CN103440897A - Silicon solar cell front silver electrode high-square-resistance slurry and manufacturing method thereof - Google Patents
Silicon solar cell front silver electrode high-square-resistance slurry and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to silicon solar cell front silver electrode high-square-resistance slurry and a manufacturing method thereof. The slurry comprises, by weight, 80-93% of silver powder, 0.5-5% glass powder, 4-19% of organic vehicle, 0-2% of inorganic addition agents and 0-1% of wetting dispersant. The organic vehicle comprises an organic solvent, a thickening agent, a thixotropic agent and wetting dispersant, wherein the ratio of the organic solvent to the thickening agent is (80-95): (2-13), the ratio of the organic solvent to the thixotropic agent is (80-95): (0.5-6), and the ratio of the organic solvent to the wetting dispersant is (80-95): (0-3). By means of the specific inorganic addition agents, the organic vehicle with good thixotropy, combined solvents with good volatility curves, the proper glass powder and the compactly stacked mixed silver powder, good printing performance and depth-width ration, low contact resistance and high conversion efficiency and adhesive force are achieved on a high-square-resistance crystalline silicone battery piece.
Description
Technical field
The present invention relates to a kind of high square resistance silicon solar cell front silver electrode paste and preparation method thereof.
Background technology
In recent years, tradition fossil energy worsening shortages, people are more and more stronger to the demand of new forms of energy, people are more and more higher to the concern of environmental problem in addition, exploitation, utilize solar energy to become a large focus, the transformation of energy resource structure is imperative, being widely used of the clean reproducible energies such as solar energy power generating becomes the tendency of the day, with moral, day is the advanced country of representative, taked effective government subsidy policy owing to taking the lead in, impel the demand of photovoltaic cell sharply to increase, also driven the rapid emergence of each photovoltaic production and market of the world that comprises China, China successfully surmounted Europe in 2007, Japan is world's manufacture of solar cells the first big country.
The crystal silicon solar energy battery cost mainly concentrates on silicon chip and slurry, and cost of sizing agent accounts for 9% of solar cell cost.China consumes approximately 500 tons of left and right of solar battery front side slurry in 2012, and basic dependence on import.Because solar battery front side Size Technology difficulty is large, it is high to drop into, enter threshold trip higher, up to the present, China market solar energy front electrode silver slurry is mainly three American-European major companies and monopolizes, and a R&D direction in crystal silicon solar energy battery front slurry future will be the future development to the cell piece that mates high square resistance.The every raising of sheet resistance 10 Europe, approximately can realize 0.2% improved efficiency, greatly improves the utilance of solar energy, the invention provides the following sheet resistance that can significantly promote higher than the cell piece front silver electrode paste in 80 Europe and preparation method thereof.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of high square resistance silicon solar cell front silver electrode paste and preparation method thereof.
High square resistance silicon solar cell of the present invention front silver electrode paste, made by the raw material that comprises following percentage by weight: silver powder 80-93, glass dust 0.5-5, organic carrier 4-19, inorganic assistant 0-2, wetting dispersing agent 0-1; Organic carrier is comprised of organic solvent, thickener, thixotropic agent, wetting dispersing agent, wherein organic solvent: thickener=(80-95): (2-13); Organic solvent: thixotropic agent=(80-95): (0.5-6); Organic solvent: wetting dispersing agent=(80-95): (0-3); Inorganic assistant is selected from simple substance, oxide, carbonic acid thing, alloy or the organic substance in Mg, Ca, Mn, Zn, P, Al, Ag, Pt, Au, La, Ce, Nd, Hf, Ta, W, Ba, Cr, Rb, Y, Mo, Rh, Pd, In, Sn, Sb, Te, Pb, Si element, and inorganic assistant is also one or more mixtures in above-mentioned simple substance, oxide, carbonic acid thing, alloy, organic substance.
The preparation method of high square resistance silicon solar cell of the present invention front silver electrode paste comprises the following steps:
1) prepare glass dust: the raw material according to following percentage by weight is prepared, is mixed: SiO
23-35, B
2o
31-15, PBO35-80, TiO
20.5-5, Al
2o
30.5-5, ZnO0.5-10, MgO0.5-3, V
2o
50.5-5, Li
2o0.5-3, additive 0-10; Then making average particle size range through hot melt, cooling, pulverizing, ball milling, dried and screened is that 0.5 μ m-10 μ m, softening point are the glass dust that 350-20 ℃, specific area are less than 5g/cm3; Wherein additive is selected from simple substance, oxide, carbonic acid thing, alloy or the organic substance in Ca, Mn, P, Ag, Pt, Au, La, Ce, Nd, Hf, Ta, W, Ba, Cr, Rb, Y, Mo, Rh, Pd, In, Sn, Sb, Te element, and additive is also one or more mixtures in above-mentioned simple substance, oxide, carbonic acid thing, alloy, organic substance;
2) prepare organic carrier: organic carrier is comprised of organic solvent, thickener, thixotropic agent, wetting dispersing agent, wherein organic solvent: thickener=(80-95): (2-13); Organic solvent: thixotropic agent=(80-95): (0.5-6); Organic solvent: wetting dispersing agent=(80-95): (0-3); Be positioned over after mixing according to aforementioned proportion in the water bath of 70-95 ℃ and stir insulation 1.5 hours, cross afterwards 400 eye mesh screens and obtain organic carrier;
3) prepare silver powder: silver powder is comprised of silver powder A and silver powder B, and silver powder A and silver powder B are spherical, and the mixing quality ratio of silver powder A and silver powder B is 7-15; The D50 of silver powder A is that 1.5-4 μ m, D90 are less than 10 μ m, tap density is greater than 3.5g/cm
3, silver powder A surface coats one or more in butyl carbitol, butyl carbitol acetate, tributyl citrate, phenmethylol, turpentine oil, terpinol, triethyl citrate, acetylation tributyl citrate, lecithin, diethylene glycol ether; The D50 of silver powder B is that 0.1-1 μ m, D90 are less than 4 μ m, tap density is greater than 5g/cm
3, silver powder B surface coats one or more in butyl carbitol, butyl carbitol acetate, tributyl citrate, phenmethylol, turpentine oil, terpinol, triethyl citrate, acetylation tributyl citrate, lecithin, diethylene glycol ether;
4) prepare silver paste: according to following percentage by weight preparation raw material: silver powder 80-93, glass dust 0.5-5, organic carrier 4-19, inorganic assistant 0-2, wetting dispersing agent 0-1, wherein inorganic assistant is selected from Mg, Ca, Mn, Zn, P, Al, Ag, Pt, Au, La, Ce, Nd, Hf, Ta, W, Ba, Cr, Rb, Y, Mo, Rh, Pd, In, Sn, Sb, Te, Pb, simple substance in the Si element, oxide, the carbonic acid thing, alloy or organic substance, inorganic assistant is also above-mentioned simple substance, oxide, the carbonic acid thing, alloy, one or more mixtures in organic substance: then with mixer, carry out dispersed with stirring, carry out rolling with three-roll grinder afterwards, require granularity to be less than 12 μ m, during 25 ℃ of viscosity, be 80kep-180kcp, make silver electrode paste.
The preparation method of high square resistance silicon solar cell of the present invention front silver electrode paste, in step 1) in: described PbO and SiO
2mass ratio is 4-10.
The preparation method of high square resistance silicon solar cell of the present invention front silver electrode paste, in step 2) in: organic solvent is selected from one or more in butyl carbitol, butyl carbitol acetate, tributyl citrate, phenmethylol, turpentine oil, terpinol, triethyl citrate, acetylation tributyl citrate, alcohol ester 12, lecithin, diethylene glycol ether; Thickener is selected from one or more in ethyl cellulose, acrylic resin, nitrocellulose, phenolic resins, abietic resin, cellaburate, epoxy resin, polymethacrylates; Thixotropic agent is selected from one or more in rilanit special, modified hydrogenated castor oil, polyamide wax and modified polyamide wax, O-phthalic base dibutyl ester; Wetting dispersing agent is selected from that enlightening is high by 655, one or more in BYKl05, Lu Borun 20000/24000.
Compared with prior art beneficial effect of the present invention is:
1, glass dust takes low temperature and high temp glass powder to mix, thereby control speed and the degree of depth of each temperature section glass dust erosion silicon nitride layer in high-temperature sintering process by resize ratio, to form good contact, erosion effect and adhesive force, particularly adapt to the high square resistance crystal-silicon battery slice;
2, mix silver powder and take large small particle diameter silver powder to arrange in pairs or groups to realize closestpacking, to reduce the volume resistance of entire slurry, thereby realize the purpose that reduces in-fighting, raises the efficiency, improves silver layer compactness;
3, organic carrier is taked the thickener of combination solvent appropriate mix, good thixotropic agent and wetting dispersing agent, realize controlling viscosity, improve thixotropy, make slurry there is good thixotropy and printing performance, thereby improve hypermutation than reaching the purpose that improves battery efficiency;
4, the present invention adopts specific inorganic assistant, realizes highly doped, low surface recombination at slurry and high square resistance silicon cell contact-making surface, thereby makes the high square resistance silicon cell have low contact resistance and high conversion efficiency.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples are used for the present invention is described, but are not used for limiting the scope of the invention.
Embodiment 1
A kind of high square resistance silicon solar cell front silver electrode paste, it is prepared according to following formula, and its preparation method comprises the following steps:
1) prepare glass dust: SiO
2: 15%, B
2o
3: 3%, PbO:72%, TiO
2: 0.5%, Al
2o
3: 1%, ZnO:2%, MgO:0.5%, V
2o
5: 1.5%, Li
2o:1.5%, additive: 3%, after taking by weight percentage above-mentioned substance and mixing, under 900 ℃, insulation is 60 minutes, and after shrend, ball milling is 8 hours, standby after 400 eye mesh screen filtering dryings are crossed 200 eye mesh screens;
2) prepare organic carrier: by weight percentage 7% ethyl cellulose resin is joined in the mixed solvent of butyl carbitol acetate of 63% butyl carbitol and 30%, be heated to 70 ℃-95 ℃ to after dissolving 1.5 hours fully in water bath with thermostatic control, through 400 orders, filter to obtain organic carrier;
3) prepare slurry: by weight percentage by above-mentioned 4% glass dust, 77% silver powder A, 10% silver powder B, 8% organic carrier, 1% inorganic assistant, they are mixed in planetary or other mixer, at three-roll grinder machine top roll, be rolled to below 12 μ m again, finally in 400 eye mesh screens, filter, with Brookfield DV-II viscosimeter, record the front side silver paste that viscosity is 120kcps;
4) use silk screen printing upper at 156*156 monocrystalline silicon piece (90 Ω/) in this slurry, drying, sintering, detail parameters is in Table 1.
Embodiment 2
A kind of high square resistance silicon solar cell front silver electrode paste, it is prepared according to following formula, and its preparation method comprises the following steps:
1) prepare glass dust: SiO
2: 20%, B
2o
3: 3%, PbO:67%, TiO
2: 0.5%, Al
2o
3: 1%, ZnO:2%, MgO:0.5%, V
2o
5: 1.5%, Li
2o:1.5%, additive: 3%, after taking by weight percentage above-mentioned substance and mixing, under 900 ℃, insulation is 60 minutes, and after shrend, ball milling is 8 hours, standby after 400 eye mesh screen filtering dryings are crossed 200 eye mesh screens;
2) prepare organic carrier: by weight percentage 7% ethyl cellulose resin is joined in the mixed solvent of butyl carbitol acetate of 63% butyl carbitol and 30%, be heated to 70 ℃-95 ℃ to after dissolving 1.5 hours fully in water bath with thermostatic control, through 400 orders, filter to obtain organic carrier;
3) prepare slurry: by weight percentage by above-mentioned 4% glass dust, 77% silver powder A, 10% silver powder B, 8% organic carrier, 1% inorganic assistant, they are mixed in planetary or other mixer, at three-roll grinder machine top roll, be rolled to below 12 μ m again, finally in 400 eye mesh screens, filter, with Brookfield DV-II viscosimeter, record the front side silver paste that viscosity is 120kcps;
4) use silk screen printing upper at 156*156 monocrystalline silicon piece (90 Ω/) in this slurry, drying, sintering, detail parameters is in Table 1.
Embodiment 3
A kind of high square resistance silicon solar cell front silver electrode paste, it is prepared according to following formula, and its preparation method comprises the following steps:
1) prepare glass dust: SiO
2: 20%, B
2o
3: 3%, PbO:70%, TiO
2: 0.5%, Al
2o
3: 1%, ZnO:2%, MgO:0.5%, V
2o
5: 1.5%, Li
2o:1.5%, after percentage takes above-mentioned substance and mixes by weight, under 900 ℃, insulation is 60 minutes, and after shrend, ball milling is 8 hours, standby after 400 eye mesh screen filtering dryings are crossed 2200 eye mesh screens;
2) prepare organic carrier: by weight percentage 7% ethyl cellulose resin is joined in the mixed solvent of butyl carbitol acetate of 63% butyl carbitol and 30%, be heated to 70 ℃-95 ℃ to after dissolving 1.5 hours fully in water bath with thermostatic control, through 400 orders, filter to obtain organic carrier:
3) prepare slurry: by weight percentage by above-mentioned 4% glass dust, 78% silver powder l, 10% silver powder 2,8% organic carrier, they are mixed in planetary or other mixer, at three-roll grinder machine top roll, be rolled to below 12 μ m again, finally in 400 eye mesh screens, filter, with Brookfield DV-II viscosimeter, record the front side silver paste that viscosity is 120kcps;
4) use silk screen printing upper at 156*156 monocrystalline silicon piece (90 Ω/) in this slurry, drying, sintering, detail parameters is in Table 1.
Embodiment 4
A kind of high square resistance silicon solar cell front silver electrode paste, it is prepared according to following formula, and its preparation method comprises the following steps:
1) prepare glass dust: SiO
2: 25%, B
2o
3: 3%, PbO:62%, TiO
2: 0.5%, Al
2o
3: 1%, ZnO:2%, MgO:0.5%, V
2o
5: 1-5%, Li
2o:1.5%, additive: 3%, after percentage takes above-mentioned substance and mixes by weight, under 900 ℃, insulation is 60 minutes, and after shrend, ball milling is 8 hours, standby after 400 eye mesh screen filtering dryings are crossed 200 eye mesh screens;
2) prepare organic carrier: by weight percentage 7% ethyl cellulose resin is joined in the mixed solvent of butyl carbitol acetate of 63% butyl carbitol and 30%, be heated to 70 ℃-95 ℃ to after dissolving 1.5 hours fully in water bath with thermostatic control, through 400 orders, filter to obtain organic carrier;
3) prepare slurry: by weight percentage by above-mentioned 4% glass dust, 77% silver powder A, 10% silver powder B, 8% organic carrier, 1% inorganic assistant, they are mixed in planetary or other mixer, at three-roll grinder machine top roll, be rolled to below 12 μ m again, finally in 400 eye mesh screens, filter, with Brookfield DV-II viscosimeter, record the front side silver paste that viscosity is 120kcps;
4) use silk screen printing upper at 156*156 monocrystalline silicon piece (90 Ω/) in this slurry, drying, sintering, detail parameters is in Table 1.
The experiment parameter of the obtained slurry of each embodiment of table 1
| ? | Uoc | NCell | FF | Rs | Isc | Rsh | Irev2 |
| Embodiment 1 | 0.6313 | 0.1846 | 78.4500 | 0.00227 | 8.9094 | 28.9642 | 1.2802 |
| Embodiment 2 | 0.6324 | 0.1854 | 78.6368 | 0.00208 | 8.9088 | 31.6450 | 1.1249 |
| Embodiment 3 | 0.6313 | 0.1827 | 77.8428 | 0.00229 | 8.8847 | 26.3318 | 2.3533 |
| Embodiment 4 | 0.6327 | 0.1852 | 78.3605 | 0.00228 | 8.9261 | 24.1793 | 1.4079 |
| The contrast sample | 0.6307? | 0.1831 | 78.0949 | 0.00241 | 8.8842 | 27.0036 | 1.4553 |
Illustrate: this experiment printed sheet number is that 20/sample, upper table data are that peak temperature is 800 ℃ to 20 rear data of averaging.
The above is only the preferred embodiment of the present invention; it 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 improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (4)
1. a high square resistance silicon solar cell front silver electrode paste, is characterized in that, by the raw material that comprises following percentage by weight, made: silver powder 80-93, glass dust 0.5-5, organic carrier 4-19, inorganic assistant 0-2, wetting dispersing agent 0-1; Organic carrier is comprised of organic solvent, thickener, thixotropic agent, wetting dispersing agent, wherein organic solvent: thickener=(80-95): (2-13); Organic solvent: thixotropic agent=(80-95): (0.5-6); Organic solvent: wetting dispersing agent=(80-95): (0-3); Inorganic assistant is selected from simple substance, oxide, carbonic acid thing, alloy or the organic substance in Mg, Ca, Mn, Zn, P, Al, Ag, Pt, Au, La, Ce, Nd, Hf, Ta, W, Ba, Cr, Rb, Y, Mo, Rh, Pd, In, Sn, Sb, Te, Pb, Si element, and inorganic assistant is also one or more mixtures in above-mentioned simple substance, oxide, carbonic acid thing, alloy, organic substance.
2. the preparation method of a high square resistance silicon solar cell front silver electrode paste, is characterized in that, comprises the following steps:
1) prepare glass dust: the raw material according to following percentage by weight is prepared, is mixed: SiO
23-35, B
2o
31-15, PbO35-80, TiO
20.5-5, Al
2o
30.5-5, ZnO0.5-10, MgO0.5-3, V
2o
50.5-5, Li
2o0.5-3, additive 0-10; Then making average particle size range through hot melt, cooling, pulverizing, ball milling, dried and screened is that 0.5 μ m-10 μ m, softening point are the glass dust that 350-720 ℃, specific area are less than 5g/cm3; Wherein additive is selected from simple substance, oxide, carbonic acid thing, alloy or the organic substance in Ca, Mn, P, Ag, Pt, Au, La, Ce, Nd, Hf, Ta, W, Ba, Cr, Rb, Y, Mo, Rh, Pd, In, Sn, Sb, Te element, and additive is also one or more mixtures in above-mentioned simple substance, oxide, carbonic acid thing, alloy, organic substance;
2) prepare organic carrier: organic carrier is comprised of organic solvent, thickener, thixotropic agent, wetting dispersing agent, wherein organic solvent: thickener=(80-95): (2-13); Organic solvent: thixotropic agent=(80-95): (0.5-6); Organic solvent: wetting dispersing agent=(80-95): (0-3); Be positioned over after mixing according to aforementioned proportion in the water bath of 70-95 ℃ and stir insulation 1.5 hours, cross afterwards 400 eye mesh screens and obtain organic carrier;
3) prepare silver powder: silver powder is comprised of silver powder A and silver powder B, and silver powder A and silver powder B are spherical, and the mixing quality ratio of silver powder A and silver powder B is 7-15; The D50 of silver powder A is that 1.5-4 μ m, D90 are less than 10 μ m, tap density is greater than 3.5g/cm
3, silver powder A surface coats one or more in butyl carbitol, butyl carbitol acetate, tributyl citrate, phenmethylol, turpentine oil, terpinol, triethyl citrate, acetylation tributyl citrate, lecithin, diethylene glycol ether; The D50 of silver powder B is that 0.1-1 μ m, D90 are less than 4 μ m, tap density is greater than 5g/cm
3, silver powder B surface coats one or more in butyl carbitol, butyl carbitol acetate, tributyl citrate, phenmethylol, turpentine oil, terpinol, triethyl citrate, acetylation tributyl citrate, lecithin, diethylene glycol ether;
4) prepare silver paste: according to following percentage by weight preparation raw material: silver powder 80-93, glass dust 0.5-5, organic carrier 4-19, inorganic assistant 0-2, wetting dispersing agent 0-1; Wherein inorganic assistant is selected from simple substance, oxide, carbonic acid thing, alloy or the organic substance in Mg, Ca, Mn, Zn, P, Al, Ag, Pt, Au, La, Ce, Nd, Hf, Ta, W, Ba, Cr, Rb, Y, Mo, Rh, Pd, In, Sn, Sb, Te, Pb, Si element, and inorganic assistant is also one or more mixtures in above-mentioned simple substance, oxide, carbonic acid thing, alloy, organic substance; Then carrying out dispersed with stirring with mixer, carry out rolling with three-roll grinder afterwards, require granularity to be less than 12 μ m, is 80kep-180kcp during 25 ℃ of viscosity, makes silver electrode paste.
3. the preparation method of high square resistance silicon solar cell according to claim 2 front silver electrode paste, is characterized in that, in step 1) in: described PbO and SiO
2mass ratio is 4-10.
4. the preparation method of high square resistance silicon solar cell according to claim 2 front silver electrode paste, it is characterized in that, in step 2) in: organic solvent is selected from one or more in butyl carbitol, butyl carbitol acetate, tributyl citrate, phenmethylol, turpentine oil, terpinol, triethyl citrate, acetylation tributyl citrate, alcohol ester 12, lecithin, diethylene glycol ether; Thickener is selected from one or more in ethyl cellulose, acrylic resin, nitrocellulose, phenolic resins, abietic resin, cellaburate, epoxy resin, polymethacrylates; Thixotropic agent is selected from one or more in rilanit special, modified hydrogenated castor oil, polyamide wax and modified polyamide wax, O-phthalic base dibutyl ester.
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