CN105118545A - Front electrode silver paste of lead-free solar cell - Google Patents
Front electrode silver paste of lead-free solar cell Download PDFInfo
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- CN105118545A CN105118545A CN201510585057.7A CN201510585057A CN105118545A CN 105118545 A CN105118545 A CN 105118545A CN 201510585057 A CN201510585057 A CN 201510585057A CN 105118545 A CN105118545 A CN 105118545A
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Abstract
The invention discloses the front electrode silver paste of a lead-free solar cell. The front conductive silver paste comprises the following components by weight in part: 75-91 parts of silver conductive phase, 5-12 parts of organic solvent, 0.7-1 part of ethyl cellulose, 0.4-0.8 part of butyl cellulose, 0.4-0.8 part of hydroxypropyl-cellulose, 0.3-0.6 part of sodium oxide, 0.7-1.3 part of tellurium dioxide, 0.55-1 part of tungsten trioxide, 0.25-0.5 part of oxide additives, 0.08-0.2 part of silicon dioxide, and 0.04-0.1 part of lithium oxide. According to the invention, the existing performances in the prior art are maintained by the front electrode silver paste of the lead-free solar cell, while the glass is low in viscosity and good in wettability with other components. After the printing and sintering process of the paste, the paste is good in contractility and does not easily diffuse. Therefore, the fineness of printed graphics is improved.
Description
Technical field
The present invention relates to a kind of front conductive silver slurry of crystal silicon solar batteries, belong to solar cell technical field of function materials.
Background technology
The traditional energy increasingly serious problem of environmental pollution that is exhausted and that bring more and more highlights, and utilizes solar power generation to obtain tremendous development in recent years.Solar-energy photo-voltaic cell is, by photoelectric effect, solar energy is converted into electric energy.Its operation principle is generally: by diffuseing to form N-type layer in P type substrate, and critical part forms P-N junction, will produce photo-generated carrier when illumination is mapped to P-N junction, and charge carrier derives battery by good conductor material, thus forms current electric power generation.This good conductor material is exactly front electrode silver slurry, back electrode silver paste and backplate aluminium paste, is printed on solar cell positive pole and backplane by screen printing mode.
Front electrode of solar battery silver slurry is one of main raw material(s) affecting solar cell electrical property.Front side silver paste forms primarily of three parts: conductive phase, organic phase and inorganic phase.Conductive phase has been the metal dust of electric action, the general micro silver powder adopting electric conductivity best; Organic phase is the organic carrier being applicable to screen printing technique, and organic carrier, primarily of compositions such as organic solvent, plasticizer, thixotropic agent, levelling agent and surfactants, is that slurry has the rheological property such as viscosity, thixotropy being applicable to silk screen printing; Inorganic phase is mainly low glass dust and metal oxide, plays and grills thoroughly anti-reflection layer and cementation.
Have higher requirements to its performance: because it is at sensitive surface, require higher depth-width ratio, realizing high conductivity, shading rate is minimum simultaneously; Can contact and good cohesive strength with silica-based formation good ohmic by corroding silicon nitride layer; Solderability is good, is convenient to weld with plain conductor; Printing performance is good, is convenient to typography operation.
Traditional most glass powder with low melting point used containing PbO of front electrode of solar battery silver slurry, mainly because PbO significantly can reduce the softening temperature of glass dust, and have good wettability containing flint glass powder and basis material, molten silver-colored ability is strong.But lead not only contaminated environment also has larger harm to human body.Prepare environmentally friendly lead free solar cell front electrode silver slurry, most critical develops lead-free glass powder exactly, at alternative flint glass powder simultaneously, ensures size performance.The lead-free glass powder being applicable to solar cell has had more research, but is difficult to meet or exceed flint glass mealiness energy, the problem that mainly vitrification point is higher and wettability is poor.
Summary of the invention
The invention provides a kind of lead free solar cell front electrode silver slurry, this lead free solar cell front electrode silver slurry maintains prior art performance simultaneously, and glass viscosity is low, good with other component wettability, be not easy diffusion after slurry printing-sintering, improve printed pattern fineness.
For achieving the above object, the technical solution used in the present invention is: a kind of lead free solar cell front electrode silver slurry, and described front conductive silver slurry is made up of the component of following weight portion:
Silver conductive phase 75 ~ 91 parts,
Organic solvent 5 ~ 12 parts,
Ethyl cellulose 0.6 ~ 1 part,
Butyl cellulose 0.4 ~ 0.8 part,
Hydroxylated cellulose 0.4 ~ 0.8 part,
Sodium oxide molybdena 0.3 ~ 0.6 part,
Tellurium dioxide 0.7 ~ 1.3 part,
Tungstic acid 0.55 ~ 1 part,
Oxide addition 0.25 ~ 0.5 part,
Silicon dioxide 0.08 ~ 0.2 part,
Lithia 0.04 ~ 0.1 part.
The technical scheme of the further improvement in technique scheme is as follows:
1., in such scheme, described oxide addition is at least one in aluminium oxide, molybdenum oxide, lanthana, bismuth oxide, calcium oxide, boron oxide, zinc oxide, selenium dioxide, barium monoxide, strontium oxide strontia, niobium pentaoxide, zirconium dioxide, potassium oxide, chromium trioxide, di-iron trioxide and nickel oxide.
2., in such scheme, described oxide addition is made up of 2 parts of aluminium oxide, 2 parts of lanthanas, 3 parts of bismuth oxides, 2 parts of barium monoxide, 2 parts of zirconium dioxides; Or be made up of 3 parts of molybdenum oxides, 2 parts of calcium oxide, 2 parts of boron oxides, 2 parts of strontium peroxides, 2 parts of chromium trioxides; Or be made up of 2 parts of zinc oxide, 2 parts of selenium dioxide, 2 parts of niobium pentaoxides, 3 parts of potassium oxides, 2 parts of di-iron trioxides; Or be made up of 3 parts of molybdenum oxides, 2 parts of selenium dioxide, 2 parts of barium monoxide, 2 parts of niobium pentaoxides, 2 parts of nickel oxide; Or be made up of 2 parts of bismuth oxides, 2 parts of boron oxides, 2 parts of zirconium dioxides, 3 parts of potassium oxides, 2 parts of chromium trioxides.
3., in such scheme, described organic solvent is at least one in terpinol, butyl carbitol, butyl carbitol acetate and 1-Methoxy-2-propyl acetate.
4., in such scheme, described silver-colored conductive phase is 0.5 ~ 10 micro-silver powder.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect:
1. lead free solar cell front electrode silver slurry of the present invention, containing sodium oxide molybdena 0.3 ~ 0.6 part, tellurium dioxide 0.7 ~ 1.3 part, tungstic acid 0.55 ~ 1 part in its formula, maintain prior art performance simultaneously, glass viscosity is low, good with other component wettability, be not easy diffusion after slurry printing-sintering, improve printed pattern fineness; Secondly, in its front electrode silver slurry, sodium oxide molybdena 0.3 ~ 0.6 part, tellurium dioxide 0.7 ~ 1.3 part, tungstic acid 0.55 ~ 1 part coordinate ethyl cellulose 0.6 ~ 1 part, butyl cellulose 0.4 ~ 0.8 part, hydroxylated cellulose 0.4 ~ 0.8 part, adjusting viscosity, improve front electrode silver slurry glass performance, as viscosity, softening temperature, chemical stability, glass transition point, coefficient of linear expansion etc.
2. lead free solar cell front electrode silver slurry of the present invention, its front electrode silver slurry contains silicon dioxide 0.08 ~ 0.2 part, lithia 0.04 ~ 0.1 part further, oxide addition 0.25 ~ 0.5 part not only increases front electrode silver slurry has good contacting with silicon chip, and electrode metal grid line itself also has good electric conductivity, and the thin grid line in the front that can obtain depth-width ratio.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1 ~ 5: a kind of lead free solar cell front electrode silver slurry, described front conductive silver slurry is made up of the component of following weight portion, as shown in table 1:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Silver conductive phase | 80 parts | 85 parts | 76 parts | 88 parts | 90 parts |
| Organic solvent | 9 parts | 10.2 parts | 12 parts | 11 parts | 5.95 part |
| Ethyl cellulose | 0.8 part | 0.6 part | 1 part | 0.9 part | 0.6 part |
| Butyl cellulose | 0.7 part | 0.6 part | 0.5 part | 0.8 part | 0.7 part |
| Hydroxylated cellulose | 0.5 part | 0.6 part | 0.7 part | 0.65 part | 0.75 part |
| Sodium oxide molybdena | 0.6 part | 0.48 part | 0.5 part | 0.5 part | 0.3 part |
| Tellurium dioxide | 1.15 part | 1.21 part | 1.3 part | 1.25 part | 0.78 part |
| Tungstic acid | 0.7 part | 0.83 part | 0.9 part | 1 part | 0.55 part |
| Oxide addition | 0.35 part | 0.33 part | 0.45 part | 0.3 part | 0.25 part |
| Silicon dioxide | 0.12 part | 0.15 part | 0.15 part | 0.2 part | 0.08 part |
| Lithia | 0.06 part | 0.075 part | 0.075 part | 0.1 part | 0.04 part |
Described oxide addition is made up of the component of following weight portion, as shown in table 2:
Table 2
Above-mentioned organic solvent is at least one in terpinol, butyl carbitol, butyl carbitol acetate and 1-Methoxy-2-propyl acetate.
Above-mentioned silver-colored conductive phase is 0.5 ~ 10 micro-silver powder.
The preparation method of above-mentioned lead free solar cell front electrode silver slurry, comprises the following steps:
Step one, sodium oxide molybdena 0.3 ~ 0.6 part, tellurium dioxide 0.7 ~ 1.3 part, tungstic acid 0.55 ~ 1 part, oxide addition 0.25 ~ 0.5 part, silicon dioxide 0.08 ~ 0.2 part, lithia 0.04 ~ 0.1 part are put in batch mixer and mixed, be placed in Muffle furnace, 850 degree of insulations 30 minutes, glass shrend annealing after abundant melting doping, frit after acquisition shrend;
After step 2, the shrend that step one obtained, frit is with star lapping machine grinding in alcohol system, and drying and obtaining particle diameter is 0.4 ~ 0.6 μm of glass powder;
Step 2, by organic solvent 5 ~ 12 parts, ethyl cellulose 0.7 ~ 1 part, butyl cellulose 0.4 ~ 0.8 part, hydroxylated cellulose 0.4 ~ 0.8 part, 60 degree of mix and blends 30 minutes, obtain carrier;
Step 4, silver-colored conductive phase 75 ~ 91 parts, the glass powder of step 2, the carrier of step 3 are stirred after, three-roller grinding distribution three times, filter, obtain described lead free solar cell front electrode silver slurry;
Step 5, lead free solar cell front electrode silver slurry of the present invention to be printed onto on polycrystalline silicon battery plate through screen process press and to sinter, sintering temperature 890 degree, doing benchmark with slurry best in industry.
The test electrical property of embodiment 1 is as described in Table 3:
Table 3
| Unit for electrical property parameters | η/% | Isc/A | Voc/V | FF/% |
| Benchmark | 17.89 | 8.639 | 0.631 | 77.88 |
| Embodiment 1 | 18.01 | 8.692 | 0.635 | 78.04 |
The test electrical property of embodiment 2 is as described in Table 4:
Table 4
| Unit for electrical property parameters | η/% | Isc/A | Voc/V | FF/% |
| Benchmark | 17.89 | 8.639 | 0.631 | 77.88 |
| Embodiment 2 | 18.03 | 8.683 | 0.637 | 78.12 |
The test electrical property of embodiment 3 is as described in Table 5:
Table 5
| Unit for electrical property parameters | η/% | Isc/A | Voc/V | FF/% |
| Benchmark | 17.89 | 8.639 | 0.631 | 77.88 |
| Embodiment 3 | 17.98 | 8.675 | 0.643 | 77.95 |
The test electrical property of embodiment 4 is as described in Table 6:
Table 6
| Unit for electrical property parameters | η/% | Isc/A | Voc/V | FF/% |
| Benchmark | 17.89 | 8.639 | 0.631 | 77.88 |
| Embodiment 4 | 18.05 | 8.694 | 0.64 | 78.08 |
The test electrical property of embodiment 5 is as described in Table 7:
Table 7
| Unit for electrical property parameters | η/% | Isc/A | Voc/V | FF/% |
| Benchmark | 17.89 | 8.639 | 0.631 | 77.88 |
| Embodiment 5 | 18.06 | 8.695 | 0.642 | 78.1 |
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. a lead free solar cell front electrode silver slurry, is characterized in that: described front conductive silver slurry is made up of the component of following weight portion:
Silver conductive phase 75 ~ 91 parts,
Organic solvent 5 ~ 12 parts,
Ethyl cellulose 0.6 ~ 1 part,
Butyl cellulose 0.4 ~ 0.8 part,
Hydroxylated cellulose 0.4 ~ 0.8 part,
Sodium oxide molybdena 0.3 ~ 0.6 part,
Tellurium dioxide 0.7 ~ 1.3 part,
Tungstic acid 0.55 ~ 1 part,
Oxide addition 0.25 ~ 0.5 part,
Silicon dioxide 0.08 ~ 0.2 part,
Lithia 0.04 ~ 0.1 part.
2. front electrode silver slurry according to claim 1, is characterized in that: described oxide addition is at least one in aluminium oxide, molybdenum oxide, lanthana, bismuth oxide, calcium oxide, boron oxide, zinc oxide, selenium dioxide, barium monoxide, strontium peroxide, niobium pentaoxide, zirconium dioxide, potassium oxide, chromium trioxide, di-iron trioxide and nickel oxide.
3. front electrode silver slurry according to claim 2, is characterized in that: described oxide addition is made up of 2 parts of aluminium oxide, 2 parts of lanthanas, 3 parts of bismuth oxides, 2 parts of barium monoxide, 2 parts of zirconium dioxides; Or be made up of 3 parts of molybdenum oxides, 2 parts of calcium oxide, 2 parts of boron oxides, 2 parts of strontium oxide strontias, 2 parts of chromium trioxides; Or be made up of 2 parts of zinc oxide, 2 parts of selenium dioxide, 2 parts of niobium pentaoxides, 3 parts of potassium oxides, 2 parts of di-iron trioxides; Or be made up of 3 parts of molybdenum oxides, 2 parts of selenium dioxide, 2 parts of barium monoxide, 2 parts of niobium pentaoxides, 2 parts of nickel oxide; Or be made up of 2 parts of bismuth oxides, 2 parts of boron oxides, 2 parts of zirconium dioxides, 3 parts of potassium oxides, 2 parts of chromium trioxides.
4. front electrode silver slurry according to claim 1, is characterized in that: described organic solvent is at least one in terpinol, butyl carbitol, butyl carbitol acetate and 1-Methoxy-2-propyl acetate.
5. front electrode silver slurry according to claim 1, is characterized in that: described silver-colored conductive phase is 0.5 ~ 10 micro-silver powder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108109716A (en) * | 2017-12-13 | 2018-06-01 | 天津宝兴威科技股份有限公司 | A kind of nano silver coating fluid formula |
| CN108666005A (en) * | 2017-03-27 | 2018-10-16 | 苏州晶银新材料股份有限公司 | Conductive silver paste for photovoltaic cell |
| CN109422461A (en) * | 2017-09-01 | 2019-03-05 | 苏州晶银新材料股份有限公司 | Microbead glass and its preparation process for conductive silver paste |
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| CN103155159A (en) * | 2010-10-07 | 2013-06-12 | 昭荣化学工业株式会社 | Solar cell element and method for manufacturing same |
| CN104412333A (en) * | 2013-02-15 | 2015-03-11 | 第一毛织株式会社 | The composition for forming solar cell electrode comprising the same, and electrode prepared using the same |
| CN104681122A (en) * | 2015-01-21 | 2015-06-03 | 浙江中希电子科技有限公司 | Silver paste for front surface of solar battery and preparation method of silver paste |
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Patent Citations (5)
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| US20110126897A1 (en) * | 2009-05-20 | 2011-06-02 | E. I. Du Pont De Nemours And Company | Composition for extruding fibers |
| CN101964219A (en) * | 2010-08-10 | 2011-02-02 | 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 |
| CN103155159A (en) * | 2010-10-07 | 2013-06-12 | 昭荣化学工业株式会社 | Solar cell element and method for manufacturing same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108666005A (en) * | 2017-03-27 | 2018-10-16 | 苏州晶银新材料股份有限公司 | Conductive silver paste for photovoltaic cell |
| CN109422461A (en) * | 2017-09-01 | 2019-03-05 | 苏州晶银新材料股份有限公司 | Microbead glass and its preparation process for conductive silver paste |
| CN108109716A (en) * | 2017-12-13 | 2018-06-01 | 天津宝兴威科技股份有限公司 | A kind of nano silver coating fluid formula |
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Address after: 215000 100 Zhenbei Road, Tongan town, high tech Zone, Suzhou City, Jiangsu Province Patentee after: Suzhou Jingyin New Material Technology Co.,Ltd. Address before: 215011 north side of 2nd floor, building 2, No.189, Kunlunshan Road, high tech Zone, Suzhou, Jiangsu Province Patentee before: SUZHOU ISILVER MATERIALS Co.,Ltd. |