CN102139368B - High-dispersion silver powder and solar battery electrode conductive silver paste - Google Patents
High-dispersion silver powder and solar battery electrode conductive silver paste Download PDFInfo
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Abstract
The invention discloses high-dispersion silver powder and solar battery electrode conductive silver paste, wherein the conductive silver paste is prepared from the following components in mass percentage: 53-61.8% of high-dispersion silver powder in claim 1, 21.5-31% of glass cement and 15-17.6% of organic carrier. The high-dispersion silver powder provided by the invention has very good dispersity and by means of the conductive silver paste prepared by the high-dispersion silver powder, the usage amount of the silver powder is reduced and the conductive efficiency is improved in the mean time; in addition, the conductive silver paste provided by the invention is clean and environmental-friendly and is suitable for popularization and application. By means of the high-dispersion silver powder and the solar battery electrode conductive silver paste which are provided by the invention, the defects of poor dispersity of the conventional silver powder and large usage amount of the silver powder of the conventional conductive silver paste are overcome.
Description
Technical field
The invention belongs to the photovoltaic generation Material Field, be specifically related to a kind of high dispersive type silver powder and a kind of conductive silver paste of solar battery electrode.
Background technology
At present, the actual development amount of wind energy, geothermal energy and hydraulic power potentials can not satisfy human demand to the energy far away in the world, and solar energy resources is one of the abundantest regenerative resource, and it is widely distributed, renewable, free from environmental pollution, is the desirable alternative energy source of generally acknowledging in the world.Therefore, the development potentiality of solar cell industry correspondingly is huge, becomes emerging Chaoyang industry.
The cephalopodium but development speed is had a contest is started late in China's New Energy Industrialization development.China's photovoltaic generation industry starts to walk in 20 century 70s, has obtained in recent years fast development.Point out that in " the New Energy Industry rejuvenation and development planning (draft) " of the up-to-date promulgation of country solar electrical energy generation installation scale reaches respectively 2,000,000 kW and 2,000 ten thousand kW, the year two thousand twenty in 2011.Solar cell yield had reached 4011 megawatts in 2009, accounted for 40% of world's solar cell total output.The cell piece of upstream in 2010 and battery component company are all enhancing production capacities, and about 8000 megawatts of cell piece output have become the first producing country of world's solar cell.Because China is populous, energy resource consumption is large, so the development speed of future solar energy can be faster, will become the core industry in the new energy field.Yet, China's manufacture of solar cells line key equipment, raw material and the serious dependence on import of assembly.
In the solar cell of at present extensive use, except crystal silicon chip, positive and negative electrode also is very crucial part, wherein the time spent of doing of front electrode utilizes thin grid line wherein to collect the photoelectron that produces because of photovoltaic effect in the silicon chip, and these photoelectrons are transferred on the main grid line, final derivation battery, so electrode is directly to affect one of the conductance of solar cell and key core material of photoelectric transformation efficiency.
The method of making electrode is a lot, and wherein the technology of preparing of front electrode has photoetching, magnetron sputtering, vacuum evaporation, grooving and grid burying and serigraphy etc.But the production cost of photoetching, magnetron sputtering, grooving and grid burying and vacuum evaporation is high, and production efficiency is low, and silk screen print method has the efficient height, cost is low and the characteristics of equipment simple and durable, can be used as the method for suitability for industrialized production solar cell.Serigraphy be adopt the mode of impression with predetermined graphic printing on substrate, comprise the cell front side silver paste printing, cell backside silver aluminium paste printing and the printing of cell backside aluminium paste.The used for solar batteries conductive silver paste has good printing, electric conductivity, non-oxidizability, weatherability and chemical-resistance, can with back electrode slurry co-sintering, the sensitive surface electrode width is narrow behind the sintering, thickness is high, compactness is good, non-microcracked, adhesive force is good, with the contact resistance of silicon chip low (can effectively permeate antireflection layer), can obtain high electricity conversion, be desirable front electrode slurry.Also alternative back side aluminium paste prepares high performance solar cell negative pole.
According to present manufacture of solar cells technique, in general, the front side silver paste consumption is about 70kg/MW, the about 20kg/MW of the demand of back side slurry, therefore the solar battery sheet of 1000 megawatt production capacities needs about 70 tons of anode silver paste, and negative electrode needs about 20 tons of silver slurry, and domestic demand solar electrical energy generation installation scale reached 8000MW approximately in 2010, therefore need altogether anode silver paste about 560 tons, backplate is starched about 160 tons with silver.According to national new forms of energy development plan, following solar energy industry is huger for the demand of solar energy conductive silver paste.
The solar cell size quality requirements is high, technological difficulties are many, product is with strong points, fund input is large.At present, solar cell and assembly thereof are produced in the raw and auxiliary material, and most equipment and consumptive material are realized production domesticization fully.But solar cell conductive silver slurry is as the main raw material(s) of making solar cell, and its market is basically by U.S. DUPANT, U.S. FERRO and this three companies monopolization of German Hereaus.
Domestic also have minority silver to starch manufacturer, but compare with external advanced producer, the problems such as sintering range was narrow when there was sintering in domestic silver slurry, the solar cell transformation efficiency low and percent defective is higher, be only suitable for preparing the conductive silver paste that low-grade electronic applications is used, can't satisfy solar cell to the high-end requirement of conductive silver powder.Therefore China manufacture of solar cells producer adopts import silver slurry mostly, Du Pont, Fu Lu, ESL, the he Li Shi of Germany and some producers of Japan etc. such as the U.S., this situation causes silver paste of solar cells to become than the external interdependency of polycrystalline silicon material higher raw material also, has seriously restricted development and the growth of China's photovoltaic industry.
Silver paste of solar cells mainly is comprised of silver powder, glass dust, fluoropolymer resin, solvent and auxiliary agent etc., and wherein, silver powder accounts for overall more than 80% of weight of silver slurry.The main dependence on import of domestic silver paste of solar cells, trace it to its cause, that the core component of usefulness---quality of cathode silver requires very high because solar energy silver is starched, the quality that is to say silver powder directly determines conductance and the electricity conversion of electrode of solar battery, also determines simultaneously the cost of conductive silver paste.On the market of the special-purpose silver powder of high-end solar cell, made in China still is in space state, so cause in the used high-end conductive silver paste of domestic manufacture of solar cells, institute's silver powder that adopts almost all is the employing import.The special-purpose silver powder price of external solar cell is very high, even some producers silver powder not for sale.Cause domestic solar energy silver slurry manufacturer production not go out the silver slurry of superior performance under this situation, thereby make manufacture of solar cells merchant cost higher, the market competitiveness is limited.Therefore, the special-purpose silver powder of silver paste of solar cells is produced in research and development, to reduce production costs, improve the performance (as: high-tap density, high conversion efficiency, high dispersive, pattern are controlled, particle diameter distributes rationally) of silver powder, thereby improving the level of production of solar cell, also is the needs of domestic solar cell industry development.
The several critical problems that improve at present the required solution of quality of the special-purpose silver powder of domestic solar cell are: the control that the pattern of (1) silver powder, particle diameter and particle diameter distribute: it is one of main performance index of the special-purpose silver powder of solar cell that the pattern of silver powder, particle diameter and particle diameter distribute, and also is finally to prepare the conductance of electrode of solar battery and the major influence factors of photoelectric transformation efficiency.Present domestic silver powder manufacturer is differing greatly with international counterparts aspect control, silver powder particle diameter and the particle diameter distribution of pattern, the main threshold that this silver powder that also is domestic silver powder manufacturer produces faces when area of solar cell is used.(2) dispersion problem of silver powder: in electrode of solar battery, because the chemical property of other two components of silver powder is different, so silver powder is difficult to disperse.The electricity of the dispersed determining electrode of silver powder and optical property improve the dispersiveness of silver powder in electrode material, then need its modifying surface.
The dispersion of silver powder in conductive silver paste is very important, improve the dispersiveness of silver powder, just need to be to its modifying surface, because the 1. easy oxidation of silver powder, although its oxide also has certain conductance, but can reduce to a certain extent its performance, appropriate surface modification then can prevent the oxidation of silver powder.When 2. silver powder is applied on the solar cell, generally need through high temperature sintering (600 ℃～900 ℃), silver powder is melted the formation conductive network, high temperature sintering not only can improve the power consumption in the manufacture of solar cells process, and the performance of some assembly can be affected on the battery, especially the thin film solar cell of development in recent years non-refractory especially.And silver powder carries out after the surface modification through certain method, can reduce the sintering temperature of silver powder, avoids the problems referred to above.3. the particle diameter of the special-purpose silver powder of solar cell is less, apparent activation energy is higher, therefore easily gathering, the difficult dispersion.In addition, when silver powder prepares solar cell conductive silver slurry, need to add some auxiliary substances, mix such as unorganic glass oxide, organic polymer etc., there is larger difference in the chemical property of these materials, so silver powder is difficult to be evenly dispersed in wherein, finally cause silver slurry cost to rise and hydraulic performance decline.And according to the system of the required dispersion of silver powder, to its modifying surface, can prevent effectively that silver powder from assembling, improving silver powder and disperseing in polymeric system.At present, domestic silver powder production firm lacks for the silver powder surface modification aspect and payes attention to, although the appearance of Patents is arranged, still has certain shortcoming, below just at present both at home and abroad for the problems referred to above, a little simple summaries are done in the work of doing aspect conductive silver paste.
Mention among the patent CN 101834004A (a kind of silver powder for conductive silver paste of solar battery electrode and preparation method thereof), adopt chemical reduction method, namely make reducing agent with glucose, ascorbic acid, hydrazine hydrate, hydroquinones, with polyoxyethylene alkyl amine, as dispersant.The reduction silver nitrate obtains average grain diameter at 0.3～1.5 μ m, and span is 1.1～1.6, and thermal weight loss is less than 0.3% silver powder after the calcination.In this patent, thermal weight loss is little behind the purity of silver powder height, the sintering, the electrode of solar battery good conductivity of making.This patent thinks that silver powder particles size and span have a great impact for sintering and the dissolving of silver powder particles, so this patent is by the average grain diameter of control silver powder and the improve that the particle diameter span realizes conductance.But this patent is to adopt polyoxyethylene alkyl amine class material as dispersant, although can improve the dispersiveness of silver powder, adopt the method for this physics not good for the dispersion effect of silver powder, and too much use dispersant also can reduce the electric conductivity of silver powder.
Patent 200610027065.0 (electrode of solar battery with the preparation method of silver powder in the printing slurry) discloses a kind of electrode of solar battery with the preparation method of silver powder in the printing slurry; the method adopts a large amount of ammoniacal liquor to make catalyst; and cook protective agent with gelatin or oleic acid, obtain the ball shape silver powder of 0.2～1 micron narrowly distributing.Protectant consumption that the method is used is large, causes the surperficial coating of silver powder many, and its thermal weight loss also increases, thereby has reduced the conductive effect of silver powder.That is to say in order to reach the silver powder high dispersive, and lost certain electric property.
The high dispersive silver powder of mentioning among the patent CN 101569937A (a kind of preparation method of high-dispersing silver powder used for conductive silver paste) adopts following method to obtain, namely under the condition that stirs, liquor argenti nitratis ophthalmicus and reducing agent are added in the hyper-dispersant solution simultaneously, in the constant situation of the reaction temperature that keeps reaction system and pH value, by adjusting mixing speed and reaction time, obtain the high dispersive silver powder of the different-grain diameter of 0.1～5.0 μ m.The high score powder that adopts in this invention is a kind of polymer dispersant that contains anchoring group and solvent chain.This dispersant can be realized silver powder fine dispersion in macromolecule resin.But these hyper-dispersants generally need and surfactant emulsification after use, simultaneously and since its minute solvation segment part molecular weight too large, and cause its percent grafting on the silver powder surface not high enough, so can reduce its dispersion effect.
Chinese patent CN 1966586A (a kind of reactive, monodispersed surface modify silver nano-grain and preparation method thereof) with the dialkyl disulfides base for the phosphoric acid modification sodium borohydride the resulting graininess Nano Silver of reduction silver nitrate during as reducing agent.Although the method that this invention provides is simple, and prepared graininess Nano Silver has preferably stability in nonpolar and weak polar solvent, but the preparation cost of the dialkyl dithiophosphoric acid that this invention provides is higher, and mainly be the dispersiveness that improves the graininess Nano Silver, and the not solution of problem of easily assembling after disperseing in polymer for the Nano Silver of the patterns such as wire, bar-shaped, dendroid, hedgehog, cylindrical shape.
A kind of high-temperature sintered silver paste micro silver powder preparation method is disclosed among the Chinese patent CN 101972855A (a kind of high-temperature sintered silver paste micro silver powder preparation method); it prepares first the silvering solution system of colloidal sol shape; the reduction system of colloidal sol shape and protection solution; again the three is mixed; in this invention; by adopting sol-gal process and liquid phase chemical reduction method to be used; course of reaction has been carried out effective control; can be stable carry out suitability for industrialized production; and guarantee to amplify under the production and still can react by pretty space; silver-colored granule-morphology when greatly having improved reaction and the homogeneity of other feature; the cotton-shaped soft-agglomerated silver powder of final generation, but the conductive silver paste of solar battery electrode of processability excellence.This invention provides a kind of highly effective method to go the control that realizes that morphologies, particle diameter and particle diameter distribute, and still chemical modification is not carried out on the surface of silver powder, the problem that existence is easily assembled when therefore using this silver powder, difficulty is disperseed.
In sum: use in the conductive silver paste at electrode of solar battery, silver powder is a kind of very important critical material, present domestic silver powder manufacturer also is being difficult to produce high-quality silver powder for conductive silver paste, because the pattern of silver powder, dispersiveness, particle diameter, particle diameter distribution, surface nature, crystallinity, tap density etc. all have great impact to the electrode performance of conductive silver paste preparation.Especially the pattern of silver powder and dispersiveness thereof have obvious impact to electric conductivity, compactness and electricity conversion after the conductive silver paste film forming.And present domestic enough attention that on the dispersiveness of silver powder for conductive silver paste of solar battery electrode, also do not cause.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, primary and foremost purpose of the present invention is to provide a kind of high dispersive type silver powder, this silver powder has good dispersiveness in polymer, can reduce electrode of solar battery with the silver powder use amount in the conductive silver paste, also can improve its electrical efficiency.
Another object of the present invention is to provide by the preparation-obtained conductive silver paste of solar battery electrode of above-mentioned high dispersive type silver powder.
A further object of the present invention is to provide the preparation method of above-mentioned conductive silver paste of solar battery electrode.
Another purpose of the present invention is to provide the application of above-mentioned conductive silver paste of solar battery electrode.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high dispersive type silver powder is prepared by following methods:
(1) silver powder surface grafting ATRP initator
Get silver powder and join in the solvent orange 2 A, add the ATRP initator again, the mass concentration of control ATRP initator in reactant is 0.5～1.3%, and the mol ratio of silver powder and ATRP initator is 1: 0.4～0.8; This reactant is placed under 20～50 ℃, ultrasonic reaction 3～4 hours, centrifugal afterwards taking precipitate with solvent B washing precipitate, obtains the silver powder of surface grafting ATRP initator;
The silver powder of resulting surface grafting ATRP initator has suc as formula the structure shown in I or the formula II:
Wherein, m=1.5 * 10
4～1.5 * 10
20, y=1 * 10
4～1 * 10
10, x=1.2 * 10
3～1.2 * 10
20, n=0～2, b=1～11;
(2) silver powder external dopant ATRP glycerol polymerization hydrophobic monomer
In the silver powder of surface grafting ATRP initator, add solvent C, hydrophobic monomer and catalyst, pass into inert gas and get rid of oxygen, then add aglucon; Wherein, hydrophobic monomer, catalyst, aglucon, surface grafting have the mol ratio of the silver powder of ATRP initator to be (5～100): (0.1～2): (0.1～3): 1; Above-mentioned reactant was placed 60～120 ℃ of lower stirring reactions 4～48 hours, and centrifugal afterwards taking precipitate is used solvent D washing precipitate again, and sediment 25～60 ℃ of lower vacuum drying, is obtained the high dispersive type silver powder through surface modification;
Resulting high dispersive type silver powder has the structure shown in formula III or formula IV:
Wherein, m=1.5 * 10
4～1.5 * 10
20, y=1 * 10
4～1 * 10
10, x=1.2 * 10
3～1.2 * 10
20,
n＝0～2，b＝1～11；
R is
Wherein, a=180～200, s=0.
The described ATRP initator of step (1) has suc as formula the structure shown in V or the formula VI:
Wherein, b=1～12, n=0～2.
The described ATRP initator of step (1) is prepared by following methods:
Under the condition of anhydrous and oxygen-free gas, will hold mercaptoalcohol to join in solvent orange 2 A and the alkalamides reagent, under 0～35 ℃ of stirring, add alpha-brominated acylbromide.Wherein alkalamides reagent, alpha-brominated acylbromide are (1～2) with the mol ratio of end mercaptoalcohol: (1～2.5): 1, in 0～25 ℃ of lower stirring reaction 1～24 hour, then stop reaction, add and the isopyknic water of solvent orange 2 A, extract again the product of reaction with toluene.Then use the saturated ammonium chloride solution washed product 1～4 time, again with anhydrous magnesium sulfate or anhydrous sodium sulfate drying, again vacuum drying, obtaining colourless oily mater is exactly the needed ATRP initator of holding sulfydryl that contains;
Described end mercaptoalcohol is HS-(CH
2)
n-OH, wherein n=2～12;
Described alkalamides reagent is a kind of in triethylamine, pyridine or the amphetamine;
Described alpha-brominated acylbromide is a kind of in 2 bromo propionyl bromide, 2-bromine butyryl bromide, 2-bromo-3-methylbutyryl bromine, 2-bromine isobutyl acylbromide, 2-bromine isoamyl acylbromide or the 2-bromo-2-methylbutyryl bromine;
Described solvent orange 2 A is a kind of in carrene, chloroform, toluene, cyclohexane, n-hexane, ether, oxolane or the carbon tetrachloride, with using after the anhydrous magnesium sulfate drying;
Described hydrophobic monomer is a kind of in styrene, (methyl) methyl acrylate, dibutene, vinyl acetate, acrylonitrile or (methyl) acrylic acid glycidol ether;
Described catalyst is the lower valency halide of transition metal, the lower valency halide of preferably copper, iron, molybdenum, rhenium, ruthenium, rhodium, nickel, palladium, particularly preferably stannous chloride.
Described aglucon is nitrogen aglucon, nickel/phosphorous ligand or halogen ligands; A kind of in preferred two pyridines, 2 ' 2 bipyridines, hexamethyl triethyl group four ammonia or the triphenyl phosphorus adopts the mode that vacuumizes applying argon gas then except oxygen before using;
Solvent B is a kind of in acetone, dimethyl sulfoxide (DMSO), chloroform or the oxolane;
Solvent C is a kind of in oxolane, acetone, cyclohexanone or the methyl iso-butyl ketone (MIBK);
Solvent D is a kind of in oxolane, acetone, carrene or the chloroform;
The described silver powder of step (1) is the mixture of the silver powder of the silver powder of micron level and Nano grade, and wherein nano-silver powder accounts for the 40-100% of quality of cathode silver; Described Nano grade silver powder is that pattern is one or more the mixture in the Nano grade silver powder of graininess, wire, bar-shaped, resin-like, cubic, octahedra shape or water chestnut column, wherein, (d is the radius of cross-section to granule size d 〉=50nm, the L of Nano Silver 〉=1 μ m, L is the length of Nano Silver), the particle diameter of Nano Silver is distributed as: d ± 20nm; L ± 100nm.
A kind of conductive silver paste of solar battery electrode is prepared by the composition of following mass percent:
Above-mentioned high dispersive type silver powder: 53～61.8%
Glass glue: 21.5～31%
Organic carrier: 15～17.6%;
Described glass glue is grouped into by the one-tenth of following mass percent:
Bi
2O
3：46.7～53％
ZnO：6.8～8.7％
B
2O
3：6.7～7.3％
Al
2O
3：6.5～8.3％
SiO
2：11～14.7％
CaO：7～8％
TiO
2：6～7.3％；
Described organic carrier is more than one mixtures in BC, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol methyl-n-butyl ether acetate, benzinum, turpentine oil, terpinol, castor oil or the cyclohexanone.
The preparation method of described conductive silver paste of solar battery electrode is:
(1) takes by weighing 46.7～53%Bi
2O
3, 6.8～8.7%ZnO, 6.7～7.3%B
2O
3, 6.5～8.3%Al
2O
3, 11～14.7%SiO
2, 7～8%CaO, 6～7.3%TiO
2, above-mentioned oxide is mixed, be heated to 1200 ℃, be incubated 2 hours, then pour in the cold water and quench, the material ball milling that quenches 5 hours, namely get glass glue after the discharging oven dry;
(2) take by weighing 53～61.8% high dispersive type silver powder, 21.5～31% glass glues, 15～17.6% organic carriers, above-mentioned mixing of materials is stirred, until material is silvery white in color, get final product discharging, obtain conductive silver paste of solar battery electrode;
Described percentage is mass percent.
Above-mentioned conductive silver paste of solar battery electrode can be used for preparing solar cell.
Mechanism of the present invention is: silver powder is the critical material in the solar cell conductive silver slurry, and the dispersiveness of silver powder is the key factor that determines resistivity of material and silver powder filling rate.And the method that improves silver powder mainly is the modifying surface to silver powder, and surface modification has again dividing of physical method and chemical method, and wherein the effect of chemical method modification is more obvious.In the method for chemical modification, adopt the method for surperficial initiated polymerization, effect is better.Because surperficial initiated polymerization is first low-molecular-weight initator grafting to be got on, obviously, the low molecule initator of grafting is easier than grafting large molecule surface modifier.ATRP (ATRP) is a kind of controllable/active free radical polymerization method, can prepare the polymer (composition, distribution of sizes, shape, sequence distribution and regularity, side chain and end-group structure) with accurate primary structure, the molecular weight of polymer can by the design prediction, obtain the polymer (M of narrow molecular weight distribution simultaneously
w/ M
n＜1.3), and the mild condition that should react, the MOLECULE DESIGN ability is stronger.The present invention adopts the ATRP technology, at the surperficial initiation grafting hydrophobicity long-chain of silver powder (the Nano grade silver powder that comprises the micro-silver powder of spherical, sheet and graininess, wire, bar-shaped, resin-like, cubic, octahedra shape, water chestnut column).In the hydrophobicity system, has better dispersiveness through the silver powder after the surface modification.Can reduce silver powder filling rate in the solar cell conductive silver slurry, improve electric conductivity.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention adopts high dispersive type silver powder as the conductive filler in the conductive silver paste, can reduce the excess effusion value of silver powder, so that silver powder just can be realized higher conductance and electricity conversion under lower content, therefore can reduce the filling rate of silver powder and the cost of conductive silver paste, also can improve simultaneously the mechanical property of electrode material.
(2) the silver powder surface modification method of the present invention's proposition is to adopt up-to-date surface to cause the ATRP polymerization technique, polymer molecule brush regular, that length is controlled on the surface grafting of silver powder, thus realize the modification on silver powder surface, can improve the dispersiveness of silver powder.Traditional nano-material surface chemic modified method, to utilize first polymerisation to be prepared into required silver powder coating material, being grafted to silver powder gets on (also claiming grafting to method) again, in the method, owing to be connected to the steric restriction effect of lip-deep macromolecular chain, stoped the diffusion of the macromolecular chain in the solution to material surface, thereby suppressed further carrying out of reaction, make the macromolecular chain density of final grafting very low, the polymeric layer of gained is very thin, thereby so that the surface modification effect of silver powder is not good.And the technology (also claiming grafting from method) that adopts this patent to adopt, owing to be first low-molecular-weight initator to be grafted on the surface of silver powder, the trigger monomer controlled large molecule of length that is polymerized again.Therefore there are not the problems referred to above.
(3) the present invention has also adopted Nano Silver as conductive filler in the conductive silver paste, the silver powder of relative micron level, the sintering temperature of nano-silver powder is lower, excess effusion value is also much lower, therefore can realize at a lower temperature the sintering of silver powder, reduce the contact resistance between the silver powder particles, thereby improve the conductance of conductive silver paste.
(4) electrode of solar battery provided by the invention uses conductive silver paste except using polymolecularity silver powder, also used the glass dust of environmental protection as binding agent, the environment-friendly type solvent is as solvent and diluent, preparation silver slurry does not contain the noxious material that RoHS Directive is forbidden, and the content of phthalic acid ester has wherein also reached the standard of European Union, be a kind of conductive silver paste of environment-friendly type, be conducive to the development of China's solar cell industry.
(5) excellent performance of the electrode of solar battery material of the silver powder good dispersion after simple, the modification of silver powder surface modification method provided by the invention, its preparation, the technique that this method provides is simpler, method is more reliable, cost is cheaper.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
The preparation of high dispersive type silver powder
Under the condition of anhydrous and oxygen-free gas, just the sulfydryl lauryl alcohol joins in 20ml carrene, the triethylamine, under 15 ℃ of stirrings, add dibromo isoamyl acylbromide, wherein the mol ratio of triethylamine, dibromo isoamyl acylbromide and sulfydryl lauryl alcohol is 1.5: 2: 1,0 ℃ of lower stirring reaction 24 hours, then stop reaction, the water that adds 20ml, extract again the product of reaction with toluene, and then with saturated ammonium chloride solution washed product 4 times, with anhydrous magnesium sulfate or anhydrous sodium sulfate drying, vacuum drying obtains containing the ATRP initiator A of sulfydryl more again.
The structural formula that can obtain initiator A according to the acylation reaction that occurs between dibromo isoamyl acylbromide and the sulfydryl lauryl alcohol is as follows:
N=2 wherein; B=11.
Line taking shape nano-silver powder (d=60 ± 5nm, then L=1500 ± 50nm) join in the 50g cyclohexane adds initiator A, wherein the mol ratio of silver powder and ATRP initiator A is 1: 0.4, with this system under 25 ℃, ultrasonic reaction 4 hours.Take out product through after centrifugal, use again the acetone washed product 4 times, can get the silver powder of surface grafting ATRP initiator A.
Then join in the 50ml cyclohexanone in the silver powder with surface grafting ATRP initiator A, add styrene and stannous chloride, pass into the inert gas deoxygenation, then 2 ' 2 bipyridines that add deoxygenation, wherein the mol ratio of the silver powder of styrene, stannous chloride, 2 ' 2 bipyridines, surface grafting ATRP initiator A is 5: 0.1: 3: 1,80 ℃ of lower stirring reactions 28 hours, adopt again oxolane washing, then centrifugal, taking precipitate, sediment in 25 ℃ of lower vacuum drying, is obtained the high dispersive type silver powder through surface modification.
After ATRP initiator A and Nano Silver generation bonding reaction, have the reaction of the silver powder surface of ATRP initiator A after causing styrene can obtain the high dispersive type silver powder of following structural formula at surface grafting again:
R is:
M=1.5 * 10 wherein
4Y=1 * 10
10X=1.2 * 10
20N=2; A=200; B=11.
Embodiment 2
The preparation of high dispersive type silver powder
Under the condition of anhydrous and oxygen-free gas, mercaptoethanol is joined in 20ml chloroform, the triethylamine, under 25 ℃ of stirrings, add the dibromo-isobutyl acylbromide, wherein the mol ratio of triethylamine, dibromo-isobutyl acylbromide and mercaptoethanol is 2: 2: 1,8 ℃ of lower stirring reactions 16 hours, then stop reaction, the water that adds 20ml, extract again the product of reaction with toluene, then use saturated ammonium chloride solution washed product 4 times, with anhydrous magnesium sulfate or anhydrous sodium sulfate drying, vacuum drying obtains containing the ATRP initiator B of sulfydryl more again.
The structure of initiator formula that can obtain the ATRP initiator B according to the acylation reaction that occurs between dibromo-isobutyl acylbromide and the mercaptoethanol is as follows:
B=12 wherein
Get rod-like nano silver powder (d=100 ± 15nm, L=15000 ± 65nm) and micro-silver powder (d=1.5 ± 0.150 μ m) join in the 50g chloroform, wherein the mol ratio of silver powder and ATRP initator is 1: 0.5, then add the 0.38g initiator B, with this system under 20 ℃, ultrasonic 4 hours.Take out product through after centrifugal, use again the dimethyl sulfoxide (DMSO) washed product 4 times, can get the silver powder of surface grafting ATRP initiator B.
Then will add in the silver powder of surface grafting ATRP initiator B in the 80ml acetone, then add methyl methacrylate and stannous chloride, pass into the inert gas deoxygenation, then hexamethyl triethyl group four ammonia that add deoxygenation, the wherein silver powder 100: 2: 3 of methyl methacrylate, stannous chloride, hexamethyl triethyl group four ammonia, surface grafting ATRP initiator B: 1; 100 ℃ of lower stirring reactions 16 hours, adopt again the chloroform washing, centrifugal, taking precipitate in 60 ℃ of lower vacuum drying, obtains the high dispersive type silver powder through surface modification with sediment.
After ATRP initiator B and Nano Silver generation bonding reaction, have the reaction of the silver powder surface of ATRP initiator B after causing styrene can obtain the high dispersive type silver powder of following structural formula at surface grafting again:
R is:
M=1 * 10 wherein
20Y=1 * 10
4X=1.2 * 10
3N=2; A=200; B=1
Embodiment 3
The preparation of high dispersive type silver powder
Under the condition of anhydrous and oxygen-free gas, sulfydryl eight alcohol are joined in 20ml toluene, the amphetamine, under 35 ℃ of stirrings, add 2 bromo propionyl bromide, wherein the mol ratio of amphetamine, 2 bromo propionyl bromide and sulfydryl eight alcohol is 1: 2.5: 1,16 ℃ of lower stirring reactions 8 hours, then stop reaction, the water that adds 20ml, extract again the product of reaction with toluene, then washing 4 times with saturated ammonium chloride solution, with anhydrous magnesium sulfate or anhydrous sodium sulfate drying, vacuum drying obtains containing the ATRP initator C of sulfydryl more again.
The structure of initiator formula that can obtain ATRP initator C according to the acylation reaction that occurs between 2 bromo propionyl bromide and sulfydryl eight alcohol is as follows:
Get the dendritic nano-silver powder (d=40 ± 15nm, then L=1000 ± 50nm) join in the 50g ether adds initator C, wherein the mol ratio of silver powder and ATRP initator is 1: 0.6, with this system under 50 ℃, ultrasonic 3 hours.Through taking out product after centrifugal, washed product is 4 times in using chloroform, can get the silver powder of surface grafting ATRP initator C.
Then will add in the silver powder of surface grafting ATRP initator C in the 50ml cyclohexanone, then add acrylonitrile and stannous chloride, pass into the inert gas deoxygenation, then the triphenyl phosphorus that adds deoxygenation, wherein the mol ratio of the silver powder of ATRP initator C is arranged is 100: 1: 2 for acrylonitrile, stannous chloride, triphenyl phosphorus, surface grafting: 1; 120 ℃ of lower stirring reactions 4 hours, adopt again the acetone washing, centrifugal, taking precipitate in 50 ℃ of lower vacuum drying, obtains the polymolecularity silver powder through surface modification with sediment.
After ATRP initator C and Nano Silver generation bonding reaction, have the reaction of the silver powder surface of ATRP initator C after causing styrene can obtain the high dispersive type silver powder of following structural formula at surface grafting again:
R is:
M=1.5 * 10 wherein
20Y=1 * 10
8X=1.2 * 10
5A=200; B=7.
Embodiment 4
The preparation of high dispersive type silver powder
Under the condition of anhydrous and oxygen-free gas, mercaptoethanol is joined in 20ml oxolane, the triethylamine, under 0 ℃ of stirring, add 2-bromo-2-methylbutyryl bromine, wherein the mol ratio of triethylamine, 2-bromo-2-methylbutyryl bromine and mercaptoethanol is 1: 2.5: 1,25 ℃ of lower stirring reactions are 1 hour again, then stop reaction, the water that adds 20ml, extract again the product of reaction with toluene, and then with saturated ammonium chloride solution washing 4 times, again with anhydrous magnesium sulfate or anhydrous sodium sulfate drying, vacuum drying obtains containing the ATRP initator E of sulfydryl again.
The structure of initiator formula that can obtain ATRP initator C according to the acylation reaction that occurs between 2-bromo-2-methylbutyryl bromine and the mercaptoethanol is as follows:
Get flake silver powder (d=0.5～1 μ m, average grain diameter is at 0.8 μ m) and the wire Nano Silver join in the 50g n-hexane, wherein the mol ratio of silver powder and ATRP initator is 1: 0.8, then add 0.28g initator E, this system under 40 ℃, ultrasonic 3.5 hours, is taken out product after process is centrifugal, washed product is 4 times in using oxolane, can get the silver powder of surface grafting ATRP initator E.
Then will add in the silver powder of surface grafting ATRP initator E in the 60ml methyl iso-butyl ketone (MIBK), then add vinyl acetate and stannous chloride, pass into the inert gas deoxygenation, then the two pyridines that add deoxygenation, wherein the mol ratio of the silver powder of ATRP initator E is arranged is 50: 1: 0.1 for vinyl acetate, stannous chloride, two pyridine, surface grafting: 1; 60 ℃ of lower stirring reactions 48 hours, adopt again washed with dichloromethane, centrifugal, taking precipitate in 40 ℃ of lower vacuum drying, obtains the polymolecularity silver powder through surface modification with sediment.
After ATRP initator E and Nano Silver generation bonding reaction, have the reaction of the silver powder surface of ATRP initator E after causing styrene can obtain the high dispersive type silver powder of following structural formula at surface grafting again:
R is:
M=1.5 * 10 wherein
8Y=1 * 10
6X=1.2 * 10
5A=180; B=1
Embodiment 5
The preparation of conductive silver paste of solar battery electrode
Prepare conductive silver paste of solar battery electrode with the resulting high dispersive type of embodiment 1-4 silver powder.The raw material of conductive silver paste of solar battery electrode forms as shown in table 1, and its preparation method is as described below:
Take by weighing Bi according to table 1
2O
3, ZnO, B
2O
3, Al
2O
3, SiO
2, CaO, TiO
2, the crucible and be placed on and be heated to 1200 ℃ in the high temperature resistance furnace of packing into after these oxides are mixed is incubated 2 hours.Then above-mentioned material is poured in the cold water rapidly and quenched, the material ball milling that quenches 5 hours, just make glass glue after the discharging oven dry.
Take by weighing high dispersive type silver powder, glass glue, organic carrier according to proportioning in the table 1 again, be positioned in the homogenizer and stir, and then it is transferred to continue on the muller to mix, until occur silvery white, get final product discharging, obtain conductive silver paste of solar battery electrode;
The performance of prepared conductive silver paste is also in table 1.
Table 1 (unit: g)
In sum, the conductive silver paste of solar battery electrode that adopts high dispersive type silver powder of the present invention to prepare, can be under lower silver powder filling rate (about 55%), just can realize preferably conductance (resistance per square is about 4m Ω), therefore can improve the dispersiveness of silver powder through the mode that adopts surperficial initiated polymerization, thereby under low filling rate, realize high electrical conductivity.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. high dispersive type silver powder it is characterized in that being prepared by following steps:
(1) get silver powder and join in the solvent orange 2 A, add the ATRP initator again, the mass concentration of control ATRP initator in reactant is 0.5～1.3%, and the mol ratio of silver powder and ATRP initator is 1: 0.4～0.8; This reactant is placed under 20～50 ℃, ultrasonic reaction 3～4 hours, centrifugal afterwards taking precipitate with solvent B washing precipitate, obtains the silver powder of surface grafting ATRP initator;
(2) in the silver powder of surface grafting ATRP initator, add solvent C, hydrophobic monomer and catalyst, pass into inert gas and get rid of oxygen, then add aglucon; Wherein, hydrophobic monomer, catalyst, aglucon, surface grafting have the mol ratio of the silver powder of ATRP initator to be (5～100): (0.1～2): (0.1～3): 1; These reactants were placed 60～120 ℃ of lower stirring reactions 4～48 hours, and centrifugal afterwards taking precipitate with solvent D washing precipitate, 25～60 ℃ of lower vacuum drying, obtains high dispersive type silver powder with sediment;
Described solvent orange 2 A is a kind of in carrene, chloroform, toluene, cyclohexane, n-hexane, ether, oxolane or the carbon tetrachloride, uses after dry;
Described silver powder is the mixture of micro-silver powder and nano-silver powder, and wherein nano-silver powder accounts for the 40-100% of quality of cathode silver;
Described hydrophobic monomer is a kind of in styrene, (methyl) methyl acrylate, dibutene, vinyl acetate, acrylonitrile or (methyl) acrylic acid glycidol ether;
Described catalyst is the lower valency halide of transition metal;
Described aglucon is nitrogen aglucon, nickel/phosphorous ligand or halogen ligands;
Described solvent B is a kind of in acetone, dimethyl sulfoxide (DMSO), chloroform or the oxolane;
Described solvent C is a kind of in oxolane, acetone, cyclohexanone or the methyl iso-butyl ketone (MIBK);
Described solvent D is a kind of in oxolane, acetone, carrene or the chloroform.
2. described a kind of high dispersive type silver powder according to claim 1, it is characterized in that: described ATRP initator is prepared by following methods:
Under the condition of anhydrous and oxygen-free gas, to hold mercaptoalcohol to join in solvent orange 2 A and the alkalamides reagent, under 0～35 ℃ of stirring, add alpha-brominated acylbromide, wherein alkalamides reagent, alpha-brominated acylbromide are (1～2) with the mol ratio of end mercaptoalcohol: (1～2.5): 1, in 0～25 ℃ of lower stirring reaction 1～24 hour, then add and the isopyknic water of solvent orange 2 A, add again toluene and extract the product of reaction, use the saturated ammonium chloride solution washed product, product is dry, obtain the ATRP initator;
Described end mercaptoalcohol is HS-(CH
2)
n-OH, wherein n=2～12;
Described alkalamides reagent is a kind of in triethylamine, pyridine or the amphetamine;
Described alpha-brominated acylbromide is a kind of in 2 bromo propionyl bromide, 2-bromine butyryl bromide, 2-bromo-3-methylbutyryl bromine, 2-bromine isobutyl acylbromide, 2-bromine isoamyl acylbromide or the 2-bromo-2-methylbutyryl bromine.
3. a conductive silver paste of solar battery electrode is characterized in that: be to be prepared by high dispersive type silver powder claimed in claim 1.
4. described a kind of conductive silver paste of solar battery electrode according to claim 3 is characterized in that: be that composition by following mass percent prepares:
High dispersive type silver powder claimed in claim 1: 53～61.8%
Glass glue: 21.5～31%
Organic carrier: 15～17.6%.
5. described a kind of conductive silver paste of solar battery electrode according to claim 4, it is characterized in that: described glass glue is grouped into by the one-tenth of following mass percent:
Bi
2O
3：46.7～53％
ZnO：6.8～8.7％
B
2O
3：6.7～7.3％
Al
2O
3：6.5～8.3％
SiO
2：11～14.7％
CaO：7～8％
TiO
2：6～7.3％。
6. described a kind of conductive silver paste of solar battery electrode according to claim 4, it is characterized in that: described organic carrier is more than one mixtures in BC, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol methyl-n-butyl ether acetate, benzinum, turpentine oil, terpinol, castor oil or the cyclohexanone.
7. the preparation method of each described conductive silver paste of solar battery electrode of claim 3-6 is characterized in that may further comprise the steps:
(1) takes by weighing 46.7～53%Bi
2O
3, 6.8～8.7%ZnO, 6.7～7.3%B
2O
3, 6.5～8.3%Al
2O
3, 11～14.7%SiO
2, 7～8%CaO, 6～7.3%TiO
2, these oxides are mixed, be heated to 1200 ℃, be incubated 2 hours, then pour in the cold water and quench, the material ball milling that quenches 5 hours, namely get glass glue after the discharging oven dry;
(2) take by weighing 53～61.8% high dispersive type silver powder, 21.5～31% glass glues, 15～17.6% organic carriers, these mixing of materials are stirred, until material is silvery white in color, get final product discharging, obtain conductive silver paste of solar battery electrode;
Percentage described in step (1) and (2) is mass percent.
8. the application of each described conductive silver paste of solar battery electrode of claim 3-6.
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| CN103586456B (en) * | 2013-11-07 | 2016-01-20 | 中科院广州化学有限公司 | A kind of High-dispersity silver powder and preparation method thereof and application |
| TWI576862B (en) * | 2013-07-19 | 2017-04-01 | 第一毛織股份有限公司 | Composition for solar cell electrodes and electrode fabricated using the same |
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