CN102324263A - Silver paste for solar cells and preparation method thereof - Google Patents
Silver paste for solar cells and preparation method thereof Download PDFInfo
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- CN102324263A CN102324263A CN201110184050A CN201110184050A CN102324263A CN 102324263 A CN102324263 A CN 102324263A CN 201110184050 A CN201110184050 A CN 201110184050A CN 201110184050 A CN201110184050 A CN 201110184050A CN 102324263 A CN102324263 A CN 102324263A
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Abstract
The invention discloses a silver paste for solar cells. The silver paste consists of silver powder, lead-free glass powder and an organic carrier, the organic carrier consists of organic solvent and organic additive, the silver powder is spherical and/or flaky, and the grain sizes of the silver powder are coarse and fine; the lead-free glass powder adopts a lanthanum-boron-zinc glass system, and the components of the lead-free glass powder are La2O3, B2O3, Al2O3, ZnO, Na2O, LiO2, V2O5 and P2O5. A preparation method for the silver paste includes the following steps: after being uniformly mixed, the materials of the lead-free glass powder are put into a high-temperature muffle furnace to heat, the temperature is preserved, and the melted glass powder particles are quenched and then ball-milled; the organic solvent and the organic additive are uniformly mixed and stirred according to proportion; the silver powder, the lead-free glass powder and the organic carrier are weighed, uniformly stirred in a container, put into a three-roll mill and ball-milled, and thereby the uniform silver paste for the solar cells is prepared. Under the premise of meeting the electrical properties of the solar cells, the silver paste also can meet the requirement on lead-free environment-friendliness.
Description
Technical field
The present invention relates to a kind of silver slurry, be specifically related to a kind of silver slurry that is used for solar cell and preparation method thereof.
Background technology
Solar cell is a kind of semiconductor device that can solar energy converting be become electric energy, and inside solar energy battery can produce photogenerated current under illumination condition, can directly electric energy be exported through electrode.
Draw for the photogenerated current that solar cell is produced, must produce positive and negative electrode on the surface of solar cell.Electrode manufacture craft commonly used has magnetron sputtering, vacuum evaporation and silk screen printing sintering etc., but the production cost of magnetron sputtering, vacuum deposition method is too high, and is less economical.At present, in manufacture of solar cells enterprise, generally use leaded solar cell conductive silver slurry, process the electrode of solar cell through silk screen printing, low temperature drying, high-sintering process.Existing conductive silver paste is prepared from by different proportionings raw material such as silver powder, glass glue, organic solvents.Wherein silver powder is conducting medium; Glass glue melts when high temperature sintering, between silver powder and silicon base, forms ohmic contact; Organic solvent mainly rises and disperses and package action, and silver powder particles is wrapped up uniformly, makes that the silver powder in the conductive silver paste is not easy to produce deposition and oxidation.
The quality of conductive silver paste directly influences the series resistance and the cell photoelectric conversion efficiency of solar cell, and it is a very crucial technical essential in the manufacture of solar cells.The glass dust adhesive that present solar cell conductive silver slurry is adopted is a kind of bismuth-silicon-lead glass mixed-powder; Advantages such as softening temperature is lower though this kind glass powder has, electric performance stablity; It is higher that but this system contains proportion, bigger to the pollution of environment, do not meet environmental requirement.Under the situation that solar cell is popularized day by day, oneself is restricted the use of leaded solar cell conductive silver slurry, will be eliminated gradually soon, must develop the unleaded conductive silver paste of high conduction performance, to satisfy large solar battery production demand.In existing silver slurry, using the particle diameter of silver powder in addition is consistent basically; Crackle occurs as if the excessive silk screen printing of silver powder particle diameter meeting like this, and can increase contact resistance, if the silver powder particle diameter is too small; Agglomeration traits can appear in silver powder, influences the uniformity that its silver powder distributes.Therefore, be necessary the particle diameter of silver powder is effectively regulated and control.
Summary of the invention
The objective of the invention is to overcome the defective that exists in the prior art; A kind of not leaded sun ability battery silver paste too is provided; Under the prerequisite that satisfies the solar cell electrical property; Make solar cell can satisfy the leadless environment-friendly requirement of international market, make silver-colored arrangement of conductors, densification after the silk screen printing simultaneously solar cell.Another object of the present invention also is, a kind of process for preparing above-mentioned silver powder is provided.
For realizing above-mentioned purpose; Technical scheme of the present invention has provided a kind of silver slurry that is used for solar cell, it is characterized in that, said silver slurry comprises: the organic carrier of the silver powder of 75～80wt%, the lead-free glass powder of 5～15wt%, 10～15wt%; Said organic carrier is made up of organic solvent and organic additive; Weight ratio between the two is 3: 1～7: 1, and described silver powder is sphere and/or scale shape, and the particle diameter of said silver powder includes two kinds of 30～58nm and 58～90nm; Said organic solvent comprises the combination of any or they in terpinol, turpentine oil, BC, BC acetate, ethers, plasticizer and the surfactant; Said organic additive is a cellulose; Said lead-free glass powder adopts lanthanum, boron, zinc glass system, and its component comprises: the La of 0.5～1wt%
2O
3, 70～85wt% B
2O
3, 2～5wt% Al
2O
3, the ZnO of 2～5wt%, the Na of 1～5wt%
2The LiO of O, 2～5wt%
2, 3～8wt% V
2O
5P with 0.5～1wt%
2O
5
Optimized technical scheme is, in said silver powder particle diameter be 30～58nm account for 20～40%, particle diameter be 58～90nm account for 60～80%.
Optimized technical scheme also has, and the particle diameter of said lead-free glass powder is 10～40 μ m.
Optimized technical scheme also has, and described cellulose comprises the combination of any or they in ethyl cellulose, hydroxypropyl cellulose and the carboxymethyl cellulose.
Optimized technical scheme also has, and described plasticizer is dibutyl phthalate and/or acrylic resin.
Optimized technical scheme also has, and described surfactant is triethanolamine, rilanit special, lecithin.
Optimized technical scheme also has, and described organic solvent also comprises the combination of any or they in coupling agent, levelling agent, dispersant and the thixotropic agent.
Further optimized technical scheme is, described coupling agent is the combination of any or they in organosilicon, metatitanic acid fat, aluminic acid lipoprotein and the organic complex.
Further optimized technical scheme is that described levelling agent is an acrylic acid ester; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is that the preparation method who provides a kind of silver that is used for solar cell to starch is characterized in that said preparation method's processing step is following:
The component of lead-free glass powder and the La that percentage by weight is equipped with raw material: 0.5～1wt% are pressed in the preparation of the first step, lead-free glass powder
2O
3, 70～85wt% B
2O
3, 2～5wt% Al
2O
3, the ZnO of 2～5wt%, the Na of 1～5wt%
2The LiO of O, 2～5wt%
2, 3～8wt% V
2O
5P with 0.5～1wt%
2O
5
Second goes on foot, above-mentioned raw materials is weighed according to weight ratio, is put in high temperature Ma Fulu after mixing and heats, and temperature is controlled at 1000-1400 ℃, is incubated 30-60 minute then, carries out ball milling after the glass powder particle after the fusing is quenched;
The 3rd step, organic carrier preparation were carried out mixing and stirring with organic solvent and organic additive in 3: 1～7: 1 according to part by weight and are got final product;
The preparation of the 4th step, solar cell conductive silver slurry; With silver powder 75～80wt%, lead-free glass powder 5～15wt%, organic carrier 10～15wt%; Weighing stirs in container puts into three-roll grinder and carries out ball milling, promptly is used for the silver slurry of solar cell uniformly.
Advantage of the present invention and beneficial effect are: the silver paste of solar cells by the present invention's prescription is obtained is not leaded; Complete compliance with environmental protection requirements; Can form the conductive electrode of strong adhesion, low ohm contact resistance in solar cell surface; The cell photoelectric conversion efficiency is high, is the desirable substituent of leaded silver slurry.Owing in this silver slurry, selected the silver powder of two kinds of particle diameters for use, the electrode that silk screen printing is gone out is evenly fine and close in addition, and contact resistance is little, and bonding firmly.
Embodiment
Below in conjunction with embodiment, specific embodiments of the invention further describes.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
Embodiment 1
The present invention is a kind of silver slurry that is used for solar cell; This silver slurry comprises: the organic carrier of the silver powder of 75wt%, the lead-free glass powder of 10wt%, 15wt%; Said organic carrier is made up of organic solvent and organic additive; Weight ratio between the two is 4: 1, and described silver powder is spherical, and the particle diameter of said silver powder includes two kinds of 40nm and 70nm; Said organic solvent comprises the combination of any or they in terpinol, turpentine oil, BC, BC acetate, ethers, plasticizer and the surfactant; Said organic additive is a cellulose; Said lead-free glass powder adopts lanthanum, boron, zinc glass system, and its component comprises: the La of 1wt%
2O
3, 70wt% B
2O
3, 5wt% Al
2O
3, the ZnO of 5wt%, the Na of 5wt%
2The LiO of O, 5wt%
2, 8wt% V
2O
5P with 1wt%
2O
5In said silver powder particle diameter be 40nm account for 20%, particle diameter be 70nm account for 60%.The particle diameter of said lead-free glass powder is 25 μ m.Described cellulose comprises ethyl cellulose.Described plasticizer is dibutyl phthalate and/or acrylic resin.Described surfactant is triethanolamine, rilanit special, lecithin.Described organic solvent also comprises the combination of any or they in coupling agent, levelling agent, dispersant and the thixotropic agent.Described coupling agent is the combination of any or they in organosilicon, metatitanic acid fat, aluminic acid lipoprotein and the organic complex.Described levelling agent is an acrylic acid ester; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is that the preparation method who provides a kind of silver that is used for solar cell to starch is characterized in that said preparation method's processing step is following:
The component of lead-free glass powder and the La that percentage by weight is equipped with raw material: 1wt% are pressed in the preparation of the first step, lead-free glass powder
2O
3, 70wt% B
2O
3, 5wt% Al
2O
3, the ZnO of 5wt%, the Na of 5wt%
2The LiO of O, 5wt%
2, 8wt% V
2O
5P with 1wt%
2O
5
Second goes on foot, above-mentioned raw materials is weighed according to weight ratio, is put in high temperature Ma Fulu after mixing and heats, and temperature is controlled at 1000-1400 ℃, is incubated 30-60 minute then, carries out ball milling after the glass powder particle after the fusing is quenched;
The 3rd step, organic carrier preparation are carried out mixing and stirring with organic solvent and organic additive according to part by weight and are got final product at 4: 1;
The preparation of the 4th step, solar cell conductive silver slurry; With silver powder 75wt%, lead-free glass powder 10wt%, organic carrier 15wt%; Weighing stirs in container puts into three-roll grinder and carries out ball milling, promptly is used for the silver slurry of solar cell uniformly.
Embodiment 2
The present invention is a kind of silver slurry that is used for solar cell; This silver slurry comprises: the organic carrier of the silver powder of 78wt%, the lead-free glass powder of 10wt%, 12wt%; Said organic carrier is made up of organic solvent and organic additive; Weight ratio between the two is 5: 1, and described silver powder is spherical, and the particle diameter of said silver powder includes two kinds of 35nm and 55nm; Said organic solvent comprises the combination of any or they in terpinol, turpentine oil, BC, BC acetate, ethers, plasticizer and the surfactant; Said organic additive is a cellulose; Said lead-free glass powder adopts lanthanum, boron, zinc glass system, and its component comprises: the La of 0.5wt%
2O
3, 80wt% B
2O
3, 3wt% Al
2O
3, the ZnO of 2wt%, the Na of 3wt%
2The LiO of O, 2wt%
2, 4wt% V
2O
5P with 0.5wt%
2O
5In said silver powder particle diameter be 40nm account for 20%, particle diameter be 70nm account for 60%.The particle diameter of said lead-free glass powder is 35 μ m.Described cellulose comprises ethyl cellulose.Described plasticizer is dibutyl phthalate and/or acrylic resin.Described surfactant is triethanolamine, rilanit special, lecithin.Described organic solvent also comprises the combination of any or they in coupling agent, levelling agent, dispersant and the thixotropic agent.Described coupling agent is the combination of any or they in organosilicon, metatitanic acid fat, aluminic acid lipoprotein and the organic complex.Described levelling agent is an acrylic acid ester; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is that the preparation method who provides a kind of silver that is used for solar cell to starch is characterized in that said preparation method's processing step is following:
The component of lead-free glass powder and the La that percentage by weight is equipped with raw material: 0.5wt% are pressed in the preparation of the first step, lead-free glass powder
2O
3, 80wt% B
2O
3, 3wt% Al
2O
3, the ZnO of 2wt%, the Na of 3wt%
2The LiO of O, 2wt%
2, 4wt% V
2O
5P with 0.5wt%
2O
5
Second goes on foot, above-mentioned raw materials is weighed according to weight ratio, is put in high temperature Ma Fulu after mixing and heats, and temperature is controlled at 1000-1400 ℃, is incubated 30-60 minute then, carries out ball milling after the glass powder particle after the fusing is quenched;
The 3rd step, organic carrier preparation are carried out mixing and stirring with organic solvent and organic additive according to part by weight and are got final product at 4: 1;
The preparation of the 4th step, solar cell conductive silver slurry; With silver powder 78wt%, lead-free glass powder 10wt%, organic carrier 12wt%; Weighing stirs in container puts into three-roll grinder and carries out ball milling, promptly is used for the silver slurry of solar cell uniformly.
Embodiment 3
The present invention is a kind of silver slurry that is used for solar cell; This silver slurry comprises: the organic carrier of the silver powder of 80wt%, the lead-free glass powder of 8wt%, 12wt%; Said organic carrier is made up of organic solvent and organic additive; Weight ratio between the two is 6: 1, and described silver powder is spherical, and the particle diameter of said silver powder includes two kinds of 40nm and 80nm; Said organic solvent comprises the combination of any or they in terpinol, turpentine oil, BC, BC acetate, ethers, plasticizer and the surfactant; Said organic additive is a cellulose; Said lead-free glass powder adopts lanthanum, boron, zinc glass system, and its component comprises: the La of 0.5wt%
2O
3, 75wt% B
2O
3, 5wt% Al
2O
3, the ZnO of 5wt%, the Na of 3wt%
2The LiO of O, 2wt%
2, 4wt% V
2O
5P with 0.5wt%
2O
5In said silver powder particle diameter be 40nm account for 35%, particle diameter be 80nm account for 65%.The particle diameter of said lead-free glass powder is 20 μ m.Described cellulose comprises ethyl cellulose.Described plasticizer is dibutyl phthalate and/or acrylic resin.Described surfactant is triethanolamine, rilanit special, lecithin.Described organic solvent also comprises the combination of any or they in coupling agent, levelling agent, dispersant and the thixotropic agent.Described coupling agent is the combination of any or they in organosilicon, metatitanic acid fat, aluminic acid lipoprotein and the organic complex.Described levelling agent is an acrylic acid ester; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is that the preparation method who provides a kind of silver that is used for solar cell to starch is characterized in that said preparation method's processing step is following:
The component of lead-free glass powder and the La that percentage by weight is equipped with raw material: 0.5wt% are pressed in the preparation of the first step, lead-free glass powder
2O
3, 75wt% B
2O
3, 5wt% Al
2O
3, the ZnO of 5wt%, the Na of 3wt%
2The LiO of O, 2wt%
2, 4wt% V
2O
5P with 0.5wt%
2O
5
Second goes on foot, above-mentioned raw materials is weighed according to weight ratio, is put in high temperature Ma Fulu after mixing and heats, and temperature is controlled at 1000-1400 ℃, is incubated 30-60 minute then, carries out ball milling after the glass powder particle after the fusing is quenched;
The 3rd step, organic carrier preparation are carried out mixing and stirring with organic solvent and organic additive according to part by weight and are got final product at 4: 1;
The preparation of the 4th step, solar cell conductive silver slurry; With silver powder 78wt%, lead-free glass powder 10wt%, organic carrier 12wt%; Weighing stirs in container puts into three-roll grinder and carries out ball milling, promptly is used for the silver slurry of solar cell uniformly.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. a silver that is used for solar cell is starched; It is characterized in that; Said silver slurry comprises: the organic carrier of the silver powder of 75～80wt%, the lead-free glass powder of 5～15wt%, 10～15wt%, and said organic carrier is made up of organic solvent and organic additive, and weight ratio between the two is 3: 1～7: 1; Described silver powder is sphere and/or scale shape, and the particle diameter of said silver powder includes two kinds of 30～58nm and 58～90nm; Said organic solvent comprises the combination of any or they in terpinol, turpentine oil, BC, BC acetate, ethers, plasticizer and the surfactant; Said organic additive is a cellulose; Said lead-free glass powder adopts lanthanum, boron, zinc glass system, and its component comprises: the La of 0.5～1wt%
2O
3, 70～85wt% B
2O
3, 2～5wt% Al
2O
3, the ZnO of 2～5wt%, the Na of 1～5wt%
2The LiO of O, 2～5wt%
2, 3～8wt% V
2O
5P with 0.5～1wt%
2O
5
2. the silver slurry that is used for solar cell as claimed in claim 1 is characterized in that, in said silver powder particle diameter be 30～58nm account for 20～40%, particle diameter be 58～90nm account for 60～80%.
3. the silver slurry that is used for solar cell as claimed in claim 1 is characterized in that the particle diameter of said lead-free glass powder is 10～40 μ m.
4. the silver slurry that is used for solar cell as claimed in claim 1 is characterized in that, described cellulose comprises the combination of any or they in ethyl cellulose, hydroxypropyl cellulose and the carboxymethyl cellulose.
5. the silver slurry that is used for solar cell as claimed in claim 1 is characterized in that described plasticizer is dibutyl phthalate and/or acrylic resin.
6. the silver slurry that is used for solar cell as claimed in claim 1 is characterized in that described surfactant is triethanolamine, rilanit special, lecithin.
7. the silver slurry that is used for solar cell as claimed in claim 1 is characterized in that, described organic solvent also comprises the combination of any or they in coupling agent, levelling agent, dispersant and the thixotropic agent.
8. the silver slurry that is used for solar cell as claimed in claim 7 is characterized in that, described coupling agent is the combination of any or they in organosilicon, metatitanic acid fat, aluminic acid lipoprotein and the organic complex.
9. the silver slurry that is used for solar cell as claimed in claim 7 is characterized in that described levelling agent is an acrylic acid ester; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
10. the said preparation method who is used for the silver slurry of solar cell of a claim 1 is characterized in that said preparation method's processing step is following:
The component of lead-free glass powder and the La that percentage by weight is equipped with raw material: 0.5～1wt% are pressed in the preparation of the first step, lead-free glass powder
2O
3, 70～85wt% B
2O
3, 2～5wt% Al
2O
3, the ZnO of 2～5wt%, the Na of 1～5wt%
2The LiO of O, 2～5wt%
2, 3～8wt% V
2O
5P with 0.5～1wt%
2O
5
Second goes on foot, above-mentioned raw materials is weighed according to weight ratio, is put in high temperature Ma Fulu after mixing and heats, and temperature is controlled at 1000-1400 ℃, is incubated 30-60 minute then, carries out ball milling after the glass powder particle after the fusing is quenched;
The 3rd step, organic carrier preparation were carried out mixing and stirring with organic solvent and organic additive in 3: 1～7: 1 according to part by weight and are got final product;
The preparation of the 4th step, solar cell conductive silver slurry; With silver powder 75～80wt%, lead-free glass powder 5～15wt%, organic carrier 10～15wt%; Weighing stirs in container puts into three-roll grinder and carries out ball milling, promptly is used for the silver slurry of solar cell uniformly.
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|---|---|---|---|
| CN 201110184050 CN102324263B (en) | 2011-07-04 | 2011-07-04 | Silver paste for solar cells and preparation method thereof |
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| CN109461515A (en) * | 2018-11-07 | 2019-03-12 | 刘紫嫣 | A kind of high temperature sintering conductive silver paste and preparation method thereof |
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