WO2019088510A1 - Procédé de production de poudre d'argent - Google Patents

Procédé de production de poudre d'argent Download PDF

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WO2019088510A1
WO2019088510A1 PCT/KR2018/012185 KR2018012185W WO2019088510A1 WO 2019088510 A1 WO2019088510 A1 WO 2019088510A1 KR 2018012185 W KR2018012185 W KR 2018012185W WO 2019088510 A1 WO2019088510 A1 WO 2019088510A1
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silver powder
silver
washing
powder
solution
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PCT/KR2018/012185
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English (en)
Korean (ko)
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김영환
이미영
진우민
강태훈
최재원
이창근
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엘에스니꼬동제련 주식회사
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Publication of WO2019088510A1 publication Critical patent/WO2019088510A1/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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold

Definitions

  • the present invention relates to a method for producing a silver powder for conductive paste for forming an electrode of an electronic component such as an electrode for a solar cell, an internal electrode of a multilayer capacitor, and a conductor pattern of a circuit board.
  • the conductive metal paste is a paste in which electricity is applied to a dried or baked coating film having a coating ability capable of forming a coating film and is dispersed with a conductive filler (metal filler) alone or in a glass frit in a vehicle made of a resin- It is widely used for the formation of an electric circuit or the formation of an external electrode of a ceramic capacitor.
  • Silver Paste is the most chemically stable and excellent in conductivity among the conductive paste of composite system, and has a wide range of applications in various fields such as conductive bonding and coating and fine circuit formation.
  • the electronic parts such as PCBs (Printed Circuit Boards), which are particularly important for reliability, the use of silver paste is used for bonding or coating materials for STH (Silver Through Hole), for internal electrodes in multilayer capacitors, Is widely used as an electrode material.
  • a slurry in which precipitated silver powder is dispersed can be obtained.
  • an organic reducing agent is added to a silver nitrate solution to reduce and precipitate silver powder to obtain a slurry in which silver powder is dispersed, and the silver powder slurry is dried The silver powder is recovered.
  • a powder manufacturing method includes a step of dewatering and drying a silver powder slurry.
  • the silver powder slurry is usually filtered and washed with water, dehydrated and then air dried, hot-air dried, or vacuum dried , And the dried product is crushed to recover silver powder.
  • the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a silver powder production method capable of increasing the cleaning efficiency of an insoluble organic substance generated at the time of reduction Method.
  • the present invention provides a cleaning method of silver powder comprising a washing step (S31) of washing a silver powder precipitated by a wet reduction method using a reducing agent with a cleaning solution containing a compound represented by the following formula .
  • x and y are each independently 1 or 2
  • R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen (H), C 1 -C 6 alkyl, C 1 -C 6 alkoxy, boranes, amino, Include hydroxy, hydroxymethyl, carboxy or mercapto.)
  • H hydrogen
  • C 1 -C 6 alkyl C 1 -C 6 alkoxy
  • boranes amino, Include hydroxy, hydroxymethyl, carboxy or mercapto.
  • the washing step (S31) is a step of washing the silver powder so that the compound is used in an amount of 0.1 to 2.0 parts by weight based on 100 parts by weight of the silver powder.
  • M is Na or Li
  • x is 1 or 2
  • y is 1
  • R 1 , R 2 , R 3 and R 4 are Characterized in that the washing is carried out using a washing solution comprising a compound comprising independently hydrogen (H), C 1 -C 6 alkyl, or boranes.
  • the reducing agent includes at least one selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin.
  • the washing step (S31) is a step of dispersing the precipitated silver powder in a solvent, adding the washing solution to a solution in which the silver powder is dispersed, and mixing and stirring.
  • the present invention is an ion, ammonia (NH 3) and nitric acid (HNO 3)
  • the first reaction solution and for producing a second reaction solution containing a reducing agent in the reaction mixture prepared step (S21) and the first reaction solution containing the and A silver salt reducing step (S2) including a precipitation step (S22) of reacting the second reaction solution to obtain silver powder; And a washing step (S31) of washing the obtained silver powder with a washing solution containing the compound represented by the formula (1).
  • the silver powder washed according to the above method is characterized in that the degree of cohesion (D 50 / D SEM ) is 1.80 or less, the chromaticity of the supernatant dissolved in the NaOH solution is 200 PCU or less, and the alkali content is 80 ppm or less.
  • a metal powder including silver powder washed according to the above method; And a glass vehicle comprising a solvent and an organic binder; And a conductive paste.
  • a metal powder including silver powder washed according to the above method; Glass frit; And an organic vehicle including a solvent and an organic binder.
  • a silver powder when a silver powder is produced using a reducing agent according to a wet reduction method, an insoluble organic material generated after silver powder precipitation reaction is washed with an aqueous solution containing alkali metal borohydrides, It is possible to increase the cleaning efficiency at a low price, to reduce the silver powder aggregation to be produced, and to reduce the residual alkali metal content, thereby providing a silver powder having improved physical properties.
  • a conductive paste having improved sintering properties as a paste containing the silver powder having the improved physical properties and to form an electrode having excellent electrical conductivity.
  • FIG. 1 illustrates the process of measuring the chromaticity of the supernatant of a cleaned silver powder according to an embodiment of the present invention.
  • a method of manufacturing a silver powder according to an embodiment of the present invention includes: a silver salt producing step (S1); Silver salt reduction step (S2); Purification step such as filtration and washing (S3); And a surface treatment step (S4).
  • the method for producing a silver powder according to the present invention necessarily includes a silver salt reducing step (S2) and a purification step (S3), and the other steps may be omitted.
  • the silver salt preparation step S1 is a step of preparing a silver salt solution containing silver ions (Ag + ) by acid treatment of silver (Ag) in the form of ingots, comprising the steps of manufacturing, but can produce a powder to prepare a salt is passed through the step the solution directly, silver nitrate was purchased commercially (AgNO 3), the salt complex, or can proceed to the later steps, using the intermediate solution have.
  • the silver salt reducing step S2 is a step of reducing silver ions by adding a reducing agent and ammonia to a silver salt solution to precipitate silver particles, and silver ions, ammonia, and nitric acid (S21) for producing a second reaction solution containing a first reaction solution containing a reducing agent and a precipitation step (S22) for obtaining a silver powder by reacting the first reaction solution and the second reaction solution .
  • reaction solution preparation step (S21) ammonia and nitric acid are added to a silver salt solution containing silver ions, and the solution is stirred and dissolved to prepare a first reaction solution.
  • the silver ions are not limited as long as they are contained in the form of silver cations.
  • silver nitrate (AgNO 3 ), silver salt complex or silver intermediate may be used. It is preferable to use silver nitrate (AgNO 3 ).
  • AgNO 3 silver nitrate
  • the use of silver nitrate (AgNO 3 ) containing an ion will be described as an example.
  • Ammonia (NH 3 ) can be used in the form of an aqueous solution.
  • 25% ammonia aqueous solution 100 to 150 parts by weight of silver nitrate (AgNO 3 ) is added in 100 parts by weight.
  • the aqueous ammonia solution is added in an amount of less than 100 parts by weight, the reaction pH is low and silver ions are not completely reduced, or there is a problem in forming a uniform particle distribution.
  • the amount is more than 150 parts by weight, There is a problem that it becomes excessively high.
  • a 25% ammonia aqueous solution is added in an amount of 120 to 140 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ).
  • the ammonia includes a derivative thereof.
  • the nitric acid (HNO 3 ) can be used in the form of an aqueous solution.
  • 60% nitric acid aqueous solution 40 to 120 parts by weight are added to 100 parts by weight of silver nitrate (AgNO 3 ).
  • the amount of the nitric acid (HNO 3 ) is less than 40 parts by weight, it is difficult to control the size of the powder.
  • the amount of the nitric acid (HNO 3 ) is more than 120 parts by weight, have.
  • a 60% nitric acid aqueous solution is added in an amount of 80 to 100 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ).
  • the nitric acid includes a derivative thereof.
  • the first reaction solution containing silver ions, ammonia and nitric acid can be prepared in an aqueous solution state by adding a silver ion, an aqueous ammonia solution and an aqueous nitric acid solution to a solvent such as water and dissolving them by stirring to form a slurry form .
  • the reaction solution preparation step (S21) according to an embodiment of the present invention also produces a second reaction solution containing a reducing agent.
  • the reducing agent may be at least one member selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin, and among them, hydroquinone can be preferably selected.
  • the content of the reducing agent is preferably 10 to 20 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ) contained in the first reaction solution. If less than 10 parts by weight is used, silver ions may not be reduced at all, and when used in excess of 20 parts by weight, organic matter content increases.
  • the second reaction liquid is prepared by using 14 to 16 parts by weight of a reducing agent per 100 parts by weight of silver nitrate.
  • the second reaction solution containing a reducing agent can be prepared in an aqueous solution state by adding a reducing agent to a solvent such as water and dissolving it by stirring.
  • the precipitation step (S22) is a step of reacting the first reaction solution and the second reaction solution to obtain a silver powder, wherein the first reaction solution produced by the reaction solution production step (S21)
  • the second reaction solution may be slowly added dropwise or the reaction may be carried out in a batch.
  • the particles are added in a batch and further stirred for 5 minutes to 10 minutes to grow the particles in the mixed solution, so that the reduction reaction can be terminated in a short period of time to prevent agglomeration of the particles and increase dispersibility.
  • the silver powder dispersed in the aqueous solution or slurry is separated by filtration or the like after completing the silver particle precipitation reaction through the silver salt reducing step S2, And washing (S31), after washing, again dispersing the silver powder in the solvent and washing the silver powder with the washing solution in the dispersed solution.
  • the cleaning step S31 is a step of washing the precipitated silver particles using an aqueous solution containing alkali metal borohydrides as a cleaning solution, (S31) can clean the insoluble organic material generated after the silver powder precipitation reaction with high efficiency when the silver powder is produced using the reducing agent according to the wet reduction method.
  • the cleaning step S31 is a step of dispersing silver powder prepared in a solvent and adding an aqueous solution containing alkali metal borohydrides as a cleaning solution to the silver powder-dispersed solution, followed by mixing and stirring. Stirring the washing solution, filtering with a centrifugal separator, and washing the filter material with pure water.
  • the solvent in which the silver powder is dispersed may be water, ethanol, isopropyl alcohol, ethylene glycol hexyl ether, diethylene glycol, butyl ether propylene glycol, propyl ether and the like, preferably water.
  • the cleaning solution uses an aqueous solution containing alkali metal borohydrides represented by the following formula (1).
  • x and y are each independently 1 or 2
  • R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen (H), C 1 -C 6 alkyl, C 1 -C 6 alkoxy, boranes, amino, Include hydroxy, hydroxymethyl, carboxy or mercapto.)
  • H hydrogen
  • C 1 -C 6 alkyl C 1 -C 6 alkoxy
  • boranes amino, Include hydroxy, hydroxymethyl, carboxy or mercapto.
  • the reducing agent used in the reduction reaction remains on the surface of the silver powder produced as the poorly soluble organic material.
  • the reducing agent oxidized by the alkali metal borohydrides of the washing solution is reduced to a water-soluble state, It is possible to increase the cleaning efficiency of the washing machine.
  • Hydroquinone is oxidized to benzoquinone to be present as a by-product in a silver powder slurry during silver powder precipitation (reduction reaction), and benzoquinone Because it is a soluble organics, cleaning efficiency is very poor in pure water.
  • the cleaning solution is washed with an aqueous solution containing alkali metal hydride boron according to the present invention, the benzoquinone is reduced again to hydroquinone by the alkali metal borohydride, so that it can be washed in a small amount to provide high cleaning efficiency.
  • the wash solution is M a and comprises a Na or Li, and x is 1 or 2, y is 1, R 1, R 2, R 3 and R 4 are each independently hydrogen (H), C 1 C 6 alkyl, or boranes.
  • the cleaning solution is an aqueous solution containing a compound wherein M is Na, x and y are 1, and R 1 , R 2 , R 3 and R 4 are each hydrogen (H) .
  • washing step S31 silver powder prepared in a solvent is dispersed, and an aqueous solution containing alkali metal borohydrides is added as a washing solution to the silver powder-dispersed solution, followed by mixing and stirring. Is cleaned with pure water.
  • Silver powder is obtained by adding silver powder to a solvent having a mass of 3 to 5 times the mass of the silver powder and stirring the powder at 3000 to 4000 rpm for 10 to 30 minutes using a mixer. Preferably at 3000 to 3500 rpm for 15 to 25 minutes to obtain a solution in which the silver powder is dispersed.
  • the aqueous solution containing the alkali metal borohydrides represented by the above formula (1) is used in an amount such that the alkali metal borohydride is treated in an amount of 0.1 to 2.0 parts by weight based on 100 parts by weight of silver powder to be washed.
  • the alkali metal borohydride is treated in an amount of less than 0.1 part by weight, insoluble organic matters remain on the surface of the powder, and when the organic matter content is high, there is a problem that the electrical conductivity is lowered in the finally used application, The surface treatment agent is not adsorbed well on the surface of the powder in the following surface treatment process, resulting in coating failure and deteriorated silver powder properties.
  • the alkali metal borohydride is used in an amount of 0.2 to 1.0 part by weight based on 100 parts by weight of silver powder to be washed.
  • the washing step (S31) is completed after completely removing the washing water from which the silver particles have been washed. If the water content is less than approximately 10%, the wash water is considered to be completely removed.
  • the purification step S3 may further include a drying step (S32) for drying after washing.
  • the drying step S32 is a step of recovering the silver particles washed through the washing solution and drying at 70 to 90 DEG C for 10 to 15 hours.
  • the purification step S3 may further include a smoothing step (S33) of smashing the silver particles after drying.
  • the surface treatment step S4 is a step of hydrophobizing the hydrophilic surface of the silver powder, and may be selectively performed.
  • an alcohol solution containing a fatty acid or a fatty acid salt is used as the surface treatment agent.
  • the alcohol may be methanol, ethanol, n-propanol, benzyl alcohol, terpineol or the like, preferably ethanol.
  • the fatty acid may be selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linolic acid, And arachidonic acid.
  • the fatty acid may be at least one selected from the group consisting of calcium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, And a fatty acid salt which forms a salt with diethylamine, triethylamine, ethanolamine, diethanolamine or triethanolamine.
  • ammonium stearate in which stearic acid forms a salt with ammonia water is preferably used.
  • the powder is dried at 70 to 90 ° C for 10 to 15 hours, and then subjected to a pulverizing process using a jet mill to obtain a silver powder.
  • the powder is surface-treated, the powder should be well dispersed to achieve sufficient surface treatment. If the water content is low, the dispersion efficiency is lowered.
  • the present invention also provides a conductive paste comprising silver powder prepared according to an embodiment of the present invention.
  • the conductive paste includes a metal powder and an organic vehicle.
  • silver powder prepared according to one embodiment of the present invention is used as the metal powder.
  • the content of the metal powder is preferably 85 to 95 wt% based on the total weight of the conductive paste composition, considering the thickness of the electrode formed during printing and the line resistance of the electrode.
  • the organic vehicle preferably contains 5 to 15% by weight, based on the total weight of the conductive paste composition, of an organic binder mixed with 5 to 15% by weight of a solvent.
  • Examples of the organic binder include a cellulose ester compound such as cellulose acetate and cellulose acetate butyrate.
  • Examples of the cellulose ether compound include ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose , And hydroxyethyl methyl cellulose.
  • Examples of the acrylic compound include polyacrylamide, polymethacrylate, polymethylmethacrylate, and polyethylmethacrylate.
  • Examples of the vinyl compound include polyvinyl butyrate Polyvinyl acetate, polyvinyl alcohol, and the like. At least one or more organic binders may be selected and used.
  • Examples of the solvent used for diluting the composition include alcohols such as methanol, ethanol, n-propanol, benzyl alcohol and terpineol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, and acetylacetone; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Ethers such as tetrahydrofuran, dioxane, methyl cellosolve, diglyme and butyl carbitol; Esters such as methyl acetate, ethyl acetate, diethyl carbonate, TXIB (1-isopropyl-2,2-dimethyltrimethylene diisobutyrate), acetic acid carbitol and acetic acid butyl carbitol; Sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; Aliphatic
  • the conductive paste according to the present invention comprises a metal powder, a glass frit, and an organic vehicle.
  • silver powder prepared according to one embodiment of the present invention is used as the metal powder.
  • the content of the metal powder is preferably 85 to 95% by weight based on the total weight of the conductive paste composition, taking into account the electrode thickness formed during printing and the line resistance of the electrode.
  • the composition, particle diameter and shape of the glass frit are not particularly limited. It is possible to use not only flexible glass frit but also lead-free glass frit.
  • the content and content of the glass frit are 5 to 29 mol% of PbO, 20 to 34 mol% of TeO 2 , 3 to 20 mol% of Bi 2 O 3 , 20 mol% or less of SiO 2 , 10 mol% or less of B 2 O 3 , 10 to 20 mol% of an alkali metal (Li, Na, K, etc.) and an alkaline earth metal (Ca, Mg, etc.)
  • the average particle diameter of the glass frit is not limited, but it may have a particle diameter in the range of 0.5 to 10 mu m, and a mixture of various particles having different average particle diameters may be used.
  • at least one kind of glass frit has an average particle diameter (D50) of not less than 2 mu m and not more than 10 mu m.
  • the content of the glass frit is preferably 1 to 5% by weight based on the total weight of the conductive paste composition. If the amount is less than 1% by weight, incomplete firing may occur to increase electrical resistivity. If the amount exceeds 5% by weight, There is a possibility that the electrical resistivity becomes too high due to too much component.
  • the organic vehicle is not limited, but organic binders, solvents, and the like may be included. Solvents may sometimes be omitted.
  • the organic vehicle is not limited, but is preferably 1 to 10% by weight based on the total weight of the conductive paste composition.
  • the organic vehicle is required to have a property of keeping the metal powder and the glass frit uniformly mixed.
  • the conductive paste becomes homogeneous, And a property to suppress the flow and to improve the discharging property and the plate separability of the conductive paste from the screen plate.
  • the organic binder contained in the organic vehicle is not limited, but examples of the cellulose ester compound include cellulose acetate and cellulose acetate butyrate.
  • examples of the cellulose ether compound include ethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose
  • examples of the acrylic compound include polyacrylamide, polymethacrylate, polymethylmethacrylate, and polyethylmethacrylate, and the like.
  • examples of the acrylic compound include polyacrylamide, polymethacrylate, polymethylmethacrylate, and polyethylmethacrylate
  • examples of vinyl based ones include polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, and the like. At least one or more organic binders may be selected and used.
  • Examples of the solvent used for diluting the composition include alpha-terpineol, texanol, dioctyl phthalate, dibutyl phthalate, cyclohexane, hexane, toluene, benzyl alcohol, dioxane, diethylene glycol, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and the like.
  • the conductive paste composition according to the present invention may further contain additives commonly known in the art, for example, dispersants, plasticizers, viscosity regulators, surfactants, oxidizing agents, metal oxides, metal organic compounds and the like.
  • the present invention also provides a method of forming an electrode of a solar cell and a solar cell electrode produced by the method, wherein the conductive paste is applied on a substrate, followed by drying and firing.
  • the methods used for producing substrates, printing, drying, and firing can be generally those used for manufacturing solar cells, except that conductive pastes containing silver powder having the above- to be.
  • the substrate may be a silicon wafer.
  • Production Example 1 was a powder
  • the first aqueous solution was stirred, and the second aqueous solution was added all at once to the first aqueous solution, and the mixture was further stirred for 5 minutes from the completion of the addition to grow particles in the mixed solution. Thereafter, the stirring was stopped, and the particles in the mixed solution were settled. Then, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, and the filter material was washed with pure water to obtain about 40 g of silver powder.
  • DMW De-Mineralized Water
  • 500 g of the silver powder prepared in the above-mentioned Production Example were put in a ball mill and dispersed in powder at 3300 rpm for 20 minutes using a homo-mixer (K & S company, Lab) .
  • the alkali metal borohydride aqueous solution was added to the silver powder-dispersed solution and further stirred for 5 minutes. Then, the mixture was filtered using a centrifugal separator, and the filter material was washed with pure water so that the electric conductivity was 50 ⁇ s or less.
  • the type and amount of the alkali metal borohydride aqueous solution are shown in Table 1 below, and the amount of alkali metal borohydride was expressed in terms of weight% of the alkali metal borohydride with respect to the weight of silver powder to be cleaned.
  • the temperature of the cleaning solution means room temperature except for the examples described separately.
  • the amount of NaOH to be used is shown in Table 1 below, and the amount of NaOH to be used is represented by the weight percentage of NaOH to the weight of silver powder to be washed.
  • NaOH (10% by weight of silver powder) was added to 2 L of pure water at room temperature, and NaOH was dissolved by homomixer (K & S company, Lab) for 5 minutes with stirring at 3300 rpm. 500 g of the silver powder prepared in the above Preparation Example was added and stirred for 20 minutes. Stirring was stopped, the mixture was filtered using a centrifugal separator, and the filter material was washed with pure water so that the electric conductivity was 50 ⁇ s or less.
  • the type and amount of the alkali metal borohydride aqueous solution are shown in Table 1 below, and the amount of alkali metal borohydride was expressed in terms of weight% of the alkali metal borohydride with respect to the weight of silver powder to be cleaned.
  • the temperature of the cleaning solution means room temperature except for the examples described separately.
  • PSA size D 50 , ⁇ m
  • SEM size D SEM , ⁇ m
  • SEM size was measured by measuring the diameter of each of 100 washed silver powders according to Examples and Comparative Examples and then averaging them.
  • the silver powder prepared by the examples and the comparative examples was put into 30 ml of ethanol, and the silver powder was dispersed in ethanol for 1 minute by ultrasonication, and the powder was put into a particle size analyzer to measure the PSA size.
  • the particle diameter at which the width is 50% from the largest particle diameter is expressed as D 50 based on the entire width of the graph.
  • Hot-NaOH aqueous solution evaluation to measure the cleaning efficiency. That is, after the organic matter remaining on the surface of the silver powder was dissolved using a hot-NaOH aqueous solution, the chromaticity of the supernatant was measured to quantify the concentration of the remaining organic matter. The higher the chromaticity of the supernatant, the higher the concentration of the remaining organic matter, which means that the washing is not good.
  • the evaluation method of the hot-NaOH aqueous solution is as follows.
  • the cleaned silver powder was placed in DMW and dispersed. Then, an ammonium stearate ethanol solution was added thereto, and the mixture was stirred at 4000 rpm for 20 minutes. After that, hot air drying was performed at 80 ° C for 12 hours, and the powder was surface-treated by jet milling to obtain silver powder.
  • the amount of organic matter remaining on the powder surface is reduced, so that the surface treating agent is adsorbed well on the powder surface in the surface treatment process after washing.
  • the water repellency (water repellency) of the silver powder was measured to determine the uniformity of the surface treatment, and it is indirectly known that the cleaning effect is excellent.
  • the agglomeration degree of the silver powder washed according to the example was lower than 1.80, the chromaticity of the supernatant was lower than 200PCU, and the alkali content was lower than 80 ppm, which was lower than that of the comparative example. It can be seen that the physical properties of the silver powder are the most excellent.
  • Comparative Example 2 shows an increase in washing efficiency due to a rise in the temperature of the washing liquid, thereby improving water repellency but increasing coagulation.
  • the conductive paste obtained in Preparation Example 2 was pattern printed on an alumina plate with a screen printing technique of 40 ⁇ m mesh, dried at about 300 ° C. for 25 seconds using a drying furnace, and then fired at 800 ° C. for 25 seconds using a firing furnace, .
  • the series resistance (Rs) of the electrode sample was measured and is shown in Table 3 below.
  • the series resistance of the electrode formed of the conductive paste containing the silver powder washed according to the example was 0.00140? Or less, which is lower than that of the comparative example.
  • the silver powder washed according to Examples 1 to 3 The best electrical conductivity is obtained.
  • the electrical properties are degraded as expected through the alkali content.

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Abstract

L'invention concerne la production de poudre d'argent à l'aide d'un agent réducteur selon un procédé de réduction par voie humide, la présente invention n'ayant pas de risque d'incendie par lavage de matières organiques insolubles générées après une réaction de précipitation de poudre d'argent avec une solution aqueuse comprenant des borohydrures de métal alcalin, étant capable d'augmenter l'efficacité de nettoyage à de faibles coûts, réduisant l'agrégation de la poudre d'argent à produire, et réduisant la teneur en métaux alcalins résiduels. Par conséquent, il est possible de fournir une poudre d'argent ayant des propriétés physiques améliorées.
PCT/KR2018/012185 2017-10-31 2018-10-16 Procédé de production de poudre d'argent WO2019088510A1 (fr)

Applications Claiming Priority (2)

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KR10-2017-0143178 2017-10-31
KR1020170143178A KR102081183B1 (ko) 2017-10-31 2017-10-31 은 분말의 제조방법

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JP2011181538A (ja) * 2010-02-26 2011-09-15 Kyoto Elex Kk 太陽電池素子の電極形成用導電性ペースト
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