CN115611519A - Glass powder for solar cell front silver paste - Google Patents
Glass powder for solar cell front silver paste Download PDFInfo
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- CN115611519A CN115611519A CN202211178388.5A CN202211178388A CN115611519A CN 115611519 A CN115611519 A CN 115611519A CN 202211178388 A CN202211178388 A CN 202211178388A CN 115611519 A CN115611519 A CN 115611519A
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- oxide
- solar cell
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses glass powder for solar cell front silver paste, which comprises the following components: 25-40% of silicon oxide, 20-30% of boron oxide, 20-30% of bismuth oxide, 10-15% of lead oxide, 5-10% of zinc oxide, 3-8% of magnesium oxide, 2-7% of lithium oxide, 1-5% of phosphorus oxide, 1-5% of calcium oxide, 1-3% of sodium oxide, 1-3% of gallium oxide and 1-3% of barium oxide; according to the invention, solid-phase reaction is adopted, and the solid raw material are subjected to sintering reaction, so that high-temperature modification is carried out, the performance of a glass body is enhanced, the smelted glass body has better performance, the glass powder has the advantages of good transparency, high hardness and uniform particle size distribution, the photoelectric conversion efficiency of the solar cell is improved, and the problems that the existing glass powder is not subjected to solid-phase reaction and is not modified, so that the dispersibility of the glass powder is general, and the photoelectric conversion efficiency of the solar cell is not high in the use process of the solar cell, and the use requirement of the existing solar cell cannot be met are solved.
Description
Technical Field
The invention relates to the technical field of glass powder, in particular to glass powder for solar cell front silver paste.
Background
The glass powder is inorganic amorphous hard superfine particle powder and is white powder in appearance. In the production process, raw materials such as high-temperature high-purity silicon oxide, aluminum oxide and the like are used, and then an ultra-clean production process is carried out to form the glass transparent powder with a disordered structure, and the super-weather-resistant powder material has stable chemical property, acid and alkali resistance, chemical inertia and low expansion coefficient.
The glass powder is used as a binding phase and plays an important binding role in the silver paste. The role of the glass frit in the paste can be illustrated from three points: the glass powder forms a conductive channel by corroding the silicon nitride layer; the glass melting process initiates the oxidation-reduction reaction of the silver microcrystal growing on the interface, so that the silver microcrystal can grow on the silicon substrate in an inverted pyramid shape; the interface of the paste and the emitter serves as a transmission medium, and because the thickness of the glass powder is very thin, electrons can move between the silver paste and the emitter of the battery through a tunnel effect. Although the proportion of the glass powder in the silver paste is small, the glass powder plays a vital role in corroding the silicon nitride layer to form an electrode and building a bridge for electron transportation. In summary, the content, type, etc. of the glass frit all affect the performance of the front silver paste, and further affect the photoelectric conversion efficiency of the silicon solar cell.
The Chinese patent net discloses 'a preparation method of glass powder and the glass powder', and the application numbers are as follows: 202010316166.X, publication number: AN111423127A, which comprises the following raw materials: siO 2 2 40％-50％；Bi 2 O 3 17％-28％；B 2 O 3 10％-14％；Al 2 O 3 1％-8％；ZrO 2 0.5％-3％；TiO 2 1％-3％；La 2 O 3 0.1% -2%; 4.1 to 14 percent of fluxing agent, wherein the fluxing agent comprises Li 2 O、Na 2 O and CaF 2 . By adding a proper amount of fluxing agent into the components, the glass network connection is tighter, the softening and melting temperature of a glass system is reduced, a multiphase composite system of a microcrystal phase and a glass phase is easily formed, the generation of microcrystals can enhance the network structure, the acid resistance of glass is improved, and the glass does not contain heavy metal elements such as lead and cadmium.
Disclosure of Invention
The invention aims to provide glass powder for solar cell front silver paste, which has the advantages of good transparency, high hardness, uniform particle size distribution and strong weather resistance, and improves the photoelectric conversion efficiency of a solar cell.
In order to achieve the purpose, the invention provides the following technical scheme: the glass powder for the solar cell front silver paste comprises the following components:
25-40% of silicon oxide, 20-30% of boron oxide, 20-30% of bismuth oxide, 10-15% of lead oxide, 5-10% of zinc oxide, 3-8% of magnesium oxide, 2-7% of lithium oxide, 1-5% of phosphorus oxide, 1-5% of calcium oxide, 1-3% of sodium oxide, 1-3% of gallium oxide and 1-3% of barium oxide.
Preferably, the components are as follows:
20-40% of silicon oxide, 15-20% of boron oxide, 15-20% of bismuth oxide, 12-15% of lead oxide, 6-10% of zinc oxide, 5-8% of magnesium oxide, 3-7% of lithium oxide, 2-5% of phosphorus oxide, 2-5% of calcium oxide, 2-3% of sodium oxide, 2-3% of gallium oxide and 2-3% of barium oxide.
A preparation method of glass powder for solar cell front silver paste comprises the following steps:
s1, pretreatment: selecting analytically pure lead oxide, bismuth oxide, silicon oxide, zinc oxide, magnesium oxide, lithium oxide, boron oxide, phosphorus oxide, calcium oxide, sodium oxide, gallium oxide and barium oxide;
s2, smelting modification: smelting the raw materials at high temperature, and carrying out solid-phase sintering reaction to enable the raw materials to form a vitreous body;
s3, washing: washing the glass body, and cooling;
s4, drying: drying the washed glass body in a blowing drying mode;
s5, coarse grinding: putting the dried glass body into a ball mill for ball milling;
s6, fine grinding: finely grinding the coarsely ground material;
s7, classification: and grading the finely ground materials by a grader to obtain a final product.
Preferably, in the step S1, the selected particle size of the raw material is 0.5-2 μm.
Preferably, in the step S2, the smelting temperature is 1400-1600 ℃.
Preferably, in the step S3, the cooling manner of the glass body is water spraying cooling.
Preferably, in the step S4, the drying temperature is 60 to 80 ℃.
Preferably, in the step S5, the ball milling time is 3-5h, and the rotation speed is 300-500r/min.
Preferably, in the step S6, the refining time is 4-6h, and the rotating speed is 400-600r/min.
Preferably, in the step S7, the final product is sieved, and the mesh number of the sieve is 1300-3000 meshes.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, solid-phase reaction is adopted, and the solid raw material are subjected to sintering reaction, so that high-temperature modification is carried out, the performance of a glass body is enhanced, the smelted glass body has better performance, the glass powder has the advantages of good transparency, high hardness and uniform particle size distribution, the photoelectric conversion efficiency of the solar cell is improved, and the problems that the existing glass powder is not subjected to solid-phase reaction and is not modified, so that the dispersibility of the glass powder is general, and the photoelectric conversion efficiency of the solar cell is not high in the use process of the solar cell, and the use requirement of the existing solar cell cannot be met are solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a preparation method of glass powder for solar cell front silver paste comprises the following steps:
s1, pretreatment: selecting analytically pure lead oxide, bismuth oxide, silicon oxide, zinc oxide, magnesium oxide, lithium oxide, boron oxide, phosphorus oxide, calcium oxide, sodium oxide, gallium oxide and barium oxide; the particle size of the selected raw material is 1 μm.
S2, smelting modification: smelting the raw materials at high temperature, and carrying out solid-phase sintering reaction to enable the raw materials to form a vitreous body; the melting temperature is 1500 ℃.
S3, washing: washing the glass body and cooling; the cooling mode of the glass body is water spraying cooling.
S4, drying: drying the washed glass body in a blowing drying mode; the temperature of drying was 70 ℃.
S5, coarse grinding: putting the dried glass body into a ball mill for ball milling; the ball milling time is 4h, and the rotating speed is 400r/min.
S6, fine grinding: finely grinding the coarsely ground material; the refining time is 5h, and the rotating speed is 550r/min.
S7, classification: classifying the finely ground materials by a classifier to obtain a final product, and sieving the final product with a screen mesh number of 2500 meshes.
The second embodiment:
| silicon oxide | 25％ |
| Boron oxide | 18％ |
| Bismuth oxide | 15％ |
| Lead oxide | 13％ |
| Zinc oxide | 6％ |
| Magnesium oxide | 6％ |
| Lithium oxide | 4％ |
| Phosphorus oxide | 2％ |
| Calcium oxide | 2％ |
| Sodium oxide | 3％ |
| Gallium oxide | 3％ |
| Barium oxide | 3％ |
A preparation method of glass powder for solar cell front silver paste comprises the following steps:
s1, pretreatment: selecting analytically pure lead oxide, bismuth oxide, silicon oxide, zinc oxide, magnesium oxide, lithium oxide, boron oxide, phosphorus oxide, calcium oxide, sodium oxide, gallium oxide and barium oxide; the particle size of the selected raw material is 1 μm.
S2, smelting modification: smelting the raw materials at high temperature, and carrying out solid-phase sintering reaction to enable the raw materials to form a vitreous body; the melting temperature is 1500 ℃.
S3, washing: washing the glass body and cooling; the cooling mode of the glass body is water spraying cooling.
S4, drying: drying the washed glass body in a blowing drying mode; the drying temperature was 70 ℃.
S5, coarse grinding: putting the dried glass body into a ball mill for ball milling; the ball milling time is 4h, and the rotating speed is 400r/min.
S6, fine grinding: finely grinding the coarsely ground material; the refining time is 5h, and the rotating speed is 550r/min.
S7, classification: and classifying the finely ground materials by a classifier to obtain a final product, and sieving the final product with the number of 2500 meshes.
Example three:
| silicon oxide | 20％ |
| Boron oxide | 20％ |
| Bismuth oxide | 18％ |
| Lead oxide | 13％ |
| Zinc oxide | 7％ |
| Magnesium oxide | 5％ |
| Lithium oxide | 3％ |
| Phosphorus oxide | 3％ |
| Calcium oxide | 2.5％ |
| Sodium oxide | 3％ |
| Gallium oxide | 2.5％ |
| Barium oxide | 3％ |
A preparation method of glass powder for solar cell front silver paste comprises the following steps:
s1, pretreatment: selecting analytically pure lead oxide, bismuth oxide, silicon oxide, zinc oxide, magnesium oxide, lithium oxide, boron oxide, phosphorus oxide, calcium oxide, sodium oxide, gallium oxide and barium oxide; the particle size of the selected raw material is 1 μm.
S2, smelting modification: carrying out high-temperature smelting on the raw materials, and carrying out solid-phase sintering reaction to enable the raw materials to form a vitreous body; the melting temperature is 1500 ℃.
S3, washing: washing the glass body, and cooling; the cooling mode of the glass body is water spraying cooling.
S4, drying: drying the washed glass body in a blowing drying mode; the temperature of drying was 70 ℃.
S5, coarse grinding: putting the dried glass body into a ball mill for ball milling; the ball milling time is 4h, and the rotating speed is 400r/min.
S6, fine grinding: finely grinding the coarsely ground material; the refining time is 5h, and the rotating speed is 550r/min.
S7, classification: classifying the finely ground materials by a classifier to obtain a final product, and sieving the final product with a screen mesh number of 2500 meshes.
Example four:
a preparation method of glass powder for solar cell front silver paste comprises the following steps:
s1, pretreatment: selecting analytically pure lead oxide, bismuth oxide, silicon oxide, zinc oxide, magnesium oxide, lithium oxide, boron oxide, phosphorus oxide, calcium oxide, sodium oxide, gallium oxide and barium oxide; the particle size of the selected raw material is 1 micron.
S2, smelting modification: smelting the raw materials at high temperature, and carrying out solid-phase sintering reaction to enable the raw materials to form a vitreous body; the melting temperature is 1500 ℃.
S3, washing: washing the glass body, and cooling; the cooling mode of the glass body is water spraying cooling.
S4, drying: drying the washed glass body in a blowing drying mode; the drying temperature was 70 ℃.
S5, coarse grinding: putting the dried glass body into a ball mill for ball milling; the ball milling time is 4h, and the rotating speed is 400r/min.
S6, fine grinding: finely grinding the coarsely ground material; the refining time is 5h, and the rotating speed is 550r/min.
S7, classification: and classifying the finely ground materials by a classifier to obtain a final product, and sieving the final product with the number of 2500 meshes.
Glass powder performance test experiment
The test method comprises the following steps: testing the coefficient of thermal expansion by using a method for testing the linear expansion coefficient of SJ689-83 electric vacuum glass;
group a (control group): selecting glass powder sold in the market, dividing into 4 parts, and marking as A1, A2, A3 and A4;
group B (experimental group): selecting the glass powder prepared in the first, second, third and fourth embodiments, and marking the glass powder as B1, B2, B3 and B4;
the two groups of samples were tested, and the results were as follows:
as can be seen from the above table, the expansion coefficient of the glass powder prepared by the technical scheme is lower than that of the control group, the melting point temperature is low, and as can be seen from the above table, in the fourth embodiment, the mixture ratio of the glass powder is optimal.
The test method comprises the following steps: softening temperature test, SJ 3232.1-1989 method for testing softening temperature of low-melting-point welding glass powder
Group C (control group): selecting glass powder sold in the market, dividing the glass powder into 4 parts, and marking the parts as C1, C2, C3 and C4;
group D (experimental group): selecting the glass powder prepared in the first, second, third and fourth embodiments, and marking the glass powder as D1, D2, D3 and D4;
the two groups of samples were tested, and the results were as follows:
| glass properties | C1 | C2 | C3 | C4 | D1 | D2 | D3 | D4 |
| Softening temperature of | 463 | 468 | 471 | 473 | 447 | 445 | 450 | 442 |
As can be seen from the above table, the softening temperature of the glass powder prepared by the technical scheme is lower than that of a control group, and it can be seen from the above table that in the fourth embodiment, the softening temperature of the glass powder prepared by the technical scheme is the lowest, and the softening temperature is combined with the result of the expansion coefficient test method, so that it is obvious that the performance of the glass powder prepared by the fourth embodiment is the best.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The glass powder for the solar cell front silver paste is characterized by comprising the following components:
25-40% of silicon oxide, 20-30% of boron oxide, 20-30% of bismuth oxide, 10-15% of lead oxide, 5-10% of zinc oxide, 3-8% of magnesium oxide, 2-7% of lithium oxide, 1-5% of phosphorus oxide, 1-5% of calcium oxide, 1-3% of sodium oxide, 1-3% of gallium oxide and 1-3% of barium oxide.
2. The glass powder for the solar cell front silver paste according to claim 1, which is characterized by comprising the following components:
20-40% of silicon oxide, 15-20% of boron oxide, 15-20% of bismuth oxide, 12-15% of lead oxide, 6-10% of zinc oxide, 5-8% of magnesium oxide, 3-7% of lithium oxide, 2-5% of phosphorus oxide, 2-5% of calcium oxide, 2-3% of sodium oxide, 2-3% of gallium oxide and 2-3% of barium oxide.
3. A preparation method of glass powder for solar cell front silver paste is characterized by comprising the following steps: the method comprises the following steps:
s1, pretreatment: selecting analytically pure lead oxide, bismuth oxide, silicon oxide, zinc oxide, magnesium oxide, lithium oxide, boron oxide, phosphorus oxide, calcium oxide, sodium oxide, gallium oxide and barium oxide;
s2, smelting modification: smelting the raw materials at high temperature, and carrying out solid-phase sintering reaction to enable the raw materials to form a vitreous body;
s3, washing: washing the glass body and cooling;
s4, drying: drying the washed glass body in a blowing drying mode;
s5, coarse grinding: putting the dried glass body into a ball mill for ball milling;
s6, fine grinding: finely grinding the coarsely ground material;
s7, classification: and grading the finely ground materials by a grader to obtain a final product.
4. The method for preparing the glass powder for the solar cell front silver paste according to claim 3, wherein the method comprises the following steps: in the step S1, the grain diameter of the selected raw material is 0.5-2 μm.
5. The method for preparing the glass powder for the solar cell front silver paste according to claim 3, wherein the method comprises the following steps: in the step S2, the smelting temperature is 1400-1600 ℃.
6. The preparation method of the glass powder for the solar cell front silver paste according to claim 3, characterized by comprising the following steps: in the step S3, the cooling mode of the glass body is water spraying cooling.
7. The method for preparing the glass powder for the solar cell front silver paste according to claim 3, wherein the method comprises the following steps: in the step S4, the drying temperature is 60-80 ℃.
8. The method for preparing the glass powder for the solar cell front silver paste according to claim 3, wherein the method comprises the following steps: in the step S5, the ball milling time is 3-5h, and the rotating speed is 300-500r/min.
9. The preparation method of the glass powder for the solar cell front silver paste according to claim 3, characterized by comprising the following steps: in the step S6, the fine grinding time is 4-6h, and the rotating speed is 400-600r/min.
10. The method for preparing the glass powder for the solar cell front silver paste according to claim 3, wherein the method comprises the following steps: in the step S7, the final product is sieved, and the mesh number is 1300-3000.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211178388.5A CN115611519A (en) | 2022-09-24 | 2022-09-24 | Glass powder for solar cell front silver paste |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211178388.5A CN115611519A (en) | 2022-09-24 | 2022-09-24 | Glass powder for solar cell front silver paste |
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Citations (6)
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| JP2011175750A (en) * | 2010-02-23 | 2011-09-08 | Murata Mfg Co Ltd | Conductive paste, and electronic component |
| CN102503149A (en) * | 2011-09-22 | 2012-06-20 | 上海交通大学 | Low-lead glass powder for silver paste of anode of solar cell and preparation method of low-lead glass powder |
| CN102992632A (en) * | 2012-11-10 | 2013-03-27 | 江苏瑞德新能源科技有限公司 | Lead-free glass powder for aluminium paste of solar cell |
| CN103854721A (en) * | 2014-03-25 | 2014-06-11 | 中希集团有限公司 | Metallized silver paste on front side of solar battery and preparation method of metalized silver paste |
| CN109809699A (en) * | 2019-01-21 | 2019-05-28 | 西北大学 | A kind of p-doped glass powder and preparation method and the method for preparing positive silver paste used for solar batteries using it |
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2022
- 2022-09-24 CN CN202211178388.5A patent/CN115611519A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011175750A (en) * | 2010-02-23 | 2011-09-08 | Murata Mfg Co Ltd | Conductive paste, and electronic component |
| CN101950600A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Transparent dielectric paste |
| CN102503149A (en) * | 2011-09-22 | 2012-06-20 | 上海交通大学 | Low-lead glass powder for silver paste of anode of solar cell and preparation method of low-lead glass powder |
| CN102992632A (en) * | 2012-11-10 | 2013-03-27 | 江苏瑞德新能源科技有限公司 | Lead-free glass powder for aluminium paste of solar cell |
| CN103854721A (en) * | 2014-03-25 | 2014-06-11 | 中希集团有限公司 | Metallized silver paste on front side of solar battery and preparation method of metalized silver paste |
| CN109809699A (en) * | 2019-01-21 | 2019-05-28 | 西北大学 | A kind of p-doped glass powder and preparation method and the method for preparing positive silver paste used for solar batteries using it |
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