CN105118545B - Lead free solar cell front electrode silver slurry - Google Patents
Lead free solar cell front electrode silver slurry Download PDFInfo
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- CN105118545B CN105118545B CN201510585057.7A CN201510585057A CN105118545B CN 105118545 B CN105118545 B CN 105118545B CN 201510585057 A CN201510585057 A CN 201510585057A CN 105118545 B CN105118545 B CN 105118545B
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Abstract
The present invention discloses a kind of lead free solar cell front electrode silver slurry, and the front conductive silver slurry is made up of the component of following parts by weight：Silver-colored 75 ~ 91 parts of 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 hydroxylated cellulose, 0.3 ~ 0.6 part of sodium oxide molybdena, 0.7 ~ 1.3 part of tellurium dioxide, 0.55 ~ 1 part of tungstic acid, 0.25 ~ 0.5 part of oxide addition, 0.08 ~ 0.2 part of silica, 0.04 ~ 0.1 part of lithia.Lead free solar cell front electrode silver slurry of the present invention maintains prior art performance simultaneously, and glass viscosity is low, good with other component wellabilities, and slurry printing-sintering after-contraction is not easy diffusion, improves printed pattern fineness.
Description
Technical field
The present invention relates to a kind of front conductive silver slurry of crystal silicon solar batteries, belong to solar cell functional material skill
Art field.
Background technology
Traditional energy exhaustion and its increasingly serious problem of environmental pollution brought increasingly are highlighted, near using solar power generation
Tremendous development is obtained over year.Solar-energy photo-voltaic cell is that solar energy is converted into electric energy by photoelectric effect.Its operation principle one
As be：By diffuseing to form N-type layer in P type substrate, critical part formation P-N junction will produce light when illumination is mapped to P-N junction
Raw carrier, carrier exports battery by good conductor material, so as to form current electric power generation.This good conductor material
It is exactly front electrode silver slurry, back electrode silver paste and backplate aluminium paste, solar cell is printed on by screen printing mode
Positive pole and backplane.
Front electrode of solar battery silver paste is to influence one of main raw material(s) of solar cell electrical property.Front side silver paste
Mainly it is made up of three parts：Conductive phase, organic phase and inorganic phase.Conductive phase has been the metal dust of electric action, general to use
The best micro silver powder of electric conductivity；Organic phase is the organic carrier suitable for screen printing technique, and organic carrier is mainly by organic
Solvent, plasticizer, thixotropic agent, levelling agent and surfactant etc. constitute, be slurry have suitable for silk-screen printing viscosity,
The rheological properties such as thixotropy；Inorganic phase is mainly low glass dust and metal oxide, plays and grills thoroughly anti-reflection layer and cementation.
Its performance is had higher requirements：Because it is in smooth surface, it is desirable to there is higher depth-width ratio, realizing that high conductivity is same
When shading rate it is minimum；Can corroding silicon nitride layer with silicon substrate formed good ohmic contact and good cohesive strength；Solderability is good, just
Welded in plain conductor；Printing performance is good, is easy to typography to operate.
Traditional front electrode of solar battery silver paste majority uses the glass powder with low melting point containing PbO, mainly due to PbO
The softening temperature of glass dust can be significantly reduced, and powder containing flint glass has preferable wellability, molten silver-colored energy with matrix material
Power is strong.However, lead not only pollutes environment also larger harm to human body.Prepare environmentally friendly lead free solar cell front electricity
Pole silver paste, most critical is exactly to develop lead-free glass powder, is substituting flint glass powder simultaneously, it is ensured that size performance.Suitable for too
It is positive can the lead-free glass powder of battery had more research, but be extremely difficult to or more than flint glass mealiness energy, mainly glass
The problem of changing higher temperature and poor wellability.
The content of the invention
The present invention provides a kind of lead free solar cell front electrode silver slurry, the lead free solar cell front electrode silver slurry
Maintain prior art performance simultaneously, glass viscosity is low, it is good with other component wellabilities, it is not easy to expand after slurry printing-sintering
Dissipate, improve printed pattern fineness.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of lead free solar cell front electrode silver slurry,
The front conductive silver slurry is made up of the component of following parts by weight：
Silver-colored 75 ~ 91 parts of conductive phase,
5 ~ 12 parts of organic solvent,
0.6 ~ 1 part of ethyl cellulose,
0.4 ~ 0.8 part of butyl cellulose,
0.4 ~ 0.8 part of hydroxylated cellulose,
0.3 ~ 0.6 part of sodium oxide molybdena,
0.7 ~ 1.3 part of tellurium dioxide,
0.55 ~ 1 part of tungstic acid,
0.25 ~ 0.5 part of oxide addition,
0.08 ~ 0.2 part of silica,
0.04 ~ 0.1 part of lithia.
Further improved technical scheme in above-mentioned technical proposal is as follows：
1. in such scheme, the oxide addition is aluminum oxide, molybdenum oxide, lanthana, bismuth oxide, oxidation
Calcium, boron oxide, zinc oxide, selenium dioxide, barium monoxide, strontium oxide strontia, niobium pentaoxide, zirconium dioxide, potassium oxide, chromium trioxide,
At least one of di-iron trioxide and nickel oxide.
2. in such scheme, the oxide addition by 2 parts of aluminum oxide, 2 parts of lanthanas, 3 parts of bismuth oxides, 2 parts
Barium monoxide, 2 parts of zirconium dioxide compositions；Or by 3 parts of molybdenum oxides, 2 parts of calcium oxide, 2 parts of boron oxides, 2 parts of strontium peroxides, 2 part three
Chromium oxide is constituted；Or by 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
Composition；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 by
2 parts of bismuth oxides, 2 parts of boron oxides, 2 parts of zirconium dioxides, 3 parts of potassium oxides, 2 parts of chromium trioxide compositions.
3. in such scheme, the organic solvent is terpinol, butyl carbitol, butyl carbitol acetate and the third two
At least one of alcohol methyl ether acetate.
4. in such scheme, the silver-colored conductive phase is 0.5 ~ 10 micro-silver powder.
Because above-mentioned technical proposal is used, the present invention has following advantages and effect compared with prior art：
1. lead free solar cell front electrode silver slurry of the present invention, it contains 0.3 ~ 0.6 part of sodium oxide molybdena, dioxy in being formulated
Change 0.7 ~ 1.3 part of tellurium, 0.55 ~ 1 part of tungstic acid, maintain prior art performance simultaneously, glass viscosity is low, soaked with other components
Lubricant nature is good, is not easy diffusion after slurry printing-sintering, improves printed pattern fineness；Secondly, oxygen in its front electrode silver slurry
Changing 0.3 ~ 0.6 part of sodium, 0.7 ~ 1.3 part of tellurium dioxide, 0.55 ~ 1 part of tungstic acid coordinates 0.6 ~ 1 part of ethyl cellulose, butyl fine
Dimension plain 0.4 ~ 0.8 part, 0.4 ~ 0.8 part of hydroxylated cellulose, adjust viscosity, improve front electrode silver slurry glass performance, such as viscosity,
Softening temperature, chemical stability, glass transition point, linear expansion coefficient etc..
2. lead free solar cell front electrode silver slurry of the present invention, its front electrode silver slurry further contains silica
0.08 ~ 0.2 part, 0.04 ~ 0.1 part of lithia, 0.25 ~ 0.5 part of oxide addition not only increase front electrode silver slurry and silicon
Piece has good contact, and electrode metal grid line also has good electric conductivity in itself, and can obtain the front of depth-width ratio
Thin grid line.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1 ~ 5：A kind of lead free solar cell front electrode silver slurry, the front conductive silver slurry is by following weight
The component composition of part, as shown in table 1：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Silver-colored 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 |
| Silica | 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 |
The oxide addition is made up of the component of following parts by weight, as shown in table 2：
Table 2
Above-mentioned organic solvent is in terpinol, butyl carbitol, butyl carbitol acetate and propylene glycol methyl ether acetate
At least one.
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 1: 0.3 ~ 0.6 part of sodium oxide molybdena, 0.7 ~ 1.3 part of tellurium dioxide, 0.55 ~ 1 part of tungstic acid, oxide are added
Plus 0.25 ~ 0.5 part of agent, 0.08 ~ 0.2 part of silica, 0.04 ~ 0.1 part of lithia are put in batch mixer and are well mixed, and are placed in Muffle
In stove, 850 degree are incubated 30 minutes, are annealed after glass water quenching after abundant melting doping, obtain frit after water quenching；
Step 2: frit is ground in alcohol system with star lapping machine after the water quenching that step one is obtained, dry
It is 0.4 ~ 0.6 μm of glass powder to particle diameter；
Step 2: 5 ~ 12 parts of organic solvent, 0.7 ~ 1 part of ethyl cellulose, 0.4 ~ 0.8 part of butyl cellulose, hydroxyl is fine
0.4 ~ 0.8 part of dimension element, 60 degree mix 30 minutes, obtain carrier；
Step 4: after the carrier of silver-colored 75 ~ 91 parts of conductive phase, the glass powder of step 2, step 3 is stirred, three rollers
Machine grinding distribution three times, filtering obtains the lead free solar cell front electrode silver slurry；
Step 5: lead free solar cell front electrode silver slurry of the present invention is printed onto into polycrystal silicon cell through screen process press
On piece and sinter, 890 degree of sintering temperature, benchmark is done with best slurry 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 |
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (4)
1. a kind of lead free solar cell front electrode silver slurry, it is characterised in that：The lead free solar cell front electrode silver
Slurry is made up of the component of following parts by weight：
Silver-colored 75 ~ 91 parts of conductive phase,
5 ~ 12 parts of organic solvent,
0.6 ~ 1 part of ethyl cellulose,
0.4 ~ 0.8 part of butyl cellulose,
0.4 ~ 0.8 part of hydroxylated cellulose,
0.3 ~ 0.6 part of sodium oxide molybdena,
0.7 ~ 1.3 part of tellurium dioxide,
0.55 ~ 1 part of tungstic acid,
0.25 ~ 0.5 part of oxide addition,
0.08 ~ 0.2 part of silica,
0.04 ~ 0.1 part of lithia；
The oxide addition is aluminum oxide, molybdenum oxide, lanthana, bismuth oxide, calcium oxide, boron oxide, zinc oxide, two
Selenium oxide, barium monoxide, strontium peroxide, niobium pentaoxide, zirconium dioxide, potassium oxide, chromium trioxide, di-iron trioxide and nickel oxide
At least one of.
2. front electrode silver slurry according to claim 1, it is characterised in that：The oxide addition by 2 parts of aluminum oxide,
2 parts of lanthanas, 3 parts of bismuth oxides, 2 parts of barium monoxide, 2 parts of zirconium dioxide compositions；Or by 3 parts of molybdenum oxides, 2 parts of calcium oxide, 2
Part boron oxide, 2 parts of strontium oxide strontias, 2 parts of chromium trioxides compositions；Or by 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 trioxide compositions；Or by 3 parts of molybdenum oxides, 2 parts of selenium dioxide, 2 parts of barium monoxide, 2 part of five oxidation two
Niobium, 2 parts of nickel oxide compositions；Or by 2 parts of bismuth oxides, 2 parts of boron oxides, 2 parts of zirconium dioxides, 3 parts of potassium oxides, 2 part of three oxygen
Change chromium composition.
3. front electrode silver slurry according to claim 1, it is characterised in that：The organic solvent is terpinol, butyl card
Must at least one of alcohol, butyl carbitol acetate and propylene glycol methyl ether acetate.
4. front electrode silver slurry according to claim 1, it is characterised in that：The silver-colored conductive phase is 0.5 ~ 10 micron of silver
Powder.
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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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| 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 |
| JP5011428B2 (en) * | 2010-10-07 | 2012-08-29 | 昭栄化学工業株式会社 | Solar cell element and method for manufacturing the same |
| KR101587683B1 (en) * | 2013-02-15 | 2016-01-21 | 제일모직주식회사 | The composition for forming solar cell electrode comprising the same, and electrode prepared using the same |
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