CN105880626A - Preparation method of sphere-like shaped superfine silver powder for front silver paste of solar cell - Google Patents

Preparation method of sphere-like shaped superfine silver powder for front silver paste of solar cell Download PDF

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CN105880626A
CN105880626A CN201610315689.6A CN201610315689A CN105880626A CN 105880626 A CN105880626 A CN 105880626A CN 201610315689 A CN201610315689 A CN 201610315689A CN 105880626 A CN105880626 A CN 105880626A
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solution
silver powder
solar cell
powder
front side
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李兴亮
柴良
唐元勋
肖强
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ZHEJIANG GUANGDA ELECTRONIC TECHNOLOGY Co Ltd
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ZHEJIANG GUANGDA ELECTRONIC TECHNOLOGY Co Ltd
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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
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention belongs to the technical field of silver powder preparation, and relates to a preparation method of sphere-like shaped superfine silver powder for front silver paste of a solar cell. The method comprises the following steps: 1) preparing a silver nitrate aqueous solution at a concentration of 0.14 to 0.4 mol/L, then adding an alkaline agent to obtain paste of which the pH is 11 to 13.5, and marking the solution as a solution A; 2) preparing a sodium hydroxide aqueous solution at the concentration of 0.005 to 0.05 mol/L, then adding a reducing agent to obtain a reducing solution at the concentration of 3 to 10 mol/L, and marking the solution as a solution B; 3) preparing a dispersant solution at the concentration of 0.01 to 0.4 mol/L, and marking the solution as a solution C; 4) weighting the solution A, the solution B and the solution C based on the volume ratio of 400: 50: 1, adding the solution B at the speed of 0.5 to 1.5 L/min to the solution A while stirring, reacting for 0.1 to 0.5 hour, then adding the solution C, and uniformly stirring; collecting silver powder from the product through a solid-liquid separating device, and then washing and drying; sieving the obtained powder, and smoothing the powder surface through a high-speed mixing treating device, so as to obtain the sphere-like shaped superfine silver powder. The preparation method is simple in process and operation; the obtained silver powder has the characteristics of being high in dispersing performance, high in tap density, and uniform in grain size and shape.

Description

A kind of preparation method of solar cell front side silver paste class spherical super fine silver powder
Technical field
The invention belongs to technical field prepared by silver powder, more particularly it relates to an solar cell front side silver The slurry preparation method of class spherical super fine silver powder.
Background technology
Due to the finiteness of non-renewable resources and its in use global climate and environment are caused and have a strong impact on And destruction, people increasingly pay close attention to the utilization of the renewable resources such as wind energy, water energy, solar cell, especially solar cell Paid close attention to by people.Along with research and development and the use of solar cell, promote the conductive silver paste that solar cell cell piece uses Also constantly updating, updating, the requirement of silver powder is also being improved constantly by it, especially ball shape silver powder.Spherical silver Powder, as the main body of silver paste, warp and glass dust and organic carrier furnishing slurry, is screen-printed on silicon chip, is formed and lead after sintering Electric network structure, is widely used in front electrode of solar battery and grid line.Silver powder rises in solar cell front side silver paste and leads The function of electricity, the quality good or not of silver powder directly affects battery performance, especially the dispersiveness of ball shape silver powder, tap density, particle diameter Size and distribution directly influence the compactness of electrode thick film, uniformity, screen printability, thus have influence on its electric conductivity, Therefore obtain the spherical super fine silver powder of high dispersive micron or submicron-scale be improve solar cell properties key factor it One.Additionally, the mass production of silver powder is the most difficult, complex operation, difficult quality guarantee.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of solar cell front side silver paste class spherical super fine silver powder Preparation method, this preparation method technological operation is simple, and the silver powder obtained has good dispersion, tap density is high, granularity form is equal The characteristic that even purity is high.
In order to realize foregoing invention purpose, this invention takes techniques below scheme:
The preparation method of a kind of solar cell front side silver paste class spherical super fine silver powder, specifically includes following steps:
1) compound concentration is the silver nitrate aqueous solution of 0.05-0.4mol/L, adds alkaline reagent, obtains the slurry that pH is 11-13.5 Liquid, is labeled as solution A；
2) compound concentration is the sodium hydrate aqueous solution of 0.005-0.05mol/L, adds reducing agent, and obtaining concentration is 3-10mol/ The reducing solution of L, is labeled as solution B；；
3) compound concentration is the dispersant solution of 0.01-0.4mol/L, is labeled as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with 0.5-1.5 L/ The speed of min adds in solution A, reacts 0.1-0.5h, adds solution C, stirs, set through separation of solid and liquid by the product obtained Standby collection silver powder also washs, dries, and is sieved by the powder obtained, and makes powder surface smooth by mixed at high speed processor, i.e. Obtain solar cell front side silver paste class spherical super fine silver powder.
In one embodiment, described reducing agent is ascorbic acid, alkanolamine, formaldehyde, quinhydrones, hydrazine hydrate, grape One or more in sugar.
In one embodiment, described dispersant is aliphatic acid, soap, surfactant, organic metal, protection One or more in colloid, chelating agent.
In one embodiment, the temperature of solution A described in step 1) is not less than 35 DEG C.
In one embodiment, washing described in step 4) is that the electrical conductivity repeatedly washed by deionized water to silver powder is 10-100μs /cm。
In one embodiment, temperature is dried described in step 4) less than 100 DEG C.
Another object of the present invention is to provide the solar cell front side silver paste class prepared by the method spherical super Thin silver powder.In one embodiment, the tap density of this silver powder described is not less than 5g/cm3, BET specific surface is not less than 0.4m2/ g。
Another object of the present invention is to provide described solar cell front side silver paste class spherical super fine silver powder conducting electricity Application in silver paste.
Compared with prior art, the invention have the benefit that
1) the solar cell front side silver paste class spherical super fine silver powder that prepared by the inventive method has good dispersion, tap density The characteristic high, the most even purity of granularity form is high.
2) the inventive method operation is the easiest, during mass production, it is possible to well guarantee production batch it Between stability.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Accompanying drawing explanation
Fig. 1: embodiment 1 class spherical super fine silver powder retouch Electronic Speculum figure
Fig. 2: embodiment 2 class spherical super fine silver powder retouch Electronic Speculum figure
Fig. 3: embodiment 3 class spherical super fine silver powder retouch Electronic Speculum figure
Fig. 4: embodiment 1 class spherical super fine silver powder retouch Electronic Speculum figure
Fig. 5: comparative example 1 class spherical super fine silver powder retouch Electronic Speculum figure
Fig. 6: comparative example 2 class spherical super fine silver powder retouch Electronic Speculum figure.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have skill common with art of the present invention The identical implication that art personnel are generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ", " have ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, the combination of listed elements is comprised Thing, step, method, goods or device are not necessarily solely those key elements, but can include other not expressly listed key element or The key element that this kind of composition, step, method, goods or device are intrinsic.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this Phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe, but relative often Except rule impurity.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme, It is only limited to the key element described in this clause；Other key element is not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this scope separately discloses.Such as, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc..When number range is described in this article, unless otherwise indicated, otherwise this scope be intended to include its end value and All integers within the range and mark.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number The key element of form or component also include plural form, unless described quantity substantially refers to singulative.
In order to solve the problems referred to above, the invention provides a kind of solar cell front side silver paste class spherical super fine silver powder Preparation method, specifically includes following steps:
1) compound concentration is the silver nitrate aqueous solution of 0.05-0.4mol/L, adds alkaline reagent, obtains the slurry that pH is 11-13.5 Liquid, is labeled as solution A；
2) compound concentration is the sodium hydrate aqueous solution of 0.005-0.05mol/L, adds reducing agent, and obtaining concentration is 3-10mol/ The reducing solution of L, is labeled as solution B；
3) compound concentration is the dispersant solution of 0.01-0.4mol/L, is labeled as solution C；
4) solution A, solution B and solution C are that 400:50:1 takes according to volume ratio, under stirring, by solution B with 0.5-1.5 L/min Speed add in solution A, react 0.1-0.5h, add solution C, stir, by the product that obtains through solid-liquid separating equipment Collect silver powder and wash, dry, the powder obtained being sieved, and makes powder surface smooth by mixed at high speed processor, to obtain final product Solar cell front side silver paste class spherical super fine silver powder.
Heretofore described " alkaline reagent " refers to ammoniacal liquor, ammonia salt, NaOH or sodium carbonate, prepares silver with silver nitrate Intermediate；Preferably, described alkaline reagent is ammoniacal liquor.
Heretofore described " dispersant solution " is that dispersant dissolves with solvent, stirs prepared, described solvent For absolute ethyl alcohol or deionized water.
In the present invention, B solution adds the speed preferably 0.5-1.5 L/min of solution A in order to prevent silver powder from sending out Raw gathering, it is preferable that it is 1L/min that B solution adds the speed of solution A.
Heretofore described " reducing agent " can be selected from: ascorbic acid, alkanolamine, sulphite, formic acid, formaldehyde, first Acid ammonium, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, quinhydrones, hydrazine hydrate, glucose, aqueous hydrogen peroxide solution, hypophosphorous acid Sodium, sodium borohydride, hydrazine, hydrazine compound, dried sodium sulfate and carving hundred powder etc..In order to obtain, there is suitable crystalline substance degree and particle diameter Argent grain, in one is preferably carried out mode, described reducing agent is formaldehyde.
In one is preferably carried out mode, described dispersant is aliphatic acid, soap, surfactant, You Jijin One or more in genus, protecting colloid, chelating agent.Described aliphatic acid includes propionic acid, octanoic acid, laurate, myristic acid, palm Acid, stearic acid, behenic acid, acrylic acid, oleic acid, linoleic acid and arachidonic acid；Described aliphatic acid includes by aliphatic acid and metal The salt formed, these metals are, such as lithium, sodium, potassium, barium, magnesium, calcium, aluminium, iron, cobalt, manganese, lead, zinc, tin, strontium, zirconium, silver and copper； Described surfactant includes: anionic surfactant, such as alkylbenzenesulfonate and ether phosphates；Sun Ionic surfactant, such as aliphatic quaternary ammonium salt；Amphoteric surfactant, such as imidazolinium betaine；And non-ionic surface Activating agent, such as polyoxyethylene alkyl ether and polyoxyethylene fatty acid ester；Described organic metal include acetylacetone,2,4-pentanedione three butoxy zirconium, Magnesium citrate, diethyl zinc, Dibutyltin oxide, zinc methide, four n-butoxy zirconiums, triethylindium, triethyl-gallium, trimethyl Indium, trimethyl gallium, Mono-n-butyltin, tetraisocyanate silane, tetramethylsilane, tetramethoxy-silicane, polymethoxy silica Alkane, monomethyl triisocyanate silane, silane coupler, titanate coupling agent and aluminum coupling agent；Described chelating agent include imidazoles, Azoles, thiazole, selenazoles, pyrazoles, isoxazole, isothiazole, 1H-1,2,3-triazoles, 2H-1,2,3-triazoles, 1H-1,2,4-triazoles, 4H-1,2,4-triazoles, 1,2,3-diazole, 1,2,4-diazole, 1,2,5-diazole, 1,3,4-diazole, 1,2,3-thiophenes two Azoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1H-1,2,3,4-tetrazoliums, 1,2,3,4-triazoles, 1,2, 3,4-thiatriazoles, 2H-1,2,3,4-tetrazoliums, 1,2,3,5-triazoles, 1,2,3,5-thiatriazoles, indazole, benzimidazole, benzo three Azoles and salt thereof and oxalic acid, butanedioic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, double ten Two alkanoic acids, maleic acid, fumaric acid, phthalandione, isophathalic acid, terephthalic acids, glycolic, lactic acid, hydroxybutyric acid, glyceric acid, tartaric acid, Malic acid, tartronic acid, hydracrylic acid, mandelic acid, citric acid and ascorbic acid；Described protecting colloid includes: gelatin, white egg In vain, gum arabic, agar, alginate, carragheen, pectin, xanthans, your tower Bick general acid and lysalbic acid.In order to realize Beneficial effects of the present invention, preferably；Described dispersant is selected from gum arabic or stearic acid and the like.
In one is preferably carried out mode, the temperature of solution A described in step 1) is not less than 36 DEG C.
In one is preferably carried out mode, described in step 4), washing is repeatedly to wash the electricity to silver powder by deionized water Conductance is 10-100 μ s/cm.
In one is preferably carried out mode, dry temperature described in step 4) less than 100 DEG C.
Another object of the present invention is to provide the solar cell front side silver paste class prepared by the method spherical super Thin silver powder.In one is preferably carried out mode, the tap density of this silver powder described is not less than 5g/cm3, BET specific surface is the lowest In 0.4m2/g。
Another object of the present invention is to provide described solar cell front side silver paste class spherical super fine silver powder conducting electricity Application in silver paste.
Embodiment:
Embodiment 1, the preparation method of a kind of solar cell front side silver paste class spherical super fine silver powder, specifically include following step Rapid:
1) compound concentration is the silver nitrate aqueous solution of 0.05-0.4mol/L, adds alkaline reagent, obtains the slurry that pH is 11-13.5 Liquid, is labeled as solution A；
2) compound concentration is the sodium hydrate aqueous solution of 0.005-0.05mol/L, adds reducing agent, and obtaining concentration is 3-10mol/ The reducing solution of L, is labeled as solution B；；
3) compound concentration is the dispersant solution of 0.01-0.4mol/L, is labeled as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with 0.5-1.5 L/ The speed of min adds in solution A, reacts 0.1-0.5h, adds solution C, stirs, set through separation of solid and liquid by the product obtained Standby collection silver powder also washs, dries, and is sieved by the powder obtained, and makes powder surface smooth by mixed at high speed processor, i.e. Obtain solar cell front side silver paste class spherical super fine silver powder.
Embodiment 2, identical with embodiment 1, different places is, described reducing agent be ascorbic acid, alkanolamine, One or more in formaldehyde, quinhydrones, hydrazine hydrate, glucose.
Embodiment 3, identical with embodiment 1, different places is, described dispersant is aliphatic acid, soap, table One or more in face activating agent, organic metal, protecting colloid, chelating agent.
Embodiment 4, identical with embodiment 1, different places is, the temperature of solution A described in step 1) is not less than 35℃。
Embodiment 5, identical with embodiment 1, different places is, described in step 4), washing is many by deionized water Secondary washing is 10-100 μ s/cm to the electrical conductivity of silver powder.
Embodiment 6, identical with embodiment 1, different places is, dries temperature less than 100 DEG C described in step 4).
Embodiment 7, identical with embodiment 1, different places is, the sieve number sieved described in step 4) is 50-150 mesh.
Embodiment 8, the solar cell front side silver paste class spherical super fine silver powder that described method prepares.
Embodiment 9, identical with embodiment 1, different places is, the tap density of this silver powder described is not less than 5g/ cm3, BET specific surface is not less than 0.4m2/g。
Embodiment 10, described solar cell front side silver paste class spherical super fine silver powder is applied to conductive silver paste In.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example are served only for right The present invention is described further, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field according to Some nonessential improvement and adjustment that the content of foregoing invention is made, still fall within protection scope of the present invention.
It addition, illustrate without other, raw materials used is all commercially available.
Embodiment 1
1) being dissolved in deionized water by silver nitrate, compound concentration is the silver nitrate aqueous solution of 0.14mol/L, adds ammoniacal liquor, pH It is 11, is designated as solution A, constant temperature 36 DEG C insulation；
2) being dissolved in deionized water by NaOH, compound concentration is the sodium hydrate aqueous solution of 0.005mol/L, adds first Aldehyde, compound concentration is the reducing solution of 5mol/L, stirs, and is designated as solution B, constant temperature 30 DEG C insulation；
3) being dissolved in absolute ethyl alcohol by stearic acid, compound concentration is the dispersant solution of 0.02mol/L, is designated as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with the speed of 0.8L/min Degree joins in solution A, after stirring 10min, adds C liquid, stirs, after reaction terminates, is divided through solid-liquid by the product obtained From equipment collect silver powder and repeatedly wash by deionized water to electrical conductivity be 10-100 μ s/cm, by gained super fine silver powder at 60 DEG C Under conditions of dry 3h, then sieve with the screen cloth of 100 mesh and make silver powder particles mutually collide by mixed at high speed processor, making The surface of gained silver powder polishes, and obtains solar cell front side silver paste class spherical super fine silver powder.
Embodiment 2
1) being dissolved in deionized water by silver nitrate, compound concentration is the silver nitrate aqueous solution of 0.14mol/L, adds ammoniacal liquor, pH It is 13, is designated as solution A, constant temperature 38 DEG C insulation；
2) being dissolved in deionized water by NaOH, compound concentration is the sodium hydrate aqueous solution of 0.03mol/L, adds first Aldehyde, compound concentration is the reducing solution of 5mol/L, stirs, and is designated as solution B, constant temperature 30 DEG C insulation；
3) being dissolved in absolute ethyl alcohol by stearic acid, compound concentration is the dispersant solution of 0.02mol/L, is designated as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with the speed of 1L/min Join in solution A, after stirring 10min, add C liquid, stir, after reaction terminates, by the product that obtains through separation of solid and liquid Equipment collect silver powder and repeatedly wash by deionized water to electrical conductivity be 10-100 μ s/cm, by gained super fine silver powder at 60 DEG C Under the conditions of dry 3h, then sieve with the screen cloth of 100 mesh and make silver powder particles mutually collide by mixed at high speed processor, making institute The surface obtaining silver powder polishes, and obtains solar cell front side silver paste class spherical super fine silver powder.
Embodiment 3
1) being dissolved in deionized water by silver nitrate, compound concentration is the silver nitrate aqueous solution of 0.14mol/L, adds ammoniacal liquor, pH It is 11, is designated as solution A, constant temperature 38 DEG C insulation；
2) being dissolved in deionized water by NaOH, compound concentration is the sodium hydrate aqueous solution of 0.005mol/L, adds first Aldehyde, compound concentration is the reducing solution of 5mol/L, stirs, and is designated as solution B, constant temperature 30 DEG C insulation；
3) being dissolved in by gum arabic in 60 degrees Celsius of deionized waters, compound concentration is the dispersant solution of 5g/L, is designated as molten Liquid C；
4) solution A, solution B and solution C are that 400:50:10 weighs according to volume ratio, under stirring, by solution B with the speed of 1L/min Degree joins in solution A, after stirring 10min, adds C liquid, stirs, after reaction terminates, is divided through solid-liquid by the product obtained From equipment collect silver powder and repeatedly wash by deionized water to electrical conductivity be 10-100 μ s/cm, by gained super fine silver powder at 60 DEG C Under conditions of dry 3h, then sieve with the screen cloth of 100 mesh and make silver powder particles mutually collide by mixed at high speed processor, making The surface of gained silver powder polishes, and obtains solar cell front side silver paste class spherical super fine silver powder.
Embodiment 4
1) being dissolved in deionized water by silver nitrate, compound concentration is the silver nitrate aqueous solution of 0.14mol/L, adds ammoniacal liquor, pH It is 11, is designated as solution A, constant temperature 36 DEG C insulation；
2) being dissolved in deionized water by NaOH, compound concentration is the sodium hydrate aqueous solution of 0.005mol/L, adds water Closing hydrazine, compound concentration is the reducing solution of 5mol/L, stirs, and is designated as solution B, constant temperature 30 DEG C insulation；
3) being dissolved in absolute ethyl alcohol by stearic acid, compound concentration is the dispersant solution of 0.02mol/L, is designated as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with the speed of 1L/min Join in solution A, after stirring 10min, add C liquid, stir, after reaction terminates, by the product that obtains through separation of solid and liquid Equipment collect silver powder and repeatedly wash by deionized water to electrical conductivity be 10-100 μ s/cm, by gained super fine silver powder at 60 DEG C Under the conditions of dry 3h, then sieve with the screen cloth of 100 mesh and make silver powder particles mutually collide by mixed at high speed processor, making institute The surface obtaining silver powder polishes, and obtains solar cell front side silver paste class spherical super fine silver powder.
Comparative example 1
1) being dissolved in deionized water by silver nitrate, compound concentration is the silver nitrate aqueous solution of 0.14mol/L, adds ammoniacal liquor, pH It is 11, is designated as solution A, constant temperature 36 DEG C insulation；
2) being dissolved in deionized water by NaOH, compound concentration is the sodium hydrate aqueous solution of 0.005mol/L, adds first Aldehyde, compound concentration is the reducing solution of 5mol/L, stirs, and is designated as solution B, constant temperature 30 DEG C insulation；
3) phenylpropyl alcohol triazole sodium being dissolved in absolute ethyl alcohol, compound concentration is the dispersant solution of 0.02mol/L, is designated as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution A with the speed of 1L/min Join in solution B, after stirring 10min, add C liquid, stir, after reaction terminates, by the product that obtains through separation of solid and liquid Equipment collect silver powder and repeatedly wash by deionized water to electrical conductivity be 10-100 μ s/cm, by gained super fine silver powder at 60 DEG C Under the conditions of dry 3h, then sieve with the screen cloth of 100 mesh and make silver powder particles mutually collide by mixed at high speed processor, making institute The surface obtaining silver powder polishes, and obtains solar cell front side silver paste class spherical super fine silver powder.
Comparative example 2
1) being dissolved in deionized water by silver nitrate, compound concentration is the silver nitrate aqueous solution of 0.14mol/L, adds ammoniacal liquor, pH It is 11, is designated as solution A, constant temperature 32 DEG C insulation；
2) being dissolved in deionized water by NaOH, compound concentration is the sodium hydrate aqueous solution of 0.005mol/L, adds water Closing hydrazine, compound concentration is the reducing solution of 5mol/L, stirs, and is designated as solution B, constant temperature 30 DEG C insulation；
3) phenylpropyl alcohol triazole sodium being dissolved in absolute ethyl alcohol, compound concentration is the dispersant solution of 0.02mol/L, is designated as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with the speed of 1L/min Join in solution A, after stirring 10min, add C liquid, stir, after reaction terminates, by the product that obtains through separation of solid and liquid Equipment collect silver powder and repeatedly wash by deionized water to electrical conductivity be 10-100 μ s/cm, by gained super fine silver powder at 60 DEG C Under the conditions of dry 3h, then sieve with the screen cloth of 100 mesh and make silver powder particles mutually collide by mixed at high speed processor, making institute The surface obtaining silver powder polishes, and obtains solar cell front side silver paste class spherical super fine silver powder.
Table 1 class spherical super fine silver powder the performance test results
Table 2 class spherical super fine silver powder is made into viscosity test results after slurry
Table 3 silicon solar cell (125 × 125 specification) detection performance
Aforesaid example is merely illustrative, for explaining some features of inventive feature.Appended claim is intended to Require the widest scope that it is contemplated that, and embodiments as presented herein is only the group according to all possible embodiment The explanation of the embodiment of the selection closed.Therefore, the purpose of applicant is that appended claim is not by the spy of the explanation present invention The selectional restriction of the example levied.And the progress in science and technology will be formed due to language performance inaccurate reason and not by mesh Possible equivalent or the son of front consideration are replaced, and these changes also should be interpreted in the conceived case by appended right Require to cover.

Claims (9)

1. the solar cell front side silver paste preparation method of class spherical super fine silver powder, it is characterised in that specifically include with Lower step:
1) compound concentration is the silver nitrate aqueous solution of 0.14-0.4mol/L, adds alkaline reagent, obtains the slurry that pH is 11-13.5 Liquid, is labeled as solution A；
2) compound concentration is the sodium hydrate aqueous solution of 0.005-0.05mol/L, adds reducing agent, and obtaining concentration is 3-10mol/ The reducing solution of L, is labeled as solution B；
3) compound concentration is the dispersant solution of 0.01-0.4mol/L, is labeled as solution C；
4) solution A, solution B and solution C are that 400:50:1 weighs according to volume ratio, under stirring, by solution B with 0.5-1.5 L/ The speed of min adds in solution A, reacts 0.1-0.5h, adds solution C, stirs, set through separation of solid and liquid by the product obtained Standby collection silver powder also washs, dries, and is sieved by the powder obtained, and makes powder surface smooth by mixed at high speed processor, i.e. Obtain solar cell front side silver paste class spherical super fine silver powder.
The preparation method of solar cell front side silver paste class spherical super fine silver powder the most according to claim 1, its feature Being, described reducing agent is one or more in ascorbic acid, alkanolamine, formaldehyde, quinhydrones, hydrazine hydrate, glucose.
The preparation method of solar cell front side silver paste class spherical super fine silver powder the most according to claim 1, its feature Being, described dispersant is the one in aliphatic acid, soap, surfactant, organic metal, protecting colloid, chelating agent Or it is multiple.
The preparation method of solar cell front side silver paste class spherical super fine silver powder the most according to claim 1, its feature Being, the temperature of solution A described in step 1) is not less than 35 DEG C.
The preparation method of solar cell front side silver paste class spherical super fine silver powder the most according to claim 1, its feature Be, washing described in step 4) be the electrical conductivity repeatedly washed by deionized water to silver powder be 10-100 μ s/cm.
The preparation method of solar cell front side silver paste class spherical super fine silver powder the most according to claim 1, its feature It is, dries temperature described in step 4) less than 100 DEG C.
7. the solar cell front side silver paste class spherical super fine prepared according to method described in any one of claim 1 to 6 Silver powder.
8. according to the class spherical super fine silver powder of the solar cell front side silver paste described in claim 7, it is characterised in that this silver described The tap density of powder is not less than 5g/cm3, BET specific surface is not less than 0.4m2/g。
9. the solar cell front side silver paste class spherical super fine silver powder described in claim 7 or 8 is applied in conductive silver paste.
CN201610315689.6A 2016-05-13 2016-05-13 Preparation method of sphere-like shaped superfine silver powder for front silver paste of solar cell Pending CN105880626A (en)

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CN108788175A (en) * 2017-04-28 2018-11-13 大州电子材料 Spherical silver particles and its manufacturing method, the conductive paste and device comprising it
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CN109332723A (en) * 2018-12-10 2019-02-15 西安宏星电子浆料科技有限责任公司 A kind of preparation method of low-temperature conductive adhesive silver powder
CN110227827A (en) * 2019-04-16 2019-09-13 北京氦舶科技有限责任公司 A kind of electronic ceramics electrode printing slurry silver powder and preparation method thereof
CN110355381A (en) * 2019-08-21 2019-10-22 无锡帝科电子材料股份有限公司 A kind of nano-silver powder and the preparation method and application thereof
CN110756823A (en) * 2019-12-09 2020-02-07 成都市天甫金属粉体有限责任公司 Preparation method of spherical nano silver powder
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CN112122620A (en) * 2020-09-08 2020-12-25 西安汇创贵金属新材料研究院有限公司 Preparation method of silver powder
CN112122620B (en) * 2020-09-08 2024-03-01 西安汇创贵金属新材料研究院有限公司 Silver powder preparation method
CN113290252A (en) * 2021-05-28 2021-08-24 金川集团股份有限公司 Preparation method of superfine silver powder with low tap mass and high specific surface
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Application publication date: 20160824