrice comprenant la poudre d'argent. La poudre d'argent préparée au moyen du procédé est stable dans des indices clés tels que la distribution de tailles de particules et la surface spécifique ; par réglage du dosage d'argent organique, les indices clés tels que la distribution de tailles de particules et la surface spécifique de la poudre d'argent peuvent être réglés de manière flexible de sorte que la diversification d'un produit en poudre d'argent est obtenue.
PCT/CN2022/103623 2022-03-15 2022-07-04 Poudre d'argent sphérique et procédé de préparation associé, et pâte conductrice WO2023173627A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117358941A (zh) * 2023-12-08 2024-01-09 长春黄金研究院有限公司 高比表面积花球状银粉的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114619039B (zh) * 2022-03-15 2023-01-31 江苏连银新材料有限公司 一种球形银粉及其制备方法和导电浆料
CN114426515A (zh) * 2022-03-15 2022-05-03 江苏连银新材料有限公司 一种有机银胶体及其制备方法
CN116408443A (zh) * 2023-04-14 2023-07-11 湖北银科新材料股份有限公司 一种太阳能电池正面银浆用银粉及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077372A (ja) * 2010-10-06 2012-04-19 Sumitomo Metal Mining Co Ltd 銀粉及びその製造方法
CN108714700A (zh) * 2018-06-07 2018-10-30 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） 一种单分散高结晶型银粉的制备方法及其制得的银粉
CN109128211A (zh) * 2018-08-16 2019-01-04 山东大学 水溶液体系中制备微纳米银颗粒的方法
CN110150316A (zh) * 2019-06-02 2019-08-23 上海纳米技术及应用国家工程研究中心有限公司 一种纳米银/次氯化物复合杀菌液的制备方法
CN110434355A (zh) * 2019-09-24 2019-11-12 广东先导稀材股份有限公司 一种高振实密度高分散性球形银粉的制备方法
CN112475311A (zh) * 2020-10-30 2021-03-12 山东建邦胶体材料有限公司 一种粒径可精确控制的类球形银粉及其制备方法
CN114619039A (zh) * 2022-03-15 2022-06-14 江苏连银新材料有限公司 一种球形银粉及其制备方法和导电浆料

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1300602C (zh) * 2002-12-25 2007-02-14 中国人民解放军电子工程学院 液相夹层式纳米胶体粒子激光防护材料
CN101972855B (zh) * 2010-11-11 2012-10-17 肇庆市羚光电子化学品材料科技有限公司 一种高温烧结银浆用银微粉制备方法
CN102764897B (zh) * 2012-08-09 2014-10-22 深圳市圣龙特电子有限公司 一种用于导电浆料的亚微米级银粉的制备方法
JP6003880B2 (ja) * 2013-10-28 2016-10-05 住友金属鉱山株式会社 銀粉の製造方法
CN106583746A (zh) * 2016-11-30 2017-04-26 中国东方电气集团有限公司 一种太阳能电池板银粉的制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077372A (ja) * 2010-10-06 2012-04-19 Sumitomo Metal Mining Co Ltd 銀粉及びその製造方法
CN108714700A (zh) * 2018-06-07 2018-10-30 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） 一种单分散高结晶型银粉的制备方法及其制得的银粉
CN109128211A (zh) * 2018-08-16 2019-01-04 山东大学 水溶液体系中制备微纳米银颗粒的方法
CN110150316A (zh) * 2019-06-02 2019-08-23 上海纳米技术及应用国家工程研究中心有限公司 一种纳米银/次氯化物复合杀菌液的制备方法
CN110434355A (zh) * 2019-09-24 2019-11-12 广东先导稀材股份有限公司 一种高振实密度高分散性球形银粉的制备方法
CN112475311A (zh) * 2020-10-30 2021-03-12 山东建邦胶体材料有限公司 一种粒径可精确控制的类球形银粉及其制备方法
CN114619039A (zh) * 2022-03-15 2022-06-14 江苏连银新材料有限公司 一种球形银粉及其制备方法和导电浆料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117358941A (zh) * 2023-12-08 2024-01-09 长春黄金研究院有限公司 高比表面积花球状银粉的制备方法
CN117358941B (zh) * 2023-12-08 2024-03-01 长春黄金研究院有限公司 高比表面积花球状银粉的制备方法

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