CN104157328A - Silicon solar cell front face electrode silver paste and preparing method thereof - Google Patents
Silicon solar cell front face electrode silver paste and preparing method thereof Download PDFInfo
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Abstract
The invention discloses silicon solar cell front face electrode silver paste. The silicon solar cell front face electrode silver paste comprises, by mass, 75-80 percent of silver powder, 3-10 percent of lead-free glass powder, 10-15 percent of organic vehicle and 0.5-3 percent of additive. The silver powder is the spherical micro silver powder with nano bismuth serving as the core, the silver content is 99.1-99.7 percent, the bismuth content is 0.3-0.9 percent, the particle size is 1-2 microns, the tap density is 4.5-5.0 g/ml, the specific surface area is 0.4-1.0 m<2>/g, and the silver powder is prepared by conducting liquid-phase chemical reduction on bismuth nitrate and silver nitrate through glyoxal or acetaldehyde. Bismuth-silicon-antimony-molybdenum lead-free glass powder serves as an adhesive, and potassium fluotitanate, potassium fluoroaluminate, magnesium fluoride and the like are added to serve as the silicon nitride antireflective film eroding additive. According to the silicon solar cell front face electrode silver paste, the contact resistance between a silver electrode and a silicon wafer can be reduced, the stripping strength of the electrode is improved, the electrical property of a solar cell is improved, the production cost of the conductive silver paste is reduced, and the requirement for nonexistence of lead and environmental friendliness are met.
Description
Technical field
The present invention relates to a kind of silicon solar cell front electrode silver slurry and preparation method thereof, be applicable to the silicon solar cell system of high electricity conversion, high printing precision requirement, belong to new material and area of solar cell.
Background technology
Solar cell is a kind ofly solar energy can be converted to the semiconductor device of electric energy, and under the condition of illumination, solar cell can generation current, by grid line and electrode, electric collecting is got up and transferred out.Suitability for industrialized production crystal silicon cell is by p-type crystal silicon material is cut into slices, through cleaning, chemical corrosion making herbs into wool; In the diffusion of sensitive surface phosphorus, make p-n junction; Be coated with silicon nitride antireflection layer; By silk screen print method, aluminium paste is imprinted on to silicon chip back side, silver slurry is imprinted on to silicon chip positive and negative; Being dried, being sintered into several links such as cell piece forms.Front electrode divides gate line and main electrode line, and grid is mainly to accept the majority carrier that light conversion produces; And main electrode is mainly that cell piece is connected with outside line.The electrical property of the performance impact solar cell of front electrode, as technical indicators such as open circuit voltage, short circuit current, parallel resistance, series resistance, conversion efficiencies.
Front electrode of solar battery silver slurry is than the back side large two times of the high and consumption of silver slurry specification requirement extremely, and requirement possesses following condition: 1) can penetrate antireflective coating, make slurry and silicon substrate form effective contact; 2) there is higher electric conductivity, realize low series resistance; 3) higher linear resolution, to reduce ghost image as far as possible; 4) there is good welding performance, to connect outside line.
Solar cell conductive silver slurry is mainly comprised of silver powder, glass dust adhesive, organic carrier and additive four parts.Silver powder is as conducting medium; Glass glue melts when high temperature sintering, between silver powder and silicon base, forms ohmic contact; Organic carrier mainly plays a part to disperse and parcel silver powder particles, makes the silver powder in conductive silver paste be not easy precipitation and oxidation.Additive is processing performance and the combination property that promotes silver powder slurry, further improves conductive silver paste electric conductivity.
The key technical index of solar cell conductive silver slurry is mainly determined by the performance of silver powder, and silver powder performance depends primarily on its appearance structure feature, granularity and particle size distribution.Silver powder accounts for the 70%-90% of its quality in solar cell conductive silver slurry, is the key factor that determines silver slurry and form performance of silver electrode.Silver powder structure and morphology can be spherical, class is spherical, bar-shaped, sheet, dendroid etc., it between flake silver powder particulate, is face contact, conductivity can be more better in theory, but front electrode of solar battery requires depth-width ratio as far as possible large, to reduce silver electrode line, the light of silicon chip is blocked, so the spherical or class ball shape silver powder of the general employing of solar cell conductive silver slurry.If silver powder granularity is excessive, when printing silver slurry just can not be passed through silk screen completely, also cannot densified sintering product in the short time, and easily there is hole in sintered membrane, thereby affects conductivity.If silver powder undersized, silver powder slurry is difficult for, by organic carrier complete wetting, causing printing effect bad, after sintering, silverskin shrinkage is large, hole is many be connected not fine and close.Experimental results show that and adopt particle diameter can obtain good electrical property at the ball shape silver powder of 1-3 μ m, and the good silver powder of uniform particles can reduce the reverse leakage current of battery, thereby improve open circuit voltage and short circuit current, and effectively promote the unit for electrical property parameters such as parallel resistance and conversion efficiency.
The melting when high temperature of glass dust in front electrode conductive silver paste, etching antireflective coating, and form and be connected between silicon chip and silver electrode.In order to obtain better ohmic contact, in front electrode silver slurry, glass dust must have good eating thrown to silicon nitride anti-reflecting film.In traditional front electrode conductive silver paste, the general glass dust that contains lead oxide that adopts, because flint glass powder has lower fusing point, has good eating thrown to silicon nitride anti-reflecting film, makes silver electrode have good adhesive force and good battery performance simultaneously.But traditional front electrode silver slurry medium lead crystal glass easily causes the excessive eating thrown of silicon nitride anti-reflecting film in electrode sintering process.In addition, there is environment and potential safety hazard in leaded solar cell conductive silver slurry, and it uses oneself to be restricted, and will eliminate gradually, and leadless environment-friendly type conductive silver paste could meet large solar battery production demand.
The lead-free low-melting-point glass systems such as borate glass, phosphate glass, vanadate glass and bismuthate glass are studied both at home and abroad.The vanadate glass cost of raw material is higher, phosphate glass facile hydrolysis and unstable chemcial property, and borate glass fusing point can only drop to 600 ℃ of left and right.Because bismuth is similar to plumbous character, therefore, the research and development of bismuthate glass powder are in widespread attention, and expectation replaces lead oxide to prepare lead-free glass powder with bismuth oxide.
More even for what lead-free glass powder binding agent was mixed with silver powder, the particle diameter general control of glass dust binding agent is below 10 μ m, consumption is controlled at the 0.5%-10% of conductive silver paste total weight, if by quantity not sufficient 0. 5%, can affect the etching of antireflective coating and the adhesive force between silicon substrate and silver electrode; If consumption surpasses 10%, can reduce silver electrode electric conductivity.Glass dust in silver slurry need to have suitable softening temperature.When glass dust softening temperature is too low, in organic carrier volatilization and decomposable process, glass dust just starts to soften, softening glass dust can hinder the volatilization of organic carrier, the performance that silverskin is burnt till in impact, softening glass metal more enters the formation that can hinder conductive network in follow-up sintering process between silver powder particles too early simultaneously.When glass dust softening temperature is too high, in sintering process, glass dust does not have the effect of wetting silver powder, can cause burning till in silverskin cavity more, and conductive network is imperfect.Preferred glass dust softening point is 400-600 ℃, and front electrode conductive silver paste can be at 600-800 ℃ of sintering and suitably infiltrated like this, also can be combined well with silicon substrate.
Organic carrier in conductive silver paste is comprised of organic solvent, thickener, thixotropic agent, surfactant and curtain coating controlling agent, and the simplest carrier also should comprise organic solvent and two kinds of compositions of thickener.Organic solvent content is about the 65%-90% of organic carrier gross mass, more sticky liquid, there is higher boiling point, under normal temperature, volatility is low, the thickener of energy dissolving cellulos and so on, the most frequently used organic solvent is diethylene glycol ethers acetate (butyl carbitol acetate), tributyl citrate, dibutyl phthalate etc.Thickener effect is viscosity and the plasticity that improves slurry, conventionally adopt high molecular polymer to make thickener, they have netted or chain structure, there is the more intense group of polarity, be pressed powder state or cohesion shape liquid at normal temperatures, can be by organic solvent dissolution, to take off and do not stay ash content more than 300 ℃ being divided completely, conventional thickener has ethyl cellulose, nitrocellulose, polyisobutene and various synthetic resin etc.Action of Surfactant is to make organic carrier fully soak solia particle, and conventional surfactant has toluene and ethanol etc.The effect of curtain coating controlling agent is to stop slurry Yin Wendu in drying course raise and produce secondary flow, and conventional curtain coating controlling agent has terephthalic acid (TPA) and furancarboxylic acid etc.Thixotropic agent effect is to make thick film ink obtain necessary thixotropy, and conventional thixotropic agent has bentonite, calcium silicates, aluminium oxide or silica etc.
The unleaded conductive silver paste of used for solar batteries has many disclosed technology.Chinese patent CN103943168 (2014-07-23) discloses a kind of Ag (Ti, Zr)/rare earth crystal-silicon solar cell composite mortar and preparation method thereof, and the average grain diameter of the super fine silver powder of employing is 0. 2-2 μ m; Glass dust binding agent is Bi-Zn-Al-B-Si glass system; Add the superfine Ti O that particle diameter is less than 5 μ m
2and ZrO
2powder; Add Rare-Earth Ce, Eu or Gd powder, so that make silver-colored silicon contact finer and close in sintering process, further reduced contact resistance and the adhesive force that has strengthened electrode, reduced the consumption of argent simultaneously, improved crystal-silicon solar cell efficiency and reduced battery cost.Chinese patent CN103559939 (2014-02-05) discloses a kind of solar cell positive silver paste that adapts to high temperature sintering, the silver powder particle diameter adopting is 1-3 μ m, and the composition of lead-free glass powder and percetage by weight thereof are: bismuth oxide 50-60%, zinc oxide 10-30%, boric acid 3-5%, silica 5-9%, antimony oxide 0-15% and strontium oxide strontia 0-5%; Add simple substance or the compound of sintering aids rhodium, ruthenium or iridium; Solvent is one or more the mixture in terpinol, butyl carbitol, butyl carbitol acetate, tributyl citrate and tributyl phosphate; Thickener is one or more the mixture in ethyl cellulose, CMC, nitrocellulose.Chinese patent CN103440900 (2013-12-11) discloses the unleaded positive silver paste of a kind of crystal silicon solar energy battery, and the silver powder of employing is the silver powder that average grain diameter 0.2-2 μ m, tap density are greater than 4.5g/ml; The crown glass system of lead-free glass powder for being formed by Bi-Zn-Al-B-Si, softening temperature is 350 ℃～600 ℃; Add one or more in acid additive diboron trioxide, phosphorus pentoxide, selenium dioxide, vanadic oxide, tellurium dioxide.Chinese patent CN102324263 (2013-04-10) discloses a kind of silver for solar cell slurry and preparation method thereof, and the silver powder of employing is spherical or scale shape, and the particle diameter of silver powder includes two kinds of 30～58nm and 58～90nm; Lead-free glass powder adopts lanthanum-boron-zinc glass system; Organic solvent comprises the combination of any or they in terpinol, turpentine oil, butyl carbitol, butyl carbitol acetate, ethers; Thickener is cellulose, dibutyl phthalate or acrylic resin; Surfactant is triethanolamine, rilanit special, lecithin; Levelling agent is acrylate; Dispersant is stearmide and higher alcohol; Thixotropic agent is aerosil, precipitated silica, organobentonite.Chinese patent CN102956283 (2013-03-06) discloses unleaded silver slurry and preparation and application thereof for a kind of new and effective crystal silicon solar batteries, the silver powder adopting is selected from one or more the mixing in simple metal silver powder, silver-nickel powder, silver-colored magnesium alloy powder and yellow gold powder, and particle diameter is preferably 0.5-2.5 μ m; Lead-free glass powder is Te0
2-Bi
20
3-Sb
20
3-M system, M is a kind of in Zn, Mg, Ba, Ca or their mixing; Solvent is selected from one or more in turpentine oil, terpinol, butyl carbitol, butyl carbitol acetate and tributyl citrate; Thickener is selected from ethyl cellulose and butyl cellulose; Surfactant is selected from caprylic acid, lecithin and Si Ban 85; Thixotropic agent is rilanit special.Chinese patent CN102779566 (2012-11-04) discloses the unleaded conductive silver paste in a kind of crystal silicon solar energy battery front, and adopting the average grain diameter of silver powder is that 0.2-1.0 μ m, tap density are greater than 4.5g/ml; Lead-free glass powder binding agent adopts a kind of in B-Zn-Sb glass system, Bi-B-Si glass system, Bi-Si-Zn glass system; Add the IrO of 0.1%-2%
2antioxidant; Add a kind of of Sn-Ag alloyed powder, Sn-Ag-Cu alloyed powder, Sn-Sb alloyed powder; Thickener is that a kind of one-tenth in ethyl cellulose, acrylic resin, rosin, NC Nitroncellulose is several; Organic solvent is one or more in terpinol, butyl carbitol acetate, diethylene glycol butyl ether, dibutyl phthalate.Chinese patent CN102054882 (2011-05-11) discloses conductive silver paste with grid electrode front and preparation method thereof for a kind of crystal silicon solar energy battery, the silver powder adopting is spherical silver powder, the particle diameter of silver powder is 0. 4-1.0 μ m, and tap density is 3.5-5.0g/ml; Glass dust is lead-free glass powder; Add organo-metallic compound Indium Tris acetylacetonate, acetylacetone,2,4-pentanedione gallium or copper naphthenate; Add one or more in zinc oxide, tin oxide or titanium oxide; Solvent comprises 12 ester alcohol.It is positive with silver slurry and preparation method thereof that Chinese patent CN101964219 (2011-02-02) discloses a kind of crystal silicon solar energy battery, employing micron order silver powder, and particle diameter is 0. 5-5.0 μ m; Glass dust is boron-bismuth-silicon-aluminosilicate system; Add manganese dioxide to reduce the peel strength of contact resistance and increase electrode; Organic carrier is to be dissolved in by ethyl cellulose a kind of thick liquid forming in solvent, and the viscosity of organic carrier regulates with the mass fraction of ethyl cellulose.Chinese patent CN101271929 (2008-09-24) discloses a kind of leadless solar battery silver paste and preparation method thereof, and the silver powder of employing is ball shape silver powder, and silver powder particle diameter is 0.2-2 μ m; Crown glass adhesive adopts bismuth-silicon-antimonial glass system; Organic solvent is the combination of any or they in terpinol, turpentine oil, ethers; Organic additive is the combination of any or they in ethyl cellulose, dibutyl phthalate, acrylic resin.US Patent No. 20110095240(2011-04-28) disclose a kind of solar cell conductive silver slurry, adopt tellurium tungsten zinc molybdate system glass glue to substitute traditional lead glass, it is little that electrode performance is affected by sintering temperature.
Commercialization crystal silicon solar energy battery photoelectric conversion efficiency is less than 20% at present, and cost of electricity-generating is higher, can't reach par online target, mainly relies on government subsidy to apply.Solar cell conductive silver slurry cost accounts for 17% left and right of solar module cost, at reduction conductive silver paste cost and raising aspect of performance, also has extensive work to need to carry out.Existing unleaded conductive silver paste sintering range is narrow, volume resistance is large, the adhesive force of silver layer on silicon chip general, have gap with traditional leaded conductive silver paste aspect electrode solderability and oxidative resistance, and product cost is also higher.
Summary of the invention
The object of the invention is for silicon solar cell front electrode silver slurry the deficiencies in the prior art, a kind of leadless environment-friendly type silicon solar battery electrode silver slurry is provided, its composition comprises micro aluminum powder, lead-free glass powder, organic carrier and additive.In silver slurry, the mass percentage content of silver powder is 75%-80%, and the mass percentage content of lead-free glass powder is 3%-10%, and the quality percentage composition of organic carrier is 10%-15%, and the mass percentage content of additive is 0.5%-3%.
Micro aluminum powder of the present invention is that nanometer bismuth is the spherical micro aluminum powder of core, is prepared silver content 99.1%-99.7% by glyoxal or glyoxalic acid substep liquid phase chemical reduction bismuth nitrate and silver nitrate, bi content 0.3%-0.9%, particle diameter 1-2 μ m, tap density 4. 5-5.0g/ml, specific area 0.4-1.0m
2/ g.Because bismuth fusing point only has 271 ℃, when silver slurry sintering, nanometer bismuth is that the bismuth in the spherical micro aluminum powder of core burns and generates bismuth oxide when fusing point, 824 ° of C of bismuth oxide fusing point, can be used as silver powder sintering wetting agent or flux constituents, volumetric expansion while being oxidized due to bismuth, thermal contraction problem while having overcome to a certain extent silver-colored slurry sintering, make sintering silverskin dense non-porous hole, improve compactness and the smoothness of silver electrode film, thereby increased the short circuit current of battery, improved the photoelectric conversion efficiency of cell piece.
Lead-free glass powder of the present invention adopts bismuth-silicon-antimony-Xi-molybdenum glass system, and its component and mass percent are: Bi
20
360%-75%, Si0
25%-10%, Sb
20
35%-10%, Sn0
25%-10%, Mo0
35%-10%, the softening point of this system glass dust is 400-600 ℃, because softening point is lower, silver powder sintering range is expanded, and makes silver layer and silicon substrate can form good ohmic contact, guarantees that the silver electrode after burning till has good adhesive force.
Organic carrier of the present invention is comprised of solvent and thickener, and its component and percentage by weight are: butyl carbitol 50%-60%, acetoglyceride 15%-20%, dihydroxy ethyl coco amine 15%-20%, ethyl cellulose 5%-10%.Dihydroxy ethyl coco amine boiling point more than 350 ℃, is not only good organic solvent, is also good surfactant simultaneously, can make the wetting silicon chip surface of silver slurry, improves silver electrode printing quality, reaches the depth-width ratio of silver grating line design.
Additive is silicon nitride anti-reflecting film eating thrown additive, comprise one or more of potassium fluotitanate, potassium fluoroaluminate, magnesium fluoride, stable chemical nature under their normal temperature, the quick eating thrown silicon nitride of energy under the hot conditions of silver slurry sintering, reduce the contact resistance of silver layer and silicon chip, improve the adhesive force of silver electrode on silicon chip.
Another object of the present invention is to provide a kind of preparation method of silicon solar battery electrode silver slurry, comprises lead-free glass powder preparation, organic carrier preparation and the preparation of silicon solar battery electrode silver slurry, and the technical scheme of taking is as follows.
1. lead-free glass powder preparation
(1) by formula in mass percent, by glass dust raw material with Bi
20
360%-75%, Si0
25%-10%, Sb
20
35%-10%, Sn0
25%-10%, Mo0
3after mixing, the ratio of 5%-10% packs in crucible dry 0.5-1.0 hour at 150 ℃ into;
(2) crucible that glass dust raw material is housed is heated to temperature 1000-1300 ℃ melting in Muffle furnace, insulation 1-2 hour;
(3) after glass metal clarification evenly, directly pour clear liquid in deionized water shrend, after being dried, obtain coarse glass frit;
(4) by coarse glass frit ball milling, cross 400 mesh sieves, obtain the glass dust of 3-5 μ m, the softening point of this system glass dust is 400-600 ℃.
2. organic carrier preparation
(1) press formulation ratio butyl carbitol 50%-60% and acetoglyceride 15%-20%, butyl carbitol, acetoglyceride are mixed;
(2) at 80-110 ℃, by formulation ratio dihydroxy ethyl coco amine 15%-20% and ethyl cellulose 5%-10%, add successively dihydroxy ethyl coco amine and ethyl cellulose to dissolve, stir and make transparent organic carrier.
3. silicon solar battery electrode silver slurry preparation
(1) the spherical micro aluminum powder, lead-free glass powder, organic carrier and the additive that by nanometer bismuth, are core are weighed, the mass percentage content of silver powder is 75%-80%, the mass percentage content of lead-free glass powder is 3%-10%, the quality percentage composition of organic carrier is 10%-15%, and the mass percentage content of additive is 0.5%-3%;
(2) in container, mixture is stirred, this mixture is ground 10-20 time on three-roll grinder, the fine setting by solvent reaches below 8 μ m silver slurry fineness, and viscosity is 200-300PaS, obtains silicon solar battery electrode silver slurry.
The beneficial effect that the present invention obtains is:
(1) to adopt nanometer bismuth be the spherical micro aluminum powder of core in the present invention, bismuth core burns and generates bismuth oxide when fusing point, can be used as silver powder sintering wetting agent, during bismuth oxidation, volumetric expansion makes sintering silverskin dense non-porous hole, improve compactness and the smoothness of electrode film, thereby increased the short circuit current of battery, improved the photoelectric conversion efficiency of cell piece;
(2) conductive silver paste of the present invention contains silicon nitride anti-reflecting film eating thrown additive, can reduce electrode and silicon chip contact resistance and improve stripping electrode intensity, has improved the electrical property of battery;
(3) the present invention is meeting under the prerequisite of solar cell electrical property, reaches the leadless environment-friendly requirement of solar cell, has reduced conductive silver paste production cost.
Embodiment
Embodiment 1
By glass dust raw material Bi
20
360g, Si0
210g, Sb
20
310g, Sn0
210g, Mo0
3after 10g mixes, pack in crucible, the crucible that raw material is housed is heated to 1200 ℃ of meltings of temperature and is incubated 2 hours in Muffle furnace; After glass metal clarification evenly, directly pour clear liquid in 2000mL deionized water shrend, obtain coarse glass frit, by coarse glass frit ball milling, cross 400 mesh sieves, obtain the glass dust 100g of 3-5 μ m, the softening point of glass dust is 480-490 ℃.
Butyl carbitol 50g, acetoglyceride 20g are mixed, be heated to 95 ℃, add successively dihydroxy ethyl coco amine 20g and ethyl cellulose 10g, stir and make transparent organic carrier 100g.
The spherical micro aluminum powder 80g that to get nanometer bismuth prepared by glyoxal liquid phase chemical reduction bismuth nitrate and silver nitrate be core, its silver content 99.1%, bi content 0.9%, average grain diameter 1.5 μ m, tap density 5.0g/ml, specific area 0.54m
2/ g and lead-free glass powder 5g, organic carrier 12g and additive potassium fluotitanate 3 g mixing and stirring in container, mixture is ground 10-20 time on three-roll grinder, silver slurry fineness is reached below 8 μ m, and viscosity is 200-300PaS, obtains silicon solar battery electrode silver slurry 100g.
With screen printing mode, silver slurry is printed on 125mm * 125mm silicon substrate, then dry at 200 ℃, with the speed of 150 ℃/min, heat up, at 800-900 ℃, carry out quick fired electrodes lead-in wire, the contact conductor surface silvery white of making after high temperature sintering, microscopic examination smooth surface zero defect, peel strength 10N/cm, soldering is functional, and solar cell photoelectric transformation efficiency is 19. 5%.
Embodiment 2
By glass dust raw material Bi
20
375g, Si0
210g, Sb
20
35g, Sn0
25g, Mo0
3after 5g mixes, pack in crucible, the crucible that raw material is housed is heated to 1200 ℃ of meltings of temperature and is incubated 2 hours in Muffle furnace; After glass metal clarification evenly, directly pour clear liquid in 2000mL deionized water shrend, obtain coarse glass frit, by coarse glass frit ball milling, cross 400 mesh sieves, obtain the glass dust 100g of 3-5 μ m, the softening point of glass dust is 430-440 ℃.
Butyl carbitol 50g, acetoglyceride 20g are mixed, be heated to 95 ℃, add successively dihydroxy ethyl coco amine 20g and ethyl cellulose 10g, stir and make transparent organic carrier 100g.
The spherical micro aluminum powder 75g that to get nanometer bismuth prepared by glyoxalic acid liquid phase chemical reduction bismuth nitrate and silver nitrate be core, its silver content 99.7%, bi content 0.3%, average grain diameter 1.8 μ m, tap density 4. 5g/ml, specific area 0.66m
2/ g and lead-free glass powder 8g, organic carrier 15g and additive potassium fluoroaluminate 2 g mixing and stirring in container, mixture is ground 10-20 time on three-roll grinder, silver slurry fineness is reached below 8 μ m, and viscosity is 200-300PaS, obtains silicon solar battery electrode silver slurry 100g.
With screen printing mode, silver slurry is printed on 125mm * 125mm silicon substrate, then dry at 200 ℃, with the speed of 150 ℃/min, heat up, at 800-900 ℃, carry out quick fired electrodes lead-in wire, the contact conductor surface silvery white of making after high temperature sintering, microscopic examination smooth surface zero defect, peel strength 9N/cm, soldering is functional, and solar cell photoelectric transformation efficiency is 19. 3%.
Claims (4)
1. a silicon solar cell front electrode silver slurry, comprise silver powder, lead-free glass powder, organic carrier and additive, the mass percentage content that it is characterized in that silver powder in silver slurry is 75%-80%, the mass percentage content of lead-free glass powder is 3%-10%, the quality percentage composition of organic carrier is 10%-15%, and the mass percentage content of additive is 0.5%-3%; Described silver powder is that nanometer bismuth is the spherical micro aluminum powder of core, silver content 99.1%-99.7%, bi content 0.3%-0.9%, particle diameter 1-2 μ m, tap density 4.5-5.0g/ml, specific area 0.4-1.0m
2/ g, is prepared by glyoxal or glyoxalic acid liquid phase chemical reduction bismuth nitrate and silver nitrate; Described lead-free glass powder adopts bismuth-silicon-antimony-Xi-molybdenum glass system, and its component and mass percent are: Bi
20
360%-75%, Si0
25%-10%, Sb
20
35%-10%, Sn0
25%-10%, Mo0
35%-10%; Described organic carrier is comprised of solvent and thickener, and its component and mass percent are: butyl carbitol 50%-60%, acetoglyceride 15%-20%, dihydroxy ethyl coco amine 15%-20%, ethyl cellulose 5%-10%; Described additive is silicon nitride anti-reflecting film eating thrown additive, comprises one or more combinations of potassium fluotitanate, potassium fluoroaluminate, magnesium fluoride.
2. according to the silicon solar cell front electrode silver slurry described in claim l, it is characterized in that crown glass powder, preparation method thereof and process are:
(1) by formula in mass percent, by glass dust raw material with Bi
20
360%-75%, Si0
25%-10%, Sb
20
35%-10%, Sn0
25%-10%, Mo0
3after mixing, the ratio of 5%-10% packs in crucible dry 0.5-1.0 hour at 150 ℃ into;
(2) crucible that glass dust raw material is housed is heated to temperature 1000-1300 ℃ melting in Muffle furnace, insulation 1-2 hour;
(3) after glass metal clarification evenly, directly pour clear liquid in deionized water shrend, after being dried, obtain coarse glass frit;
(4) by coarse glass frit ball milling, cross 400 mesh sieves, obtain the glass dust of 3-5 μ m, the softening point of this system glass dust is 400-600 ℃.
3. according to the silicon solar cell front electrode silver slurry described in claim l, it is characterized in that organic carrier preparation process is:
(1) press formulation ratio butyl carbitol 50%-60% and acetoglyceride 15%-20%, butyl carbitol, acetoglyceride are mixed;
(2) at 80-110 ℃, by formulation ratio dihydroxy ethyl coco amine 15%-20% and ethyl cellulose 5%-10%, add successively dihydroxy ethyl coco amine and ethyl cellulose to dissolve, stir and make transparent organic carrier solution.
4. a preparation method for silicon solar cell front electrode silver slurry described in claim l, is characterized in that preparation process is:
(1) the spherical micro aluminum powder, lead-free glass powder, organic carrier and the additive that by nanometer bismuth, are core are weighed, wherein the mass percentage content of silver powder is 75%-80%, the mass percentage content of lead-free glass powder is 3%-10%, the quality percentage composition of organic carrier is 10%-15%, and the mass percentage content of additive is 0.5%-3%;
(2) in container, above mixture is stirred, this mixture is ground 10-20 time on three-roll grinder, the fine setting by solvent reaches below 8 μ m silver slurry fineness, and viscosity is 200-300PaS, obtains silicon solar battery electrode silver slurry.
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| CN107871542B (en) * | 2016-09-27 | 2021-09-07 | 株式会社则武 | Silver paste and electronic component |
| CN107871542A (en) * | 2016-09-27 | 2018-04-03 | 株式会社则武 | Silver paste and electronic component |
| CN106601327A (en) * | 2016-12-21 | 2017-04-26 | 北京市合众创能光电技术有限公司 | Solar battery front-surface electrode conductive slurry with low solvent volatility and preparation method thereof |
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| CN108598190A (en) * | 2018-05-31 | 2018-09-28 | 苏州瑞力博新材科技有限公司 | A kind of low-density HIT low temperature silver paste used for solar batteries and preparation method |
| CN108665998A (en) * | 2018-07-25 | 2018-10-16 | 原晋波 | A kind of easy-sintering solar cell conductive paste and preparation method thereof |
| CN110415858A (en) * | 2019-06-27 | 2019-11-05 | 天津爱旭太阳能科技有限公司 | A kind of front side silver paste and preparation method thereof of crystal silicon solar energy battery gradation |
| CN110415858B (en) * | 2019-06-27 | 2022-01-14 | 天津爱旭太阳能科技有限公司 | Front silver paste for crystalline silicon solar cell in grading and preparation method thereof |
| CN110550939A (en) * | 2019-09-09 | 2019-12-10 | 长江师范学院 | Insulating material for manufacturing mineral insulated cable and preparation method thereof |
| CN111584645A (en) * | 2020-05-19 | 2020-08-25 | 江苏东鋆光伏科技有限公司 | High-efficiency solar cell and processing technology thereof |
| CN113488223A (en) * | 2021-07-09 | 2021-10-08 | 苏州晶银新材料科技有限公司 | Solar cell conductive silver paste without silicone oil and application thereof |
| CN113409986A (en) * | 2021-07-14 | 2021-09-17 | 周静璐 | Silver-aluminum paste for solar cell P + electrode and solar cell |
| CN113409986B (en) * | 2021-07-14 | 2022-11-15 | 晶澜光电科技(江苏)有限公司 | Silver-aluminum paste for solar cell P + electrode and solar cell |
| CN113764119A (en) * | 2021-09-07 | 2021-12-07 | 南通天盛新能源股份有限公司 | Silver-aluminum paste for high sheet resistance N-type solar cell front electrode and preparation method thereof |
| CN114038608A (en) * | 2021-12-24 | 2022-02-11 | 西安宏星电子浆料科技股份有限公司 | Low-resistivity solar cell conductive paste |
| CN115036056A (en) * | 2022-08-11 | 2022-09-09 | 西安拓库米电子科技有限公司 | High-weldability thick-film conductor paste |
| CN115036056B (en) * | 2022-08-11 | 2022-11-01 | 西安拓库米电子科技有限公司 | High-weldability thick-film conductor paste |
| CN115064300A (en) * | 2022-08-18 | 2022-09-16 | 西安拓库米电子科技有限公司 | Silver conductor paste for nickel-plating-free chip resistor |
| CN115064300B (en) * | 2022-08-18 | 2022-11-18 | 西安拓库米电子科技有限公司 | Silver conductor paste for nickel-plating-free chip resistor |
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