CN102324263B - 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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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 for solar cell and starch and preparation method thereof.
Background technology
Solar cell is a kind of semiconductor device that solar energy can be converted to electric energy, and inside solar energy battery can produce photogenerated current under illumination condition, can directly electric energy be exported by electrode.
Draw for the photogenerated current that solar cell is produced, must produce positive and negative electrode on the surface of solar cell.Fabrication Technology of Electrode 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, make the electrode of solar cell by silk screen printing, low temperature drying, high-sintering process.Existing conductive silver paste is prepared from by different proportionings by raw material such as silver powder, glass glue, organic solvents.Wherein silver powder is conducting medium; Glass glue melts when high temperature sintering, forms ohmic contact between silver powder and silicon base; Organic solvent mainly rises and disperses and package action, silver powder particles is wrapped up uniformly, so that the silver powder in the conductive silver paste is not easy to produce precipitation and oxidation.
The quality of conductive silver paste directly affects 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 adopts is a kind of bismuth-silicon-lead glass mixed-powder, the advantages such as softening temperature is lower although this kind glass powder has, electric performance stablity, it is higher that but this system contains lead proportion, larger to the pollution of environment, do not meet environmental requirement.In 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.Using the particle diameter of silver powder in addition in existing silver slurry is consistent basically, if crackle appears in 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, affects the uniformity that its silver powder distributes.Therefore, be necessary the particle diameter of silver powder is carried out Effective Regulation.
Summary of the invention
The object of the invention is to overcome the defective that exists in the prior art, a kind of not leaded sun energy battery silver paste too is provided, under the prerequisite that satisfies the solar cell electrical property, make solar cell can satisfy the international market to the leadless environment-friendly requirement of solar cell, make simultaneously silver-colored arrangement of conductors, densification after the silk screen printing.Another object of the present invention also is, a kind of process for preparing above-mentioned silver powder is provided.
For achieving the above object, technical scheme of the present invention has provided a kind of silver slurry for solar cell, it is characterized in that, described silver slurry comprises: the organic carrier of the silver powder of 75～80wt%, the lead-free glass powder of 5～15wt%, 10～15wt%, described organic carrier is comprised 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 described silver powder includes two kinds of 30～58nm and 58～90nm; Described organic solvent comprises the combination of any or they in terpinol, turpentine oil, butyl carbitol, butyl carbitol acetate, ethers, plasticizer and the surfactant; Described organic additive is cellulose; Described 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
Preferred technical scheme is, in described silver powder particle diameter be 30～58nm account for 20～40%, particle diameter be 58～90nm account for 60～80%.
Preferred technical scheme also has, and the particle diameter of described lead-free glass powder is 10～40 μ m.
Preferred technical scheme also has, and described cellulose comprises the combination of any or they in ethyl cellulose, hydroxypropyl cellulose and the carboxymethyl cellulose.
Preferred technical scheme also has, and described plasticizer is dibutyl phthalate and/or acrylic resin.
Preferred technical scheme also has, and described surfactant is triethanolamine, rilanit special, lecithin.
Preferred 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 preferred 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 preferred technical scheme is that described levelling agent is acrylate; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is, a kind of preparation method of the silver slurry for solar cell is provided, and it is characterized in that described preparation method's processing step is as follows:
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 step, above-mentioned raw materials is weighed according to weight ratio, be put in high temperature Ma Fulu after mixing and heat, temperature is controlled at 1000-1400 ℃, then is incubated 30-60 minute, carries out ball milling after the glass powder particle after will fusing quenches;
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, namely obtains being used for uniformly the silver slurry of solar cell.
Advantage of the present invention and beneficial effect are: not leaded by the silver paste of solar cells that the present invention's prescription obtains, meet environmental requirement fully, can form in solar cell surface the conductive electrode of strong adhesion, low ohm contact resistance, the cell photoelectric conversion efficiency is high, is the desirable substituent of leaded silver slurry.Owing to selected the silver powder of two kinds of particle diameters in this silver slurry, the electrode that screen printing is made is evenly fine and close in addition, and contact resistance is little, and bonding firmly.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is further described.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 for solar cell, this silver slurry comprises: the organic carrier of the silver powder of 75wt%, the lead-free glass powder of 10wt%, 15wt%, described organic carrier is comprised of organic solvent and organic additive, weight ratio between the two is 4: 1, described silver powder is spherical, and the particle diameter of described silver powder includes two kinds of 40nm and 70nm; Described organic solvent comprises the combination of any or they in terpinol, turpentine oil, butyl carbitol, butyl carbitol acetate, ethers, plasticizer and the surfactant; Described organic additive is cellulose; Described 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 described silver powder particle diameter be 40nm account for 20%, particle diameter be 70nm account for 60%.The particle diameter of described 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 acrylate; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is, a kind of preparation method of the silver slurry for solar cell is provided, and it is characterized in that described preparation method's processing step is as follows:
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 step, above-mentioned raw materials is weighed according to weight ratio, be put in high temperature Ma Fulu after mixing and heat, temperature is controlled at 1000-1400 ℃, then is incubated 30-60 minute, carries out ball milling after the glass powder particle after will fusing quenches;
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, namely obtains being used for uniformly the silver slurry of solar cell.
Embodiment 2
The present invention is a kind of silver slurry for solar cell, this silver slurry comprises: the organic carrier of the silver powder of 78wt%, the lead-free glass powder of 10wt%, 12wt%, described organic carrier is comprised of organic solvent and organic additive, weight ratio between the two is 5: 1, described silver powder is spherical, and the particle diameter of described silver powder includes two kinds of 35nm and 55nm; Described organic solvent comprises the combination of any or they in terpinol, turpentine oil, butyl carbitol, butyl carbitol acetate, ethers, plasticizer and the surfactant; Described organic additive is cellulose; Described 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 described silver powder particle diameter be 40nm account for 20%, particle diameter be 70nm account for 60%.The particle diameter of described 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 acrylate; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is, a kind of preparation method of the silver slurry for solar cell is provided, and it is characterized in that described preparation method's processing step is as follows:
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 step, above-mentioned raw materials is weighed according to weight ratio, be put in high temperature Ma Fulu after mixing and heat, temperature is controlled at 1000-1400 ℃, then is incubated 30-60 minute, carries out ball milling after the glass powder particle after will fusing quenches;
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, namely obtains being used for uniformly the silver slurry of solar cell.
Embodiment 3
The present invention is a kind of silver slurry for solar cell, this silver slurry comprises: the organic carrier of the silver powder of 80wt%, the lead-free glass powder of 8wt%, 12wt%, described organic carrier is comprised of organic solvent and organic additive, weight ratio between the two is 6: 1, described silver powder is spherical, and the particle diameter of described silver powder includes two kinds of 40nm and 80nm; Described organic solvent comprises the combination of any or they in terpinol, turpentine oil, butyl carbitol, butyl carbitol acetate, ethers, plasticizer and the surfactant; Described organic additive is cellulose; Described 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 described silver powder particle diameter be 40nm account for 35%, particle diameter be 80nm account for 65%.The particle diameter of described 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 acrylate; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
Another technical scheme of the present invention is, a kind of preparation method of the silver slurry for solar cell is provided, and it is characterized in that described preparation method's processing step is as follows:
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 step, above-mentioned raw materials is weighed according to weight ratio, be put in high temperature Ma Fulu after mixing and heat, temperature is controlled at 1000-1400 ℃, then is incubated 30-60 minute, carries out ball milling after the glass powder particle after will fusing quenches;
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, namely obtains being used for uniformly the silver slurry of solar cell.
The above only is 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 the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered 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, described silver slurry comprises: the organic carrier of the silver powder of 75～80wt%, the lead-free glass powder of 5～15wt%, 10～15wt%, described organic carrier is comprised of organic solvent and organic additive, weight ratio between the two is 3: 1～7: 1, described silver powder is sphere and/or scale shape, and the particle diameter of described silver powder includes two kinds of 30～58nm and 58～90nm; Described organic solvent comprises the combination of any or they in terpinol, turpentine oil, butyl carbitol, butyl carbitol acetate, ethers, plasticizer and the surfactant; Described organic additive is cellulose; Described 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 for solar cell as claimed in claim 1 is characterized in that, in described silver powder particle diameter be 30～58nm account for 20～40%, particle diameter be 58～90nm account for 60～80%.
3. the silver slurry for solar cell as claimed in claim 1 is characterized in that the particle diameter of described lead-free glass powder is 10～40 μ m.
4. the silver slurry 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 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 for solar cell as claimed in claim 1 is characterized in that described surfactant is triethanolamine, rilanit special, lecithin.
7. the silver slurry 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 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 for solar cell as claimed in claim 7 is characterized in that described levelling agent is acrylate; Described dispersant is stearmide and higher alcohol; Described thixotropic agent is aerosil, precipitated silica, organobentonite.
10. the preparation method of the described silver slurry for solar cell of a claim 1 is characterized in that described preparation method's processing step is as follows:
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 step, above-mentioned raw materials is weighed according to weight ratio, be put in high temperature Ma Fulu after mixing and heat, temperature is controlled at 1000-1400 ℃, then is incubated 30-60 minute, carries out ball milling after the glass powder particle after will fusing quenches;
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, namely obtains being used for uniformly the silver slurry of solar cell.
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| US8721931B2 (en) * | 2005-12-21 | 2014-05-13 | E I Du Pont De Nemours And Company | Paste for solar cell electrode, solar cell electrode manufacturing method, and solar cell |
| CN101271929B (en) * | 2008-05-04 | 2012-02-01 | 常州亿晶光电科技有限公司 | Leadless solar battery silver paste and method for producing the same |
| CN101483207B (en) * | 2009-01-07 | 2013-02-13 | 范琳 | Front gate line electrode silver conductor slurry for environment friendly silicon solar cell |
| CN101859609B (en) * | 2010-04-21 | 2011-09-21 | 北京科技大学 | Lead-free silver electrode slurry and preparation and using method thereof |
| CN101964219B (en) * | 2010-08-10 | 2013-02-06 | 上海九晶电子材料股份有限公司 | Silver paste for positive of crystalline silicon solar cell and preparation method thereof |
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