CN102174241A - Silver paste for photovoltaic assembly - Google Patents
Silver paste for photovoltaic assembly Download PDFInfo
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- CN102174241A CN102174241A CN 201010616218 CN201010616218A CN102174241A CN 102174241 A CN102174241 A CN 102174241A CN 201010616218 CN201010616218 CN 201010616218 CN 201010616218 A CN201010616218 A CN 201010616218A CN 102174241 A CN102174241 A CN 102174241A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses silver paste for a photovoltaic assembly. The silver paste is characterized by being prepared by mixing the following materials in percentage by weight: 60-85% of silver powder, 10-30% of resin, 1-5% of modifier, 3-8% of crosslinking agent, 0.001-0.01% of catalyst, 0.5-2% of tackifier, 0.5-3% of dispersant, 2-15% of silicone oil and 2-10% of other auxiliary materials. The silver powder with the particle size of 60nm-30mum is preferentially selected, the copolymer of bisphenol-A cyanate ester and epoxy resin is modified by the modifier to improve the curing properties of the resin. The crosslinking agent matched with the modified copolymer is preferentially selected, and a proper amount of catalyst is added to improve the curing speed. A certain amount of dispersing agent is added to the reaction system of the silver paste, thus the product is more uniform after being mixed. A proper amount of tackifier is added to improve the binding power of the product, and a certain amount of auxiliary materials is additionally added to improve the storage stability, the printing performance and the conductivity of the product.
Description
Technical field
The invention belongs to macromolecular material, relate to solar photovoltaic assembly load material field, refer in particular to a kind of EVA film that is used for the photovoltaic module conduction.
Background technology
Never just like the such incident of Copenhagen meeting in the end of the year 2009, wordings such as " energy-saving and emission-reduction ", " low-carbon (LC) " so are rooted in the hearts of the people on the human history, development of global economy direction and range marks have also turned to low-carbon economy already.Sun power is one of following low-carbon (LC) ideal of society energy as a kind of renewable energy source of cleaning, just more and more is subjected to the attention of countries in the world instantly.
Because solar energy resources is inexhaustible, the photovoltaic generation process pollution-free, do not have advantages such as discharging, noiselessness, become the renewable energy technologies of tool Sustainable development feature and the focus that application is competitively studied in countries in the world.Along with the continuous progress of photovoltaic technology, photoelectric transformation efficiency day by day improves, and solar cell of new generation emerges in large numbers, and production and application cost reduce significantly, and photovoltaic generation is expected to change to substitute energy from replenishing the energy, and market outlook are very wide.
Under the support energetically of national governments, the photovoltaic industry has obtained development fast.2006 to 2009, the average growth rate per annum of solar-energy photo-voltaic cell output was 60%.Owing to be subjected to the influence of financial crisis in 2008; before 2009 two seasons photovoltaic cell output rate of growth slow down to some extent; but along with the recovery of the market requirement second half year in 2009, annual solar cell yield had reached 10431MW in 2009, increased by 42.5% than 2008.
The cost of solar energy power generating at present approximately is 11-18 a times of coal-fired cost, and therefore the development of various countries' photovoltaic industry at present relies on the subsidy of government mostly, and the subsidy scale of government is determining the development scale of the photovoltaic industry of this country.At present on the subsidy dynamics of government, with the supporting dynamics maximum of developed countries such as Germany, Spain, France, the U.S., Japan.2008, Spain released munificent photovoltaic industry subsidy policy, made its domestic photovoltaic industry the explosive type momentum of development occur, had once occupied three/the last one of world's photovoltaic cell output.German photovoltaic module installation in 2009 accounts for 50.4% of the total installation in the whole world up to 3200MW.
At present, China has formed complete photovoltaic industrial chain.On industrial pattern, the domestic Yangtze River Delta, the ring Bohai Sea, Pearl River Delta and central and west regions had formed the regional industrial cluster that differs from one another already, and had emerged a collection of esbablished corporation.Chinese solar cell yield was 9300MW in 2009, accounted for more than 40% of global ultimate production, had become global solar battery production first big country.
Though present Chinese photovoltaic industry size occupies the whole world the first, the industrial chain development is inharmonious, and industry overall technology weakness.In the production of the polysilicon of whole photovoltaic industrial chain technology barriers maximum, what external leading firm adopted is enclosed improvement siemens method, and this is still blank in China.What the production of polysilicon enterprise of China used mostly is directly or the purification techniques of the Muscovite polysilicon of introducing indirectly, its cost height, energy consumption,, repeated construction is serious, be in a disadvantageous position in whole international competition, this also is the major cause that the polysilicon production capacity surplus appears in China at the beginning of 2009.
Secondly, Chinese domestic at present solar cell market scale is less, and 97% of the solar-energy photo-voltaic cell of domestic production has all exported to the market abroad.The industry development pattern of this transition export dependence causes industry very risky, is subject to the influence of international demand quantitative changeization.As in global financial crisis in 2008, subdued price subsidy because of western countries to photovoltaic, directly caused the bankruptcy of Chinese many photovoltaic enterprise.
China's photovoltaic industry has obtained fast development in recent years, and the demand that has also driven the peripheral product of photovoltaic industry increases sharply, and this is comprising the photovoltaic production unit, and solar cell, assembly are produced raw and auxiliary material etc.Wherein, most equipment and consumptive material are realized production domesticization fully, but still have small part equipment and raw and auxiliary material because gordian technique is grasped and limited by offshore company always, and domestic not tackling key problem as yet is difficult to realize production domesticization.Silver paste of solar cells is one of them.
The silver paste of solar cells technology of preparing is the gordian technique of high-efficiency low-cost solar battery, and silver paste of solar cells is made the main raw material(s) of solar cell especially.Silver paste of solar cells is basically by U.S. DUPANT, U.S. FERRO and this three companies monopolization of German Hereaus in the market.On silver paste of solar cells market, made in China still is in space state, the used silver slurry of domestic manufacture of solar cells is all to adopt import, cause silver paste of solar cells to become than the also higher starting material of the external interdependency of polycrystalline silicon material, serious restriction the development and the growth of China's photovoltaic industry.
Summary of the invention
The objective of the invention is to,, provide a kind of printable silver slurry that is used for photovoltaic module, after heat is solidified, have good electroconductibility, cohesive force and surface finish at the above-mentioned defective of prior art.
In order to achieve the above object, the technical solution used in the present invention is as follows: a kind of silver slurry that is used for photovoltaic module, it is characterized in that, and adopt following material to be mixed and made into by weight percentage: silver powder 60-85%, resin 10-30%, properties-correcting agent 1-5%, linking agent 3-8%, catalyzer 0.001-0.01%, tackifier 0.5-2%, dispersion agent 0.5-3%, silicone oil 2-15%, other subsidiary material 2-10%.
Preferable particle size is at the silver powder of 60nm-30um, utilize properties-correcting agent that the interpolymer of bisphenol A cyanate ester and Resins, epoxy is carried out modification, improve the curing performance of resin, preferably with modification after the linking agent that is complementary of interpolymer, add appropriate amount of catalysts and improve curing speed, because system of the present invention contains a large amount of solids and other material, add certain amount of dispersant, more even after making product mix, for further improving the cohesive force of product, we add an amount of tackifier, auxiliary simultaneously a certain amount of subsidiary material, the stability in storage of raising product of adding, printing performance and conductivity.
The present invention selects for use the interpolymer of bisphenol A cyanate ester and Resins, epoxy to be the bonding base mateiral, its existing good cohesive force, anti-oxidant, corrosion resistant characteristic, and in the present invention, the interpolymer addition is 10-30%.Discover, use polysilsesquioxane that it is carried out modification, can significantly improve the wet-hot aging performance of interpolymer, thereby improve the weathering resistance of product, and behind high temperature (280-400 ℃) sintering, compare with the interpolymer of not process modification, have better thermotolerance.In test, we are based on the epoxy group(ing) silsesquioxane, compound interpolation polyphenylene silsesquioxane, poly methyl silsesquioxane, eight vinyl cagelike silsesquioxanes, add to its modification, to reach cohesive strength, flexible unification.In the present invention, the properties-correcting agent addition is 1-5%
In order to make the interpolymer after linking agent and the modification that good matching property be arranged, through repetition test, our preferred silsesquioxane type linking agent is as the linking agent of this system.We preferably have the cage-type silsesquioxane that has terminal hydroxy group or end amino, through to multiple silsesquioxane and test, we optimize seven poly-cage-type silsesquioxane three silanols, eight hydroxyl cagelike silsesquioxanes, ten diamino cagelike silsesquioxanes, they have good rate of crosslinking and degree of crosslinking to the modified copolymer body, and has very little shrinkability after crosslinked, in the present invention, addition is 3-8%.
For the further rate of crosslinking of control product, we according to actual needs, selectivity is added catalyzer, in the present invention, our triphenylphosphine platinum chloride of preferred 1%, addition is 0.1-1%.
In the system of the present invention, existing a large amount of solid particulate also has many organic materialss, comprise solvent etc., make that product has good homogeneous, not only need solvent and filler to regulate the denseness of product, can also suitably add dispersion agent, improve and stir and the homogeneity between the shelf lives.
Stearylamide and higher alcohols are also used, can obviously improve the oilness and the thermostability of system of the present invention, in the present invention, our preferred organic dispersing agent comprises hexenyl bis-stearamides, glyceryl monostearate, Tristearoylglycerol, oleic acid acyl, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, guar gum, fatty acid polyglycol ester.In the present invention, above material mixing addition is 0.5-3%
Test is found, base mateiral system of the present invention, and behind high temperature sintering, because the resistance to elevated temperatures of interpolymer system itself is relatively poor, its cohesive force declines to a great extent, and we are some tackifier preferably, can increase the cohesive force of product and substrate behind the high temperature sintering.In the present invention, tackifier are meant following one or more mixture: γ-[(2,3)-epoxy third oxygen] propyl-triethoxysilicane, N-aniline propyl-triethoxysilicane, addition are 0.5-2%.
Add certain amount of solvent and filler as subsidiary material, can regulate the denseness of product, be beneficial to printing.Quaternary cationics, not only reduce the surface energy of system, increase the intermiscibility of solid particulate and solvent system, and quaternary cationics has certain electroconductibility, it can increase the electroconductibility of product system after test was found to solidify.
Have a certain amount of ester group or soap base on the long chain molecule of oxidized polyethlene wax, thus inside and outside lubrication comparison balance, effect is better, and its transparency might as well.Be equipped with a spot of polyoxyethylene fatty amine, can further improve the homogeneity and the stability in storage of product.
Preferred solvent of the present invention is: fatty alcohol-polyoxyethylene ether, diethylene glycol monobutyl ether and isomery C13 Soxylat A 25-7, these high boiling solvents can increase the flowability of product.Among the present invention, selecting Shawinigan black for use is filler, because Shawinigan black not only can increase denseness, and has conductivity.In the present invention, add a certain amount of hydrogenated castor oil simultaneously, not only can further improve the homogeneity of product, and significantly increase the thixotropy of product, thereby improve the impressionability energy of product.
Above subsidiary material mix interpolation according to actual needs, and overall addition is controlled at 2-10% and is advisable.
This product is behind 350-400 ℃ of sintering, and not only conductivity and cohesive force are more outstanding, and surfacing, shrinking percentage are little, inner no bubble, and anti-oxidant and cold-resistant thermal cycling characteristic is good.Be applicable to that the higher photovoltaic solar group line of conductivity requirement connects.
Embodiment
Embodiment 1
At first utilize 1 part of poly methyl silsesquioxane and 1.5 part of eight vinyl cagelike silsesquioxane that 20 parts of bisphenol A cyanate esters and Resins, epoxy interpolymer are carried out modification.
In addition in the interpolymer after modification, add 2 part of seven poly-cage-type silsesquioxane three silanol, 1.5 part ten diamino cagelike silsesquioxanes, 0.7 part γ-[(2,3)-and epoxy third oxygen] propyl-triethoxysilicane, 0.6 part N-aniline propyl-triethoxysilicane, 0.8 the triphenylphosphine platinum chloride solution of part 1%, 0.3 part glyceryl monostearate, 0.4 part oleic acid acyl, 0.5 part methyl amyl alcohol, 0.2 part fatty acid polyglycol ester, 0.6 part quaternary cationics, 0.5 part polyoxyethylene fatty amine, 0.2 part fatty alcohol-polyoxyethylene ether, 0.3 part of isomery C13 Soxylat A 25-7,0.6 part hydrogenated castor oil, 1.2 part Shawinigan black, 67.1 part silver powder
This product not only has good conductivity and cohesive force behind 300-400 ℃ of sintering, and surfacing, shrinking percentage are little, inner no bubble.Be applicable to the connection of most of photovoltaic solar group lines, and have good anti-oxidant and weather resisteant energy.
Embodiment 2
At first utilize 1.5 parts of polyphenylene silsesquioxanes and 1 part of eight vinyl cagelike silsesquioxane that 17 parts of bisphenol A cyanate esters and Resins, epoxy interpolymer are carried out modification.
In addition in the interpolymer after modification, add 1.5 part of seven poly-cage-type silsesquioxane three silanol, 1.5 part eight hydroxyl cagelike silsesquioxanes, 0.5 part γ-[(2,3)-and epoxy third oxygen] propyl-triethoxysilicane, 0.9 part N-aniline propyl-triethoxysilicane, 0.7 the triphenylphosphine platinum chloride solution of part 1%, 0.4 part hexenyl bis-stearamides, 0.3 part Tristearoylglycerol, 0.5 part methyl amyl alcohol, 0.3 triethyl hexyl phosphoric acid, 0.7 part quaternary cationics, 0.3 part polyoxyethylene fatty amine, 0.5 part fatty alcohol-polyoxyethylene ether, 0.4 part of isomery C13 Soxylat A 25-7,0.7 part hydrogenated castor oil, 1 part of Shawinigan black, 70.3 part silver powder
This product not only has good conductivity and cohesive force behind 350-400 ℃ of sintering, and surfacing, shrinking percentage are little, inner no bubble, and anti-oxidant and wet-hot aging performance is given prominence to.Be applicable to that the high photovoltaic solar group line of moisture-proof heat request connects.
This product has good cold-resistant thermal cycling characteristic, is applicable to the encapsulation of photovoltaic solar assembly under the extremely hot and cold circulation weather condition, and has good anti-xanthochromia, ageing resistance.
Embodiment 3
At first utilize 1 part of polyphenylene silsesquioxane and 1 part of eight vinyl cagelike silsesquioxane that 15 parts of bisphenol A cyanate esters and Resins, epoxy interpolymer are carried out modification.
In addition in the interpolymer after modification, add 1.2 part of seven poly-cage-type silsesquioxane three silanol, 1.3 part eight hydroxyl cagelike silsesquioxanes, 1 part of γ-[(2,3)-and epoxy third oxygen] propyl-triethoxysilicane, 0.5 part N-aniline propyl-triethoxysilicane, 0.3 the triphenylphosphine platinum chloride solution of part 1%, 0.5 part oleic acid acyl, 0.2 part Tristearoylglycerol, 0.5 part methyl amyl alcohol, 0.3 derivatived cellulose, 0.3 part guar gum, 0.9 part quaternary cationics, 0.5 part polyoxyethylene fatty amine, 0.2 part fatty alcohol-polyoxyethylene ether, 0.5 part of isomery C13 Soxylat A 25-7,0.8 part hydrogenated castor oil, 1.5 part Shawinigan black, 72.5 part silver powder.
Claims (9)
1. a silver that is used for photovoltaic module is starched, it is characterized in that, adopt following material to be mixed and made into by weight percentage: silver powder 60-85%, resin 10-30%, properties-correcting agent 1-5%, linking agent 3-8%, catalyzer 0.001-0.01%, tackifier 0.5-2%, dispersion agent 0.5-3%, silicone oil 2-15%, other subsidiary material 2-10%.
2. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that described silver powder is meant the silver powder of diameter at 60nm-30um, addition is 60-85%.
3. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that described resin is meant bisphenol A cyanate ester and Resins, epoxy interpolymer, addition is 10-30%.
4. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that, described properties-correcting agent is meant following one or several mixture: polyphenylene silsesquioxane, poly methyl silsesquioxane with eight vinyl cagelike silsesquioxanes, addition is 1-5%.
5. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that, described linking agent is meant following one or several mixture: seven poly-cage-type silsesquioxane three silanols, eight hydroxyl cagelike silsesquioxanes and ten diamino cagelike silsesquioxanes, addition is 3-8%.
6. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that described tackifier are meant following one or more mixture: γ-[(2,3)-epoxy third oxygen] propyl-triethoxysilicane, N-aniline propyl-triethoxysilicane, addition are 0.5-2%.
7. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that described catalyzer is meant: 1% triphenylphosphine platinum chloride, addition are 0.1-1%.
8. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that, described dispersion agent is meant following one or more mixture: hexenyl bis-stearamides, glyceryl monostearate, Tristearoylglycerol, oleic acid acyl, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, guar gum, fatty acid polyglycol ester, addition is 0.5-3%.
9. according to the described silver slurry that is used for photovoltaic module of claim 1, it is characterized in that, described other subsidiary material comprise: quaternary cationics, polyoxyethylene fatty amine, fatty alcohol-polyoxyethylene ether, isomery C13 Soxylat A 25-7, diethylene glycol monobutyl ether, hydrogenated castor oil, Shawinigan black, addition is 2-10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010616218.1A CN102174241B (en) | 2010-12-31 | 2010-12-31 | Silver paste for photovoltaic assembly |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010616218.1A CN102174241B (en) | 2010-12-31 | 2010-12-31 | Silver paste for photovoltaic assembly |
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| CN102174241A true CN102174241A (en) | 2011-09-07 |
| CN102174241B CN102174241B (en) | 2015-04-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602215A (en) * | 2013-10-28 | 2014-02-26 | 江苏达胜热缩材料有限公司 | Modified epoxy primer |
| CN105609163A (en) * | 2015-12-23 | 2016-05-25 | 东莞珂洛赫慕电子材料科技有限公司 | High-temperature resistant conductive silver paste and preparation method thereof |
| CN105802563A (en) * | 2016-04-20 | 2016-07-27 | 烟台德邦科技有限公司 | Flowing type chip-grade bottom filling adhesive and preparation method thereof |
| CN109215842A (en) * | 2017-05-14 | 2019-01-15 | 吴彬 | A kind of lower conductive silver paste of resistivity |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602215A (en) * | 2013-10-28 | 2014-02-26 | 江苏达胜热缩材料有限公司 | Modified epoxy primer |
| CN105609163A (en) * | 2015-12-23 | 2016-05-25 | 东莞珂洛赫慕电子材料科技有限公司 | High-temperature resistant conductive silver paste and preparation method thereof |
| CN105802563A (en) * | 2016-04-20 | 2016-07-27 | 烟台德邦科技有限公司 | Flowing type chip-grade bottom filling adhesive and preparation method thereof |
| CN105802563B (en) * | 2016-04-20 | 2018-11-06 | 烟台德邦科技有限公司 | A kind of flow model chip-level bottom filling adhesive and preparation method thereof |
| CN109215842A (en) * | 2017-05-14 | 2019-01-15 | 吴彬 | A kind of lower conductive silver paste of resistivity |
| CN109215842B (en) * | 2017-05-14 | 2021-10-26 | 吴彬 | Conductive silver paste with lower resistivity |
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| Publication number | Publication date |
|---|---|
| CN102174241B (en) | 2015-04-22 |
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