CN115178747A - Efficient preparation method of high-crystallinity silver powder - Google Patents
Efficient preparation method of high-crystallinity silver powder Download PDFInfo
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- CN115178747A CN115178747A CN202210940327.1A CN202210940327A CN115178747A CN 115178747 A CN115178747 A CN 115178747A CN 202210940327 A CN202210940327 A CN 202210940327A CN 115178747 A CN115178747 A CN 115178747A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
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- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
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- 238000001035 drying Methods 0.000 claims abstract description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
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- 239000001509 sodium citrate Substances 0.000 claims description 9
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000002159 nanocrystal Substances 0.000 claims description 8
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- 239000003607 modifier Substances 0.000 claims description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
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- 230000001276 controlling effect Effects 0.000 description 2
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Images
Classifications
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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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to the field of production of photovoltaic silver powder polycrystalline materials, in particular to a high-efficiency preparation method of high-crystallinity silver powder, which comprises the following steps: dissolving silver nitrate and a dispersant a in ethylene glycol, transferring the mixture into a hydrothermal kettle, and heating for reaction to obtain a nano seed crystal; step b: b, stirring and dissolving a reducing agent and a dispersing agent b in deionized water, adding the nano seed crystal prepared in the step a, and adjusting the pH to obtain an intermediate solution; adding a silver nitrate aqueous solution into the intermediate solution by pouring and stirring, and reacting to obtain silver powder slurry; step c: c, filtering the silver paste obtained in the step b, washing the silver paste with deionized water and ethanol until the conductivity is less than or equal to 20 mu S/cm, and then dispersing at a high speed, filtering for the second time and drying to obtain high-crystallinity silver powder; the preparation method can prepare the silver powder with high crystallinity by regulating the growth processes of different crystal faces of the silver powder by regulating the dosage of the three dispersants, has short production period and low production cost, and is very suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of production of photovoltaic silver powder polycrystalline materials, in particular to a high-efficiency preparation method of high-crystallinity silver powder.
Background
Heterojunction solar cells have been widely studied because of their advantages of thin silicon wafers, high photostability, low temperature coefficient, high light conversion efficiency, and the like. At present, the cost of silver paste consumed by a single-chip heterojunction solar cell is obviously higher than that of PERC and TOPCON solar cells, so in order to reduce the metallization cost, manufacturers try to reduce the using amount of the silver paste by adopting superfine grid lines, reducing the number of the grid lines and the like, and the silver paste is required to have more excellent performance. The high-crystallinity silver powder has excellent heat shrinkage resistance in the curing process, can improve the shape precision, and is suitable for fine grid printing; in addition, the silver powder with high crystallinity has more precise contact among particles due to the flat surface, so that the conductivity of the silver electrode can be effectively improved, and the photoelectric conversion efficiency of the solar cell is further improved. Therefore, silver powder with high tap density, high crystallinity and good dispersibility can be generally used as main silver powder to be mixed with other silver powder to prepare silver paste suitable for heterojunction solar cells.
Patent CN114188066A introduces a method that firstly inorganic powder, dispersant and anti-flocculant agent after surface smoothing treatment are mixed and ultrasonically stirred for 2 hours to be used as nano crystal seeds for standby; and then uniformly mixing and stirring the nano crystal seeds, the reducing agent and the particle size control agent, and slowly dripping 250ml of silver nitrate solution into the reducing solution within 4 hours to perform redox reaction to generate the silver-coated inorganic powder with high crystallinity. The synthesis method for preparing the high-crystallization silver powder by slowly dripping the oxidizing solution to control the reaction rate consumes long time, so that the production efficiency is low, and the method is not suitable for large-scale industrial production. Therefore, how to overcome the above technical problems and disadvantages is a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects described in the background technology, so that the high-efficiency preparation method of the silver powder with high crystallinity is realized, the silver powder with high tap density, good dispersibility and high crystallinity can be prepared by regulating the growth processes of different crystal faces of the silver powder by regulating the using amounts of the three dispersing agents, the production period is short, the production cost is low, and the method is very suitable for large-scale industrial production.
Researches show that the polyvinylpyrrolidone tends to be adsorbed on a (100) crystal face in the silver powder growth process, the hexadecyl trimethyl ammonium bromide tends to be adsorbed on a (110) crystal face of the silver powder, and the acting force between the sodium citrate and the (111) crystal face of the silver powder is stronger, so that the invention aims to regulate and control the growth processes of different crystal faces of the silver powder by regulating the dosage of the three dispersing agents under the condition of adding the nano seed crystal, and further prepare the silver powder with high crystallinity.
In order to achieve the purpose, the technical scheme of the invention is as follows: a high-efficiency preparation method of high-crystallinity silver powder comprises
A, step a: preparing nano seed crystal: dissolving silver nitrate and a dispersing agent a in ethylene glycol, transferring the silver nitrate and the dispersing agent a to a hydrothermal kettle after the silver nitrate and the dispersing agent a are completely dissolved, placing the hydrothermal kettle in an oven for heating reaction for a certain time, and obtaining nano crystal seeds after the reaction is finished;
step b: preparing silver powder slurry: b, stirring and dissolving a reducing agent and a dispersing agent b in deionized water, adding 0.1-200g of the nano seed crystal prepared in the step a after the reducing agent and the dispersing agent b are completely dissolved, uniformly stirring, and adding a pH regulator to regulate the pH to 0.1-5 to obtain an intermediate solution; under the condition of stirring, adding a silver nitrate aqueous solution into the intermediate solution in a pouring mode, and reacting for a certain time to obtain silver powder slurry;
step c: preparing high-crystallinity silver powder: and c, filtering the silver paste obtained in the step b, washing the silver paste with deionized water and ethanol until the conductivity of the wastewater is less than or equal to 20 mu S/cm, dispersing the silver paste in an organic solution containing a surface modifier at a high speed, filtering the silver paste for the second time, and drying the silver paste to finally obtain the high-crystallinity silver powder.
In the efficient preparation method of the high-crystallinity silver powder, the concentration of the dissolved silver nitrate in the step a is 0.5-30g/L, the temperature of the oven is 100-200 ℃, and the heating reaction time in the oven is 30-120min.
In the efficient preparation method of the high-crystallinity silver powder, the concentration of the dispersant a dissolved in the step a is 400-700g/L, and the dispersant a is one or at least two of tween, gelatin, arabic gum, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, sodium citrate, triethanolamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
In the efficient preparation method of the high-crystallinity silver powder, the temperature of the deionized water in the step b is 20-70 ℃, the temperature of the silver nitrate aqueous solution is 20-70 ℃, the concentration of the silver nitrate aqueous solution is 100-450g/L, and the silver nitrate aqueous solution is added into the intermediate solution to react for 3-30min.
In the above method for efficiently preparing silver powder with high crystallinity, the concentration of the reducing agent in the step b is 40-100g/L, and the reducing agent is one or at least two of hydrazine hydrate, formaldehyde, acetaldehyde, hydroxylamine sulfate, ascorbic acid, glucose, ethylene glycol, triethanolamine and the like. The concentration of the dispersing agent b in the step b is 10-50g/L, and the dispersing agent b is the combination of polyvinylpyrrolidone, sodium citrate and hexadecyl trimethyl ammonium bromide.
In the above method for efficiently preparing high-crystallinity silver powder, the PH adjuster in step b is one or at least two of ammonia water, sodium hydroxide, sodium bicarbonate, sodium carbonate, nitric acid, hydrochloric acid, and sulfuric acid.
In the above method for efficiently preparing a silver powder with high crystallinity, the stirring speed in the step b is 100-500 rpm under stirring conditions during pouring of the silver nitrate aqueous solution.
In the efficient preparation method of the high-crystallinity silver powder, the dosage of the surface modifier in the step c is 0.1-5% of the mass of the silver powder to be dispersed, the high-speed dispersion time is 10-40min, and the surface modifier is one or at least two of caprylic acid, oleic acid, stearic acid, palmitic acid, lauric acid, myristic acid, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine and the like; and the organic solvent in the step c is any one of ethanol, acetone, isopropanol, toluene and n-hexane.
In the efficient preparation method of the high-crystallinity silver powder, the drying temperature in the step c is 50-90 ℃, and the drying time is 4-12h, so that the high-crystallinity silver powder is finally prepared.
The efficient preparation method of the high-crystallinity silver powder has the beneficial effects that:
1. according to the efficient preparation method of the high-crystallinity silver powder, the oxidation liquid of the silver nitrate aqueous solution is added into the reduction liquid of the intermediate solution containing the nano crystal seeds in a pouring manner, so that the method for preparing the high-crystallinity silver powder by controlling the reaction rate by slowly dripping the oxidation liquid in the prior art is replaced, the production period is short, and the method is very suitable for large-scale industrial production.
2. Based on the following researches, polyvinylpyrrolidone tends to be adsorbed on the (100) crystal face in the silver powder growth process, cetyl trimethyl ammonium bromide tends to be adsorbed on the (110) crystal face of the silver powder, and the acting force between sodium citrate and the (111) crystal face of the silver powder is stronger, so that the silver powder with high crystallinity can be prepared by regulating and controlling the growth processes of different crystal faces of the silver powder by regulating the using amounts of the three dispersing agents under the condition of adding the nano crystal seeds, the production cost is relatively low, and the production investment can be remarkably reduced on the basis of ensuring the product quality. Verification results prove that the silver powder prepared by the method has the characteristics of high tap density, good dispersibility and high crystallinity, and is suitable for heterojunction solar cell fine grid printing.
Drawings
FIG. 1 is an SEM photograph of a silver powder prepared in example 1 using the preparation method of the present invention;
FIG. 2 is an SEM photograph of a silver powder prepared in example 2 using the preparation method of the present invention.
Detailed Description
The efficient preparation method of the high crystallinity silver powder according to the present invention is described in more detail by the following embodiments with reference to the accompanying drawings.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, are used in the orientations and positional relationships indicated in the drawings, which are based on the orientations and positional relationships indicated in the drawings, and are used for convenience of description and simplicity of description, but do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
Example 1:
the efficient preparation method of the high-crystallinity silver powder of the embodiment comprises the following steps:
a, step a: preparing nano seed crystals;
dissolving 4g of silver nitrate, 20g of gelatin and 60g of polyethylene glycol in 150g of ethylene glycol, transferring the mixture to a 500ml hydrothermal kettle after the mixture is completely dissolved, heating the mixture in a drying oven at the temperature of 120 ℃ for reaction for 30min, and preserving the prepared nano crystal seeds for later use after the reaction is finished.
Step b: preparing silver powder slurry;
and (b) preparing 3L of a mixed solution of ascorbic acid with the concentration of 60g/L, polyvinylpyrrolidone with the concentration of 5g/L, hexadecyl trimethyl ammonium bromide with the concentration of 8g/L and sodium citrate with the concentration of 12g/L, wherein the temperature of the mixed solution is 20 ℃, the stirring speed is 250rpm, after the mixed solution is completely dissolved, 10g of the nano seed crystal synthesized in the step a is added, the nano seed crystal is uniformly stirred, and the PH value is adjusted to 0.5 by using nitric acid to obtain an intermediate solution. Under the condition of stirring speed of 300 rpm, rapidly adding 2L of silver nitrate aqueous solution into the intermediate solution serving as a reducing agent by pouring, and reacting for 10 min, wherein the concentration of the silver nitrate aqueous solution is 130g/L, the temperature is 20 ℃, and after the reaction is finished, obtaining silver powder slurry.
Step c: preparing high-crystallinity silver powder;
and c, filtering the silver paste obtained in the step b, washing with deionized water and ethanol until the conductivity of the wastewater is less than or equal to 20 mu S/cm, then preparing a mixed ethanol solution of oleic acid and oleylamine with the mass of 1% of the silver powder, dispersing for 20min at a high speed, then filtering for the second time, and finally drying the silver powder filtered for the second time for 8h at the temperature of 70 ℃ to obtain the target high-crystallinity silver powder.
Example 2:
the efficient preparation method of the high-crystallinity silver powder of the embodiment comprises the following steps:
step a: preparing nano seed crystals;
this step is the same as step a in embodiment 1 and will not be described again.
Step b: preparing silver powder slurry;
2.5L of a mixed solution of 75g/L ascorbic acid, 8g/L polyvinylpyrrolidone, 12g/L hexadecyl trimethyl ammonium bromide and 9g/L sodium citrate is prepared, the temperature of the mixed solution is 25 ℃, the stirring speed is 350rpm, 12g of the nano seed crystals synthesized in the step 1 are added after complete dissolution and are stirred uniformly, and the PH value is adjusted to 0.7 by nitric acid to obtain an intermediate solution. Under the condition of a stirring speed of 400rpm, 2L of silver nitrate aqueous solution with the concentration of 150g/L and the temperature of 25 ℃ is rapidly added into the intermediate solution serving as the reducing agent by pouring to react for 15 min. And after the reaction is finished, obtaining silver powder slurry.
Step c: preparing high-crystallinity silver powder;
and c, filtering the silver powder slurry obtained in the step b, washing with deionized water and ethanol until the conductivity of the wastewater is less than or equal to 20 mu S/cm, preparing a mixed ethanol solution of caprylic acid and octadecylamine with the mass of 1.3% of the silver powder, dispersing at a high speed for 30min, filtering again, and drying the silver powder filtered twice for 10h at 75 ℃ to obtain the target high-crystallinity silver powder.
Table 1: table of Property parameters of silver powder samples prepared in examples 1 and 2
| Product numbering | D(0.1)（μm） | D(0.5)（μm） | D(0.9)（μm） | D(1.0)（μm） | Tap density (g/ml) |
| Example 1 | 1.109 | 1.68 | 2.513 | 4.26 | 5.94 |
| Example 2 | 1.102 | 1.645 | 2.441 | 4.01 | 5.5 |
As can be seen from the above table, all the silver powders had very narrow particle size distribution and high tap density. From the SEM images of fig. 1 and 2, we can see that the silver powder has high crystallinity, especially in the sample of fig. 1, the silver powder has clear edge angles and high flatness of the crystal plane.
Therefore, according to the efficient preparation method of the high-crystallinity silver powder, the growth processes of different crystal faces of the silver powder are regulated and controlled by adjusting the use amounts of the three dispersing agents, namely polyvinylpyrrolidone, sodium citrate and hexadecyl trimethyl ammonium bromide, under the condition of adding the special nano crystal seeds, so that the silver powder with high tap density, good dispersibility and high crystallinity can be prepared, and the method is suitable for fine grid printing of a heterojunction solar cell. Meanwhile, the method for preparing the high-crystalline silver powder by slowly dripping the oxidizing solution of the silver nitrate aqueous solution into the reducing solution of the intermediate solution containing the nano seed crystal replaces the method for preparing the high-crystalline silver powder by slowly dripping the oxidizing solution in the prior art, has short production period and is very suitable for large-scale industrial production.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of the terms "a" or "an" and the like in the description and in the claims of this application do not necessarily denote a limitation of quantity. The word "comprising" or "comprises", and the like, means that the element or item preceding the word comprises the element or item listed after the word and its equivalent, but does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect.
Exemplary embodiments of the present invention have been described in detail with reference to the preferred embodiments, however, it will be understood by those skilled in the art that various changes and modifications may be made to the specific embodiments described above, and various combinations of the technical features and structures proposed by the present invention may be made without departing from the concept of the present invention.
Claims (9)
1. A high-efficiency preparation method of high-crystallinity silver powder is characterized by comprising the following steps: the method comprises the following steps: preparing nano seed crystal: dissolving silver nitrate and a dispersant a in ethylene glycol, transferring the silver nitrate and the dispersant a to a hydrothermal kettle after the silver nitrate and the dispersant a are completely dissolved, placing the hydrothermal kettle in an oven for heating reaction for a certain time, and obtaining nano seed crystals after the reaction is finished; step b: preparing silver powder slurry: b, stirring and dissolving a reducing agent and a dispersing agent b in deionized water, adding 0.1-200g of the nano crystal seeds prepared in the step a after the reducing agent and the dispersing agent b are completely dissolved, uniformly stirring, and adding a pH regulator to regulate the pH to 0.1-5 to obtain an intermediate solution; under the condition of stirring, adding a silver nitrate aqueous solution into the intermediate solution in a pouring mode, and reacting for a certain time to obtain silver powder slurry; the concentration of the dispersing agent b in the step b is 10-50g/L, and the dispersing agent b is the combination of polyvinylpyrrolidone, sodium citrate and hexadecyl trimethyl ammonium bromide; step c: preparing high-crystallinity silver powder: and c, filtering the silver paste obtained in the step b, washing the silver paste with deionized water and ethanol until the conductivity of the wastewater is less than or equal to 20 mu S/cm, dispersing the silver paste in an organic solution containing a surface modifier at a high speed, filtering the silver paste for the second time, and drying the silver paste to finally obtain the high-crystallinity silver powder.
2. The efficient production method of a high-crystallinity silver powder according to claim 1, characterized in that: in the step a, the concentration of silver nitrate is 0.5-30g/L, the temperature of the oven is 100-200 ℃, and the heating reaction time in the oven is 30-120min.
3. The efficient production method of a high crystallinity silver powder according to claim 1, characterized in that: the concentration of the dispersing agent a in the step a is 400-700g/L, and the dispersing agent a is one or at least two of tween, gelatin, arabic gum, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, sodium citrate, triethanolamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
4. The efficient production method of a high crystallinity silver powder according to claim 1, characterized in that: and c, adding the silver nitrate aqueous solution into the intermediate solution for reaction for 3-30min, wherein the temperature of the deionized water in the step b is 20-70 ℃, the temperature of the silver nitrate aqueous solution is 20-70 ℃, and the concentration of the silver nitrate aqueous solution is 100-450 g/L.
5. The efficient production method of a high-crystallinity silver powder according to claim 1, characterized in that: the concentration of the reducing agent in the step b is 40-100g/L, and the reducing agent is one or at least two of hydrazine hydrate, formaldehyde, acetaldehyde, hydroxylamine sulfate, ascorbic acid, glucose, ethylene glycol, triethanolamine and the like.
6. The efficient production method of a high crystallinity silver powder according to claim 1, characterized in that: and the pH regulator in the step b is one or at least two of ammonia water, sodium hydroxide, sodium bicarbonate, sodium carbonate, nitric acid, hydrochloric acid and sulfuric acid.
7. The efficient production method of a high crystallinity silver powder according to claim 1, characterized in that: and in the step b, the stirring speed under the stirring condition is 100-500 rpm during the pouring of the silver nitrate aqueous solution.
8. The efficient production method of a high-crystallinity silver powder according to claim 1, characterized in that: in the step c, the dosage of the surface modifier is 0.1-5% of the mass of the silver powder to be dispersed, the high-speed dispersion time is 10-40min, and the surface modifier is one or at least two of caprylic acid, oleic acid, stearic acid, palmitic acid, lauric acid, myristic acid, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine and the like; the organic solvent in the step c is any one of ethanol, acetone, isopropanol, toluene and n-hexane.
9. The efficient production method of a high-crystallinity silver powder according to claim 1, characterized in that: the drying treatment temperature in the step c is 50-90 ℃, and the drying treatment time is 4-12h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116174739A (en) * | 2023-03-09 | 2023-05-30 | 深圳市哈深智材科技有限公司 | Microcrystal nano-sheet aggregation type spheroidal silver powder and preparation method thereof |
| CN116422896A (en) * | 2023-04-25 | 2023-07-14 | 深圳市哈深智材科技有限公司 | Conductive silver paste, silver powder and method for preparing silver powder by utilizing ionic dispersing agent |
| CN116765417A (en) * | 2023-06-28 | 2023-09-19 | 深圳市哈深智材科技有限公司 | Submicron silver powder preparation method with concentrated particle size distribution |
| CN117047121A (en) * | 2023-10-11 | 2023-11-14 | 长春黄金研究院有限公司 | Silver powder preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101347841A (en) * | 2008-09-03 | 2009-01-21 | 西北大学 | Method for preparing high tap density silver powder with controllable graininess |
| CN102407342A (en) * | 2011-10-31 | 2012-04-11 | 山东大学 | Preparation method of nano silver powder with accurately controllable particle size |
| CN110102777A (en) * | 2019-06-04 | 2019-08-09 | 刘焕明 | A kind of preparation method of the highly crystalline silver powder of induced growth |
| CN113600825A (en) * | 2021-07-22 | 2021-11-05 | 厦门大学 | Micron-sized spherical silver powder and preparation method thereof |
| CN114178543A (en) * | 2021-12-15 | 2022-03-15 | 苏州银瑞光电材料科技有限公司 | Preparation method of sphere-like silver powder |
-
2022
- 2022-08-05 CN CN202210940327.1A patent/CN115178747A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101347841A (en) * | 2008-09-03 | 2009-01-21 | 西北大学 | Method for preparing high tap density silver powder with controllable graininess |
| CN102407342A (en) * | 2011-10-31 | 2012-04-11 | 山东大学 | Preparation method of nano silver powder with accurately controllable particle size |
| CN110102777A (en) * | 2019-06-04 | 2019-08-09 | 刘焕明 | A kind of preparation method of the highly crystalline silver powder of induced growth |
| CN113600825A (en) * | 2021-07-22 | 2021-11-05 | 厦门大学 | Micron-sized spherical silver powder and preparation method thereof |
| CN114178543A (en) * | 2021-12-15 | 2022-03-15 | 苏州银瑞光电材料科技有限公司 | Preparation method of sphere-like silver powder |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116174739A (en) * | 2023-03-09 | 2023-05-30 | 深圳市哈深智材科技有限公司 | Microcrystal nano-sheet aggregation type spheroidal silver powder and preparation method thereof |
| CN116174739B (en) * | 2023-03-09 | 2023-09-29 | 深圳市哈深智材科技有限公司 | Microcrystal nano-sheet aggregation type spheroidal silver powder and preparation method thereof |
| CN116422896A (en) * | 2023-04-25 | 2023-07-14 | 深圳市哈深智材科技有限公司 | Conductive silver paste, silver powder and method for preparing silver powder by utilizing ionic dispersing agent |
| CN116765417A (en) * | 2023-06-28 | 2023-09-19 | 深圳市哈深智材科技有限公司 | Submicron silver powder preparation method with concentrated particle size distribution |
| CN116765417B (en) * | 2023-06-28 | 2024-02-13 | 深圳市哈深智材科技有限公司 | Submicron silver powder preparation method with concentrated particle size distribution |
| CN117047121A (en) * | 2023-10-11 | 2023-11-14 | 长春黄金研究院有限公司 | Silver powder preparation method |
| CN117047121B (en) * | 2023-10-11 | 2024-01-05 | 长春黄金研究院有限公司 | Silver powder preparation method |
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Application publication date: 20221014 |