CN102136308B - Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste - Google Patents
Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste Download PDFInfo
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- CN102136308B CN102136308B CN2010105553313A CN201010555331A CN102136308B CN 102136308 B CN102136308 B CN 102136308B CN 2010105553313 A CN2010105553313 A CN 2010105553313A CN 201010555331 A CN201010555331 A CN 201010555331A CN 102136308 B CN102136308 B CN 102136308B
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Abstract
The invention discloses an organic carrier for conductive silver paste applied to a front face electrode and a grid line of a solar cell, a preparation method of the organic carrier, silver paste containing the organic carrier and a solar cell manufactured from the silver paste. The organic carrier comprises the following components in percentage by weight: 60-75 percent of solvent, 1-10 percent of thickener, 0.3-5 percent of thixotropic agent, 1-5 percent of surfactant and 10-30 percent of plasticizer. The preparation method of the organic carrier comprises the following steps of: weighing various raw materials; adding various aids into a solvent respectively; and heating and stirring until the aids are dissolved completely. The organic carrier has proper viscosity and a simple preparation process. Paste prepared from the organic carrier has proper viscosity, fineness, leveling property, thixotropy and chemical stability. After the paste is subjected to screen printing and sintering on a cell substrate, the thicknesses of a front face electrode and a grid line thick film of a cell panel can be over 20 micros, and the prepared electrode and the grid line thick film can obtain a higher height-width ratio.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of front electrode of solar battery and grid line conductive silver paste with organic carrier and preparation method thereof with contain the silver paste of this organic carrier and contain the solar cell that this silver paste is made.
Background technology
Solar energy is a kind of green energy resource, and is pollution-free, inexhaustible because of it, do not receive advantages such as region resource limit more and more to receive people's attention, so solar cell has arisen at the historic moment.Solar cell is a kind of semiconductor device that can solar energy converting be become electric energy, and solar cell can produce electric current under the condition of illumination, electric collecting is got up and transfers out through grid line and electrode.Solar cell just, backplate and grid line all be to be processed by technologies such as the silk screen printing of conductive silver paste through high-speed, high precision, low temperature drying, high temperature sinterings.
Conductive silver paste mainly is made up of conductive phase, bonding phase and organic carrier, and conductive phase is used silver powder always, and bonding generally adopts glass dust mutually, when high temperature sintering, melts, and between silver powder and silicon base, forms ohmic contact.
Organic carrier is the polymer solution that is dissolved in organic solvent; It is the conductive phase and the carrier of particulate mutually that bonds, and plays the rheological behavior of control slurry, the viscosity of regulating slurry; With the conductive phase that makes solid forms, bonding mutually and the solid particulate mixture of other effects wrap up equably and be dispersed into slurry with fluid behaviour; Make conductive silver paste be not easy to produce deposition and oxidation so that high-speed, high precision be printed onto on the substrate, form required conductive pattern.Organic carrier mainly is made up of organic solvent and thickener, in order to improve the operating characteristics of slurry, also can add some other auxiliary agents; So the selection of solvent and various auxiliary agents and the important that just seems of filling a prescription.Organic carrier about solar cell size; One Chinese patent application numbers 200810025430.3, denomination of invention: high-viscosity solar cell front side silver paste and preparation method thereof; Introduced a kind of used organic carrier of silver slurry for preparing; This organic carrier is formulated by organic solvent and organic additive, in its organic additive by as the castor oil of rheological agent, form as a kind of in ethyl cellulose, dibutyl phthalate, acroleic acid resin or the polybutene butyral of thickener or their combination.This organic carrier is used to prepare full-bodied solar cell front side silver paste; Viscosity reaches 220-300Pa.s, though this full-bodied silver paste can make the solar energy front electrode of printing be not easy to cave in, owing to be not easy printing behind the viscosity height; Influence print speed printing speed, reduce production efficiency.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned defective that exists in the prior art; Provide a kind of front electrode of solar battery and grid line conductive silver paste with organic carrier and preparation method thereof with contain the silver paste of this organic carrier and contain the solar cell that this silver paste is made; Silver paste modest viscosity with this organic carrier preparation; Printing performance is good, is not easy to produce deposition and oxidation, and the electrode of gained and grid line have big depth-width ratio behind the sintering.
Solving the technical scheme that technical problem of the present invention adopted is that this front electrode of solar battery and grid line conductive silver paste are used organic carrier; Comprise solvent and auxiliary agent; Described auxiliary agent comprises thickener, thixotropic agent, surfactant, plasticizer, and the weight percentage of each component is solvent 60～75%, thickener 1～10%, thixotropic agent 0.3～5%, surfactant 1～5%, plasticizer 10～30%.
Solvent is other material in the dissolving organic carrier in the organic carrier, makes it become fluid; Adding thickener is for increased viscosity, does not make its trickling; Adding thixotropic agent is for increasing thixotropy, making the electrode of printing have bigger depth-width ratio; In order to improve itself and the wetability of consolidating powder, add an amount of surfactant; Adding plasticizer is to make it that better plasticity arranged, and is convenient to printing.Organic carrier is a complex system, must use multiple auxiliary agent and suitable proportioning, just can make it have good levelability, thixotropy, printing, makes performance reach required requirement.The present invention adds thickener, thixotropic agent, surfactant, plasticizer simultaneously in solvent; Synergistic action effect is good; Help having improved simultaneously organic carrier levelability and thixotropy, to the wetability of solid powder, the printing of the slurry of preparing; The battery electrode of preparation and grid line thick film obtain bigger depth-width ratio, make battery have higher electricity conversion.
Preferably solvent is one or more the combination in terpinol, BC, the BC acetate.
Preferably thickener is an ethyl cellulose.
Preferably thixotropic agent is one or more the combination in castor oil, rilanit special, aerosil, the organobentonite.
Preferably surfactant is one or more the combination in oleic acid, department class 85, the lecithin, and plasticizer is one or both the combination in ATBC, the dibutyl phthalate.
The present invention prepares the above front electrode of solar battery and grid line conductive silver paste with the method for organic carrier, may further comprise the steps:
1. the weight percentage by each component of organic carrier takes by weighing various raw materials, is that solvent 60～75%, thickener 1～10%, thixotropic agent 0.3～5%, surfactant 1～5%, plasticizer 10～30% take by weighing various raw materials by the quality percentage composition of each component promptly;
2. join various auxiliary agents in the solvent respectively;
3. the mixture with step 2 gained heats, and its various auxiliary agents all are dissolved in the solvent, promptly obtains required organic carrier.
Preferably to heat be that this mixture is placed container water-bath heating to the said mixture with step 2 gained of step 3; Temperature is 50～70 ℃, and fully stirs, and mixing speed is 60～120 rev/mins; Mixing time is 90～120 minutes, makes all dissolvings in solvent of its various auxiliary agents.
A kind of front electrode of solar battery and grid line conductive silver paste that contains the above organic carrier of the present invention; This conductive silver paste also includes silver powder, glass dust, these solid powder of additive (Gu the raw material in the powder is pressed prior art with preparation); Its weight percentage is: organic carrier 10～20%, Gu powder 80～90%.
Preferably this conductive silver paste has viscosity, levelability and the thixotropy that is suitable for allocating slurry, has suitable fineness and chemical stability with the slurry of its preparation, and its viscosity is: 170～210Pas; Levelability is: 25 ℃, and 2～3min, thixotropy is good; Can make electrode and grid line thick film depth-width ratio be: 0.25～0.28; Fineness: 5～10 μ m, chemical stability is good, and preservation can reach more than 6 months.
A kind of solar cell that contains the above conductive silver paste manufacturing of the present invention; Make solar panel front electrode and grid line with this conductive silver paste through the silk screen printing sintering; Promptly on cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with above-described conductive silver paste; Its thick film thickness can reach more than 20 microns and 20 microns; Electrode and grid line thick film depth-width ratio are: 0.25～0.28, and make the electrode of preparation and grid line obtain bigger depth-width ratio.
The advantage of organic carrier of the present invention is: through optimizing viscosity, thixotropy and the levelability of solar cell positive silver paste with organic carrier; Has suitable viscosity; Preparation technology is simple; Be suitable for allocating viscosity, levelability and the thixotropy of slurry, with the conductive silver paste of its preparation suitable viscosity, fineness, levelability, thixotropy and chemical stability arranged, its slurry can reach more than 20 microns through the thick film thickness behind silk screen printing and the sintering on the cell substrates.The electrode of the solar battery sheet of preparation and grid line thick film obtain bigger depth-width ratio, can obtain the photoelectric conversion efficiency higher than conventional solar cell simultaneously.
Embodiment
Front electrode of solar battery of the present invention and grid line conductive silver paste are used organic carrier, and the weight percentage of each component is solvent 60～75%, thickener 1～10%, thixotropic agent 0.3～5%, surfactant 1～5%, plasticizer 10～30%.The combination of one or more in solvent employing terpinol, dibutyl phthalate, the BC.Thickener adopts ethyl cellulose.Thixotropic agent adopts one or more in castor oil, rilanit special, aerosil, the organobentonite.The combination of one or more in surfactant employing oleic acid, class of department 85, the lecithin.The combination of one or both in plasticizer employing ATBC, the dioctyl phthalate.
The compound method of described organic carrier is: at first take by weighing various raw materials, then various auxiliary agents are joined respectively in the solvent, organic carrier is placed container water-bath heating; Temperature is 50～70 ℃; And fully stir, mixing speed is 60～120 rev/mins, mixing time is 90～120 minutes; Make its whole dissolvings, promptly obtain required organic carrier.
Prepare front electrode of solar battery and grid line conductive silver paste with resulting organic carrier; Be with organic carrier of the present invention and solid powder (solid powder that comprises silver powder, glass dust, additive) mixed preparing form slurry; Percentage composition is by weight: organic carrier 10～20%, Gu powder 80～90%.Measure its viscosity, control viscosity is 170～210Pas, regulates viscosity through the content that changes organic carrier or solid powder.
Make solar cell with the prepared conductive silver paste material of the present invention; Make solar panel front electrode and grid line with this conductive silver paste through the silk screen printing sintering; Promptly on cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with above-described conductive silver paste; The sintering thickness of this slurry test electrode behind the printing sintering, its thick film thickness can reach more than 20 microns and 20 microns, and electrode and grid line thick film depth-width ratio are: 0.25～0.28; And the electrical property of test battery, the photoelectric conversion efficiency of solar cell reach 17.5% and more than.
Below in conjunction with non-limiting examples of the present invention, the present invention is made further detailed description.
Embodiment 1
Press the formulated organic carrier 100g of table 1.Take by weighing solvent terpinol: 70g, thickener ethyl cellulose: 5g, thixotropic agent rilanit special: 2g, the 85:3g of class of surfactant department, plasticizer phthalic acid dibutyl ester: 20g join in the solvent successively then; This mixture places container water-bath heating; In 60 ℃ of water-bath heating; And stir with 60 rev/mins speed, make its whole dissolvings, obtain organic carrier.(wherein admittedly powder is the silver powder of 80wt% to use the solid powder of 16wt% organic carrier and 84wt% then; The plumbous borosilicate glass powder of 3wt%, the titanium dioxide additive of 1wt%) be mixed with slurry; This slurry has suitable viscosity, and viscosity is 180Pas (10rpm, 25 ℃); Printing performance is good; Satisfy the high speed, high resolution silk screen printing requirement of 325 order stainless steel web plates, on cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering, reach 20 microns with the positive silver thick film of the solar battery sheet of its preparation with this conductive silver paste; Electrode and grid line thick film depth-width ratio: 0.25, the solar cell photoelectric conversion efficiency of preparation reaches 17.5%.
Annotate: used plumbous borosilicate glass powder is an one Chinese patent application numbers 200910304311.6; Denomination of invention: the Pb-B-Si-Zn-Ti-Al-O glass frit in " front electrode of solar battery is with electric conductor slurry and preparation technology thereof ", its main component shared percentage by weight in glass dust is: PbO 50-70%, B
2O
32-5%, SiO
220-30%, ZnO 1-5%, TiO 0.1-3%, Al
2O
32-5%.Plumbous borosilicate glass powder is with PbO 64.9%, B in the present embodiment
2O
33.5%, SiO
224.8%, ZnO 2.7%, TiO 0.7%, Al
2O
33.4% is produced.
Embodiment 2
Press the formulated organic carrier 100g of table 1.Take by weighing solvent BC: 65g, thickener ethyl cellulose: 4g, thixotropic agent aerosil: 3g, surfactant lecithin: 4g, plasticizer tirbutyl citrate: 24g join in the solvent successively then, in 60 ℃ of water-baths heating, and stir with 60 rev/mins speed; Make its whole dissolvings; Solid powder (wherein powder is the silver powder of 80wt% admittedly, the plumbous borosilicate glass powder of 3wt%, the titanium dioxide additive of 1wt%) with 16wt% organic carrier and 84wt% is mixed with slurry, and this slurry has suitable viscosity; Viscosity is 191Pas (10rpm; 25 ℃), printing performance is good, satisfies the high speed, high resolution silk screen printing requirement of 325 order stainless steel web plates; On cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with this conductive silver paste; Reach 21 microns with the positive silver thick film of the solar battery sheet of its preparation, electrode and grid line thick film depth-width ratio: 0.26, the solar cell photoelectric conversion efficiency of preparation reaches 17.8%.
Annotate: identical among used plumbous borosilicate glass powder and the embodiment 1.
Embodiment 3
Press the formulated organic carrier 100g of table 1.Take by weighing solvent BC acetate: 60g, thickener ethyl cellulose: 3g, thixotropic agent organobentonite: 4g, surfactant oleic acid: 5g, plasticizer phthalic acid dibutyl ester: 28g join in the solvent successively then, in 60 ℃ of water-baths heating, and stir with 60 rev/mins speed; Make its whole dissolvings; Solid powder (wherein powder is the silver powder of 80wt% admittedly, the plumbous borosilicate glass powder of 3wt%, the titanium dioxide additive of 1wt%) with 16wt% organic carrier and 84wt% is mixed with slurry, and this slurry has suitable viscosity; Viscosity is 203Pas (10rpm; 25 ℃), printing performance is good, satisfies the high speed, high resolution silk screen printing requirement of 325 order stainless steel web plates; On cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with this conductive silver paste; Reach 22 microns with the positive silver thick film of the solar battery sheet of its preparation, electrode and grid line thick film depth-width ratio: 0.28, the solar cell photoelectric conversion efficiency of preparation reaches 18.2%.
Annotate: identical among used plumbous borosilicate glass powder and the embodiment 1.
Embodiment 4
Press the formulated organic carrier 100g of table 1.Take by weighing solvent: terpinol 36g, BC 36g; Thickener ethyl cellulose: 10g, thixotropic agent rilanit special: 0.3g, surfactant successively then: class 85 of department and each 0.5g of lecithin be 1g, plasticizer altogether: dibutyl phthalate 8.7g, ATBC 8g join in the solvent, in 60 ℃ of water-baths heating, and stir with 60 rev/mins speed; Make its whole dissolvings; Solid powder (wherein powder is the silver powder of 80wt% admittedly, the plumbous borosilicate glass powder of 3wt%, the titanium dioxide additive of 1wt%) with 16wt% organic carrier and 84wt% is mixed with slurry, and this slurry has suitable viscosity; Viscosity is 203Pas (10rpm; 25 ℃), printing performance is good, satisfies the high speed, high resolution silk screen printing requirement of 325 order stainless steel web plates; On cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with this conductive silver paste; Reach 22 microns with the positive silver thick film of the solar battery sheet of its preparation, electrode and grid line thick film depth-width ratio: 0.28, the solar cell photoelectric conversion efficiency of preparation reaches 18.2%.
Annotate: identical among used plumbous borosilicate glass powder and the embodiment 1.
Embodiment 5
Press the formulated organic carrier 100g of table 1.Take by weighing solvent: terpinol 36g, BC acetate: 39g, thickener ethyl cellulose: 8g successively then, thixotropic agent aerosil: 3g, organobentonite 2g; Surfactant lecithin: 2g, plasticizer tirbutyl citrate: 5g, dibutyl phthalate 5g join in the solvent, in 60 ℃ of water-bath heating; And stir with 60 rev/mins speed, make its whole dissolvings, (wherein consolidating powder is the silver powder of 80wt% with the solid powder of 16wt% organic carrier and 84wt%; The plumbous borosilicate glass powder of 3wt%, the titanium dioxide additive of 1wt%) be mixed with slurry; This slurry has suitable viscosity, and viscosity is 191Pas (10rpm, 25 ℃); Printing performance is good; On cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with this conductive silver paste, satisfy the high speed, high resolution silk screen printing requirement of 325 order stainless steel web plates, reach 21 microns with the positive silver thick film of the solar battery sheet of its preparation; Electrode and grid line thick film depth-width ratio: 0.26, the solar cell photoelectric conversion efficiency of preparation reaches 17.8%.
Annotate: identical among used plumbous borosilicate glass powder and the embodiment 1.
Organic carrier prescription and performance index among table 1 embodiment
Claims (8)
1. front electrode of solar battery and grid line conductive silver paste are used organic carrier; It is characterized in that comprising solvent and auxiliary agent; Described auxiliary agent comprises thickener, thixotropic agent, surfactant, plasticizer; The weight percentage of each component is solvent 60～75%, thickener 1～10%, thixotropic agent 0.3～5%, surfactant 1～5%, plasticizer 10～30%; Said thickener is an ethyl cellulose, and said thixotropic agent is one or more the combination in castor oil, rilanit special, aerosil, the organobentonite.
2. organic carrier according to claim 1 is characterized in that solvent is one or more the combination in terpinol, BC, the BC acetate.
3. organic carrier according to claim 1; It is characterized in that surfactant is an oleic acid; Or one or both the combination in oleic acid and class of department 85, the lecithin, plasticizer is one or both the combination in ATBC, the dibutyl phthalate.
4. one kind prepares the described front electrode of solar battery of one of claim 1-3 and grid line conductive silver paste with the method for organic carrier, may further comprise the steps:
(1) weight percentage by each component of organic carrier takes by weighing various raw materials;
(2) join various auxiliary agents in the solvent respectively;
(3) mixture with step (2) gained heats, and its various auxiliary agents all are dissolved in the solvent, promptly obtains required organic carrier.
5. preparation method according to claim 4; It is characterized in that it is that this mixture is placed container water-bath heating that the said mixture with step (2) gained of step (3) heats; Temperature is 50～70 ℃, and fully stirs, and mixing speed is 60～120 rev/mins; Mixing time is 90～120 minutes, makes all dissolvings in solvent of its various auxiliary agents.
6. a front electrode of solar battery and grid line conductive silver paste that contains one of claim 1-3 said organic carrier; It is characterized in that this conductive silver paste also includes silver powder, glass dust, these solid powder of additive; Its weight percentage is: organic carrier 10～20%; Gu powder 80～90%, said glass dust adopts the Pb-B-Si-Zn-Ti-Al-O glass frit, and its main component shared percentage by weight in glass dust is: PbO 50-70%, B
2O
32-5%, SiO
220-30%, ZnO 1-5%, TiO 0.1-3%, Al
2O
32-5%.
7. conductive silver paste according to claim 6 is characterized in that this conductive silver paste has viscosity, levelability and the thixotropy that is suitable for allocating slurry, has suitable fineness and chemical stability with the slurry of its preparation; Its viscosity is: 170～210Pas; Levelability is: 25 ℃, and 2～3min, thixotropy is good; Electrode and grid line thick film depth-width ratio are: 0.25～0.28, and fineness: 5～10 μ m.
8. one kind contains the solar cell that right requires 6 or 7 said conductive silver pastes to make; On cell substrates, conductive silver paste is made solar panel front electrode and grid line through the silk screen printing sintering with this conductive silver paste; Its thick film thickness can reach more than 20 microns and 20 microns; Electrode and grid line thick film depth-width ratio are: 0.25～0.28, and make the electrode of preparation and grid line obtain bigger depth-width ratio.
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| CN2010105553313A CN102136308B (en) | 2010-11-23 | 2010-11-23 | Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste |
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| CN2010105553313A CN102136308B (en) | 2010-11-23 | 2010-11-23 | Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste |
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| WO2009052141A1 (en) * | 2007-10-18 | 2009-04-23 | E. I. Du Pont De Nemours And Company | Conductive compositions and processes for use in the manufacture of semiconductor devices |
| CN101483207B (en) * | 2009-01-07 | 2013-02-13 | 范琳 | Front gate line electrode silver conductor slurry for environment friendly silicon solar cell |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101271928A (en) * | 2008-05-04 | 2008-09-24 | 常州亿晶光电科技有限公司 | High-viscosity solar cell front silver paste and preparation method thereof |
| CN101359696A (en) * | 2008-05-28 | 2009-02-04 | 华东理工大学 | Conductive slurry for front electrode of solar battery having great printing performance |
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