CN102354545B - Sliver electrode slurry for back electric field of silicon solar cell and preparation method thereof - Google Patents
Sliver electrode slurry for back electric field of silicon solar cell and preparation method thereof Download PDFInfo
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- CN102354545B CN102354545B CN2011103313095A CN201110331309A CN102354545B CN 102354545 B CN102354545 B CN 102354545B CN 2011103313095 A CN2011103313095 A CN 2011103313095A CN 201110331309 A CN201110331309 A CN 201110331309A CN 102354545 B CN102354545 B CN 102354545B
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Abstract
The invention discloses sliver electrode slurry for a back electric field of a silicon solar cell and a preparation method thereof, and the silver electrode slurry for the back electric field of the silicon solar cell comprises the following components by weight percent: 60-70% of spherical silver powder, 0-5% of flaky silver powder, 2-6% of glass powder with a high-temperature softening point, 1-3% of glass powder with a low-temperature softening point and 20-30% of organic bonding agent. The particle size of the spherical silver powder is 0.5-2.5 mu m, and the tap density is above 4.5g/ml; the particle size of the flaky silver powder is below 5 mu m, and the tap density is above 4.0g/ml; and the glass powder with the high-temperature softening point is a PbO3-B2O3-SiO2-ZnO glass system, and the glass powder with the low-temperature softening point is a Bi2O3-B2O3-SiO2 glass system. The slurry is applied to a sliver electrode of the back electric field of the silicon solar cell; furthermore, after fast high-temperature sintering by a chained belt furnace, the adhesive capability is strong, the soldering resistance is good and the photoelectric conversion efficiency of a product is high.
Description
Technical field
The present invention relates to a kind of silicon solar cell back electric field with silver electrode paste and preparation method, belong to technical field of electronic materials.
Background technology
Along with developing rapidly of modern industry, strengthen on the one hand the demand to the energy, cause energy crisis; Discharge on the other hand a large amount of carbon dioxides in the use of conventional energy resource, cause global " greenhouse effect ".As optimal regenerative resource, solar energy has the characteristics of " inexhaustible ", and utilizes solar power generation to have environmental protection, low cost, efficiency advantages of higher, and needn't consider its safety issue.In recent years, rapidly, only China's output of 2010 had surpassed 5GW to the development of domestic silicon solar cell, and therefore, the usage quantity of the solar energy slurry of using as the back of the body electric field of solar cell constantly rises.Silver paste as solar energy back of the body battery uses, can form good ohmic contact with solar energy matrix good combination layer, and give good adhesion property after the high temperature Fast Sintering, also will prevent that binder course from crossing dark and affecting conversion efficiency simultaneously.In addition, also require the silver electrode of solar energy back of the body electric field to have good to weld, soldering resistance.
At present, the back of the body electric field that slurry both domestic and external company produces is to adopt the low glass of single softening point with the glass binder that silver electrode or silver-colored aluminum electrode slurry use substantially, it is lower that this glass has a fusing point, good fluidity during high temperature sintering, well many to the infiltration of silicon chip inside simultaneously with the silicon chip surface wetability, although can obtain good adhesive force but may cause silver powder to become a contact with contacting from the face contact of silicon chip surface, thereby having had a strong impact on photoelectric conversion efficiency.Consider from another point of view, because the glassy phase infiltration is many, may cause that the glassy phase of silver electrode surface tails off, the soldering resistance variation of the silver electrode that makes.
Summary of the invention
The objective of the invention is the shortcoming and defect that exists in order to overcome prior art, and provide silver powder to contact with silicon chip formation face, guarantee photoelectric conversion efficiency, make simultaneously the good a kind of silicon solar cell back electric field silver electrode paste of soldering resistance of silver electrode.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned silicon solar cell back electric field with silver electrode paste, this preparation method makes each component of slurry have good dispersiveness, makes after sintering to make that the silicon solar cell product has well, stablizes, electric property uniformly.
For realizing first purpose of the present invention, technical scheme of the present invention is to be characterised in that to comprise following component, by percentage to the quality: ball shape silver powder 60～70 wt%, flake silver powder 0～5 wt%,, hot mastication point glass dust 2～6wt%, low temperature softening point glass dust 1～3wt%, organic bond 20～30 wt%.
Further arranging is described spherical silver powder footpath 0.5～2.5 μ m, and tap density is more than 4.5 g/ml, and described flake silver powder particle diameter is that below 5 μ m, tap density is more than 4.0g/ml.
Further arranging is that glass used is that the collocation of high and low temperature softening point glass is used, wherein:
(1) described high softening-point glass dust is PbO
3-B
2O
3-SiO
2-ZnO glass system, its weight percent consists of: PbO
360-80%, SiO
21-30%, B
2O
31-20%, ZnO 3-20%, TiO
20.2-6%, Al
2O
30-2%, CuO 0-1%, Na
2O 0-3%, K
2O 0-3%, Na
2O+K
2O≤3%;
(2) described low softening point glass dust is Bi
2O
3-B
2O
3-SiO
2Glass system, its weight percent consists of: Bi
2O
375-95%, B
2O
34-25%, SiO
21.5-8%, Ag
2O 0-7%.
Further arranging is that described organic bond is macromolecule resin and solvent.
Further arranging is that described macromolecule resin is one or more in ethyl cellulose, Foral resin, polyurethane resin.
Further arranging is that described solvent is one or more in terpinol, butyl acetate or butyl carbitol ester.
Further arrange is that described organic bond weight percent composition in silver electrode paste is macromolecule resin 1.0～4.0 wt%, solvent 18～28wt%.
Effect of the present invention has: select the silver powder of high-tap density and use the glass of two kinds of high low softening points, make slurry low temperature softening point glass when high temperature sintering fast guarantee that slurry and silicon chip have good wettability and effectively control penetration degree to silicon chip inside, not only obtaining good adhesive force but also guaranteed that silver powder contacts and guarantees photoelectric conversion efficiency with silicon chip formation face. hot mastication point glassy phase is introduced and is met silver electrode surface bonding demand simultaneously, guarantees that the soldering resistance of silver electrode is good.Finally obtain densified sintering product, uniform silver conductive layer.
For realizing another object of the present invention, technical scheme of the present invention is component proportion according to claim 1, load weighted glass dust and organic bond are packed in ball-grinding machine, in expecting: zirconium ball=1:1 ratio adds the zirconium ball, carry out 15～24 hours mixing, ball-milling treatment and filter discharging to fineness≤7 μ m, mix through the three-high mill rolling to fineness≤below 7 μ m, obtain the silicon solar cell back electric field silver electrode paste with silver powder again.
The above-mentioned existing slurry production technology of preparation technology and present numerous slurry manufacturer of stating slurry is distinguished to some extent, existing silver electrode paste production process, be each component in slurry good by formulated after, utilize three-roll grinder fully to grind rolling after being uniformly mixed, reach certain fineness.The preparation method of silver electrode paste of the present invention, mainly to consider that in component, the characteristic such as various material patterns is different, the requirement that disperses is also distinguished, at first load weighted glass dust and organic bond are packed in ball-grinding machine, in expecting: zirconium ball=1:1 ratio adds the zirconium ball, carry out mixing in 15～24 hours, ball-milling treatment to fineness reaches≤7 μ m after by after filter material, then with silver powder, mix through the silver paste of three-high mill rolling to fineness≤below 7 μ m.
Effect of the present invention has: the silver electrode paste by the preparation of this technique both can guarantee the dispersiveness that various components are good, can guarantee again the mixed uniformity of each component,, to obtain the electrode slurry of uniform and smooth silver, make after sintering that the silicon solar cell product has well, stablizes, electric property uniformly.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as the restriction to protection range of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Solar battery back electric field silver electrode paste component and proportioning, utilize first glass dust and organic bond are packed in ball-grinding machine, in expecting: zirconium ball=1:1 ratio adds the zirconium ball, carry out mixing in 15～24 hours, ball-milling treatment, then mixes through the three-high mill rolling to fineness≤7 μ m, silver paste uniformly with silver powder by filtering discharging to fineness≤7 μ m.
At first, the basic scheme of summary material prescription of the present invention: a kind of silicon solar cell back electric field silver electrode paste, its weight percent consists of: ball shape silver powder 60～70 wt%, flake silver powder 0～5 wt%, hot mastication point glass dust 2～6wt%, low temperature softening point glass dust 1～3wt%, organic bond 18～28 wt%.
Embodiment 1-9
A kind of silicon solar cell back electric field silver electrode paste, its formula, according to No. 1-9 formula (corresponding 1-9 embodiment respectively) of table 1, can obtain good dispersion, the main material of composition homogeneous after the operations such as adjustment of formula, ball milling, rolling are processed.Metallic conduction powder described in formula is by spherical silver powder footpath 0.5～2.5 μ m, and tap density is more than 4.5 g/ml, and the flake silver powder particle diameter is that below 5 μ m, tap density is more than 4.0g/ml.Described glass binder is a kind of Bi
2O
3-B
2O
3-SiO
2The low temperature softening point glass of system and a kind of PbO
3-B
2O
3-SiO
2The hot mastication point glass of-ZnO system. in described organic bond, macromolecule resin is one or more in ethyl cellulose, Foral resin, polyurethane resin, and described solvent is one or more in terpinol, butyl acetate or butyl carbitol ester.The glass formula of selecting in formula is as shown in the 1-9 of table 2 and table 3, glass dust and organic bond after reaching certain fineness, ball milling are filtered discharging, utilize three-roll grinder fully to grind rolling after mixing with the silver powder material again, reach certain fineness.
The silver electrode paste that makes by above-mentioned formula, form the back electric field silver electrode electrode of silicon solar cell (125 * 125 specification) by silk-screen printing technique, the resulting properties of product testing result of 760 ℃/10S is as shown in table 4 in chain band sintering furnace, and the silicon solar cell of gained is functional.
Table 1: the silicon solar cell back electric field material prescription of silver electrode paste
Table 2: the compositing formula of low temperature softening point frit
| Numbering | Bi2O3 | B2O3 | SiO2 | Ag2O | Add up to |
| 1 | 90.00 | 7.50 | 1.50 | 1.00 | 100.00 |
| 2 | 82.00 | 10.50 | 4.50 | 3.00 | 100.00 |
| 3 | 75.00 | 20.00 | 5.00 | ? | 100.00 |
| 4 | 91.00 | 5.50 | 3.50 | ? | 100.00 |
| 5 | 82.00 | 7.50 | 4.00 | 6.50 | 100.00 |
| 6 | 83.88 | 15.04 | 1.08 | ? | 100.00 |
| 7 | 92.11 | 4.23 | 3.65 | ? | 100.00 |
| 8 | 92.00 | 7.00 | 1.00 | ? | 100.00 |
| 9 | 85.64 | 11.81 | 2.55 | ? | 100.00 |
Table 3: the compositing formula of hot mastication point frit
Table 4: silicon solar cell (125 * 125 specification) detects performance
| Production code member | Outward appearance | Solderability | Soldering resistance | Adhesive force (N) | Conversion efficiency % |
| 1 | Well | Well | Well | 4.5 | 17.4 |
| 2 | Well | Well | Well | 3.7 | 17.7 |
| 3 | Well | Well | Well | 4.2 | 17.8 |
| 4 | Well | Well | Well | 4.7 | 17.8 |
| 5 | Well | Well | Well | 4.3 | 17.7 |
| 6 | Well | Well | Well | 4.8 | 17.3 |
| 7 | Well | Well | Well | 4.3 | 17.5 |
| 8 | Well | Well | Well | 3.8 | 17.7 |
| 9 | Well | Well | Well | 3.8 | 17.6 |
| Testing conditions | Microscope, range estimation | 240 ℃ of solder baths 5 seconds, | 260 ℃ of solder baths 10 seconds | Tensiometer | Solar battery cell testing, sorting instrument |
Claims (7)
1. silicon solar cell back electric field silver electrode paste, it is characterized in that comprising following component, by percentage to the quality: ball shape silver powder 60～70 wt%, flake silver powder 0～5 wt%, hot mastication point glass dust 2～6wt%, low temperature softening point glass dust 1～3wt%, organic bond 20～30 wt%, described hot mastication point glass dust is PbO
3-B
2O
3-SiO
2-ZnO glass system, its weight percent consists of: PbO
360-80%, SiO
21-30%, B
2O
31-20%, ZnO 3-20%, TiO
20.2-6%, Al
2O
30-2%, CuO 0-1%, Na
2O 0-3%, K
2O 0-3%, Na
2O+K
2O≤3%; Described low temperature softening point glass dust is Bi
2O
3-B
2O
3-SiO
2Glass system, its weight percent consists of: Bi
2O
375-95%, B
2O
34-25%, SiO
21.5-8%, Ag
2O 0-7%.
2. a kind of silicon solar cell back electric field silver electrode paste according to claim 1, it is characterized in that: described ball shape silver powder particle diameter 0.5～2.5 μ m, tap density is more than 4.5 g/ml, and described flake silver powder particle diameter is that below 5 μ m, tap density is more than 4.0g/ml.
3. a kind of silicon solar cell back electric field silver electrode paste according to claim 2, it is characterized in that: described organic bond is macromolecule resin and solvent.
4. a kind of silicon solar cell back electric field silver electrode paste according to claim 3, it is characterized in that: described macromolecule resin is one or more in ethyl cellulose, Foral resin, polyurethane resin.
5. according to claim 3 or 4 described a kind of silicon solar cell back electric field silver electrode pastes, it is characterized in that: described solvent is one or more in terpinol, butyl acetate or butyl carbitol ester.
6. a kind of silicon solar cell back electric field silver electrode paste according to claim 5 is characterized in that: it is macromolecule resin 1.0～4.0 wt%, solvent 18～28wt% that described organic bond weight percent in silver electrode paste forms.
7. one kind prepares the preparation method of silicon solar cell back electric field as claimed in claim 1 with silver electrode paste, it is characterized in that: component proportion according to claim 1, load weighted glass dust and organic bond are packed in ball-grinding machine, in expecting: zirconium ball=1:1 ratio adds the zirconium ball, carry out 15～24 hours mixing, ball-milling treatment and filter discharging to fineness≤7 μ m, mix through the three-high mill rolling to fineness≤below 7 μ m, obtain the silicon solar cell back electric field silver electrode paste with silver powder again.
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