CN107216041B - Glass frit for preparing solar cell electrode, paste composition comprising same, solar cell electrode and solar cell - Google Patents
Glass frit for preparing solar cell electrode, paste composition comprising same, solar cell electrode and solar cell Download PDFInfo
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- CN107216041B CN107216041B CN201710310870.2A CN201710310870A CN107216041B CN 107216041 B CN107216041 B CN 107216041B CN 201710310870 A CN201710310870 A CN 201710310870A CN 107216041 B CN107216041 B CN 107216041B
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Images
Classifications
-
- 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
-
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
Abstract
The invention discloses glass powder for preparing a solar cell electrode, a paste composition comprising the glass powder, the solar cell electrode and a solar cell. Wherein the glass powder comprises 20-50 wt% of PbO and 31-70 wt% of TeO20.1-7 wt% of IA group metal oxide, 0.1-7 wt% of IIA group metal oxide and other oxides, wherein the mass ratio of the IA group metal oxide to the IIA group metal oxide is 0.1-7: 1, and the total addition amount of the IA group metal oxide, the IIA group metal oxide and the other oxides in the glass powder is 1-25 wt%. The solar cell electrode, and the solder ribbon prepared using the paste composition of the present invention have excellent adhesive strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
Description
Technical Field
The invention relates to the technical field of solar cell manufacturing, in particular to glass powder for preparing a solar cell electrode, a paste composition comprising the glass powder, the solar cell electrode and a solar cell.
Background
Solar cells generate electrical energy by converting photons of sunlight through a p-n junction using the photovoltaic effect. In a solar cell, front and rear electrodes are formed on upper and lower surfaces of a semiconductor wafer or substrate having a p-n junction, respectively. Then, the photoelectric effect of the p-n junction is induced by solar light entering the semiconductor wafer, and electrons generated by the photoelectric effect of the p-n junction supply current to the outside through the electrodes. The composition for an electrode is disposed on a wafer, and is patterned and baked to form an electrode of a solar cell.
Increasing the efficiency of solar cells by continuously reducing the emitter thickness may instead lead to shunting, which will deteriorate the performance of the solar cell. In addition, solar cells have gradually increased in area to improve efficiency. However, in this case, there may be a problem of efficiency degradation due to an increase in contact resistance of the solar cell.
The solar cells are connected to each other by solder ribbons to constitute a solar cell module. At present, the adhesion of solar cell electrodes made of ingredients including typical lead-containing glass frit to solder ribbons is insufficient, and low adhesion between the electrodes and the solder ribbons results in high series resistance and deterioration of conversion efficiency.
Disclosure of Invention
The invention aims to provide glass powder for preparing a solar cell electrode, a paste composition comprising the glass powder, the solar cell electrode and a solar cell, and aims to solve the technical problems that in the prior art, the adhesion between the solar cell electrode and a solder strip is insufficient, and the low adhesion between the electrode and the solder strip causes the deterioration of high series resistance and conversion efficiency.
In order to achieve the above object, according to one aspect of the present invention, there is provided a glass frit for use in the preparation of an electrode of a solar cell. The glass powder comprises 20-50 wt% of PbO and 31-70 wt% of TeO20.1-7 wt% of IA group metal oxide, 0.1-7 wt% of IIA group metal oxide and other oxides, wherein the mass ratio of the IA group metal oxide to the IIA group metal oxide is 0.1-7: 1, and the total addition amount of the IA group metal oxide, the IIA group metal oxide and other oxides in the glass powder is 1-25 wt%.
Further, the group IA metal oxide is selected from Li2O、Na2O and K2O, or a combination thereof.
Further, the group IIA metal oxide is one or more selected from the group consisting of MgO, CaO, SrO, and BaO.
Further, the other oxide is selected from the group consisting of P2O5、B2O3、TiO2、WO3、NiO、SiO2And ZnO.
Further, the average particle diameter D50 of the glass frit is 0.1 to 10 μm.
According to another aspect of the present invention, there is provided a paste composition for preparing an electrode of a solar cell. The paste composition comprises 60-95 wt% of conductive powder, 1.0-20 wt% of organic vehicle, 0.1-5 wt% of the glass powder and the balance of additives.
Further, the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
Further, the conductive powder is silver powder.
According to yet another aspect of the present invention, a solar cell electrode is provided. The solar cell is prepared from any one of the paste compositions described above.
According to yet another aspect of the present invention, there is provided a solar cell including an electrode. The electrode is a solar cell electrode prepared from the paste composition of the present invention.
The solar cell electrode, and the solder ribbon prepared using the paste composition of the present invention have excellent adhesive strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic view of a solar cell manufactured using the paste composition according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
According to an exemplary embodiment of the present invention, a glass frit for use in the preparation of electrodes for solar cells is provided. The glass powder comprises 20-50 wt% of PbO and 31-70 wt% of TeO20.1 to 7 wt% of IA group metal oxide, 0.1 to 7 wt% of IIA group metal oxide and other oxides, wherein the IA group metal oxide and the IIA group metal oxide areThe mass ratio of the metal oxide to the glass frit is 0.1-7: 1, and the total amount of the IA group metal oxide, the IIA group metal oxide and the other oxides added in the glass frit is 1-25 wt%.
Other oxides refer to oxides other than group IA metal oxides and group IIA metal oxides.
The solar cell electrode, and the solder ribbon prepared using the paste composition of the present invention have excellent adhesive strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
Preferably, the group IA metal oxide is selected from the group consisting of Li2O、Na2O and K2One or more of the group consisting of O; the group IIA metal oxide is one or more selected from the group consisting of MgO, CaO, SrO, and BaO.
According to a typical embodiment of the invention, the other oxide is selected from the group consisting of P2O5、B2O3、TiO2、WO3、NiO、SiO2And ZnO.
According to an exemplary embodiment of the present invention, a paste composition for preparing an electrode of a solar cell is provided. The paste composition comprises 60-95 wt% of conductive powder, 1.0-20 wt% of organic vehicle, 0.1-5 wt% of the glass powder and the balance of additives. Wherein the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
According to an exemplary embodiment of the present invention, a solar cell electrode is provided. The solar cell is prepared from any one of the paste compositions described above.
According to an exemplary embodiment of the present invention, a solar cell is provided, including an electrode. The electrode is a solar cell electrode prepared from the paste composition of the present invention.
According to an exemplary embodiment of the present invention, a solar cell electrode composition includes silver powder, a lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide-based glass frit, and an organic vehicle. Now, the composition of the solar cell electrode of the present invention will be described in more detail.
(A) Silver powder
According to one exemplary embodiment of the present invention, the paste composition for preparing the solar cell electrode includes silver powder as the conductive powder. The particle size of the silver powder may be in the nanometer or micrometer range. For example, the silver powder may have a particle size of several tens to several hundreds of nanometers, or several to several tens of micrometers. Alternatively, the silver powder may be a mixture of two or more silver powders having different particle diameters.
The silver powder may have a spherical, flake, or amorphous shape.
The silver powder preferably has an average particle diameter (D50) of about 0.1 μm to about 10 μm, more preferably an average particle diameter (D50) of about 0.5 μm to about 5 μm. The average particle size can be measured using an instrument such as Mastersize 2000(Malvern co., Ltd.) after dispersing the conductive powder in isopropyl alcohol (IPA) by ultrasonic waves at 25 ℃ for 3 minutes. Within this average particle size range, the composition can provide low contact resistance and low line resistance.
The silver powder can be present in an amount of about 60 wt% to about 95 wt%, based on the total weight of the composition. Within this range, the conductive powder can prevent the deterioration of the conversion efficiency due to the increase in resistance. More preferably, the conductive powder is present in an amount of about 70 wt% to about 95 wt%.
(B) Lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide based glass powder
The glass frit serves to enhance adhesion between the conductive powder and the wafer or the substrate, and to reduce contact resistance by forming silver grains in the emitter region by etching the anti-reflection layer and melting the silver powder during sintering of the conductive paste. In addition, during the sintering process, the glass frit softens and lowers the sintering temperature.
When the area of the solar cell is increased in order to improve the efficiency of the solar cell, there may be a problem in that the contact resistance of the solar cell is increased. Therefore, there is a need to minimize the series resistance (Rs) and the effect on the p-n junction. In addition, as the suitable sintering temperature varies over a wide range using various wafers having different surface resistances, the glass frit needs to ensure sufficient thermal stability to withstand a large sintering temperature window.
The solar cells are connected to each other by solder ribbons to constitute a solar cell module. In this case, the low adhesive strength between the solar cell electrode and the solder ribbon may cause detachment of the cell or decrease reliability. In the present invention, in order to ensure that the solar cell has desired electrical and physical properties such as adhesive strength, a lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide-based glass frit is used.
In the present invention, the lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide-based glass frit may contain 20 to 50 wt% of PbO, 31 to 70 wt% of TeO20.1-7 wt% of IA group metal oxide, 0.1-7 wt% of IIA group metal oxide and other oxides RO, wherein the mass ratio of the IA group metal oxide to the IIA group metal oxide is 0.1-7: 1, and the total addition amount of the IA group metal oxide, the IIA group metal oxide and other oxides in the glass powder is 1-25 wt%. Within this range, the glass frit can ensure excellent adhesive strength and excellent conversion efficiency.
According to an exemplary embodiment of the present invention, the lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide based glass frit may further comprise at least one other oxide selected from the group consisting of phosphorus oxide (P)2O5) Boron oxide (B)2O3) Titanium oxide (TiO)2) Tungsten oxide (WO)3) Nickel oxide (NiO), silicon dioxide (SiO)2) Zinc oxide (ZnO).
The glass frit may be prepared from the lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide by any typical method. For example, the oxide is mixed with lead oxide-bismuth oxide-tellurium oxide-tungsten oxide in a certain ratio. The mixing may be performed using a ball mill or a planetary mill. The mixed composition is melted at about 900 ℃ to about 1300 ℃ and then quenched to about 25 ℃. The resultant material is pulverized using a disk mill, a planetary mill, or the like, thereby providing glass frit.
The average particle size D50 of the glass frit may be from about 0.1 μm to about 10 μm and is present in an amount of from about 0.1 wt% to about 5 wt% based on the total amount of the composition. The glass frit may have a spherical or amorphous shape.
(C) Organic vehicle
The organic vehicle imparts the appropriate viscosity and rheological characteristics required for the conductive paste printing process by mechanical mixing with the inorganic components in the solar cell electrode.
The organic vehicle may be any typical organic vehicle used in a solar cell electrode composition, and may include a binder resin, a solvent, and the like.
The binder resin may be selected from acrylate resins or cellulose resins. Ethyl cellulose is generally used as the binder resin. Further, the binder resin may be selected from ethyl hydroxyethyl cellulose, nitrocellulose, a blend of ethyl cellulose and phenolic resin, alkyd resin, phenol, acrylate, xylene, polybutene, polyester, urea, melamine, vinyl acetate resin, wood rosin, polymethacrylate of alcohol, and the like.
The solvent may be selected from, for example, hexane, toluene, ethyl cellosolve, cyclohexanone, butyl cellosolve, butyl carbitol (diethylene glycol monobutyl ether), dibutyl carbitol (diethylene glycol dibutyl ether), butyl carbitol acetate (monobutyl ether acetate), propylene glycol monomethyl ether, hexylene glycol, terpineol, methyl ethyl ketone, benzyl alcohol, gamma-butyrolactone, ethyl lactate, and combinations thereof.
The organic vehicle can be present in an amount of about 1 wt% to about 20 wt%, based on the total weight of the composition. Within this range, the organic vehicle may provide sufficient adhesive strength and excellent printability to the composition.
(D) Additive agent
The composition may further include typical additives to enhance flow properties, processability and stability, as desired. The additives may include, but are not limited to, a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent, and the like. These additives may be used alone or as a mixture thereof. These additives may be present in an amount of about 0.1 wt% to about 5 wt% of the composition, but the amount may vary as desired.
According to a typical embodiment of the present invention, a solar cell manufactured using the paste composition. As shown in fig. 1, the back surface electrode 210 and the front surface electrode 230 may be formed by printing a cell electrode composition on a wafer or substrate 100 including a p layer 101 and an n layer 102 serving as an emitter, and sintering. For example, a preliminary process for preparing the back electrode is performed by printing the composition on the back surface of the wafer and drying the printed composition at about 200 to about 400 ℃ for about 10 to 60 seconds. In addition, a preliminary process for preparing the front electrode may be performed by printing the slurry on the front surface of the wafer and drying the printed composition. The front and back electrodes may then be formed by sintering the wafer at about 400 ℃ to about 950 ℃, preferably about 850 ℃ to about 950 ℃, for about 30 seconds to 50 seconds.
Next, the present invention will be described in more detail by referring to examples. It should be noted, however, that these examples are provided only for illustrating the present invention and should not be construed as limiting the present invention in any way.
Detailed descriptions that are clear to those skilled in the art are omitted for the sake of clarity.
Examples and comparative examples
The oxides were mixed according to the composition shown in Table 1 and melted and sintered at 900 to 1400 ℃ to prepare lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide-based glass frit having an average particle diameter (D50) of 2.0 μm.
As an organic binder, 1.0 wt% of ethyl cellulose was sufficiently dissolved in 9.0 wt% of butyl carbitol at 60 ℃, and a solution including 86 wt% of spherical silver powder having an average particle size of 1.5 μm, 1.5 wt% of the prepared lead oxide-tellurium oxide-group IA metal oxide-group IIA metal oxide glass frit, and 0.5 wt% of a thixotropic agent thixatrol st was added to the binder, followed by grinding in a three-roll machine, thereby preparing a solar cell electrode composition.
The electrode composition prepared as above was deposited on the front surface of a single crystal silicon wafer in a predetermined pattern by screen printing, followed by drying in an infrared drying oven. The composition used to prepare the back aluminum electrode was then printed on the back side of the wafer and dried in the same manner. The battery piece treated in the above procedure was fired at 910 ℃ for 40 seconds in a belt furnace. The conversion efficiency (%) of the cell, the series resistance Rs (m Ω), the open-circuit voltage (Voc), and the like were measured using a solar energy efficiency tester (CT-801). Then, the electrode of the battery is soldered to the solder ribbon with solder at 300 to 400 ℃ using a soldering iron. Then, the adhesive strength (N/mm) of the battery electrode to the solder ribbon was measured using a tester at a peel angle of 180 ° and a tensile rate of 50 mm/min. The measured conversion efficiency and tensile force tests are shown in table 1.
Examples 1 to 11 and comparative examples 1 to 7
Examples 1 to 11 and comparative examples 1 to 7 compositions for solar cell electrodes were prepared in the same manner using the compositions of glass frit as shown in table 1, and physical properties were evaluated. It should be noted that the examples and comparative examples in Table 1 are intended to highlight one or more of the features of the inventive examples, and are not intended to limit the scope of the invention, nor are they intended to illustrate comparative examples outside the scope of the invention. Furthermore, the inventive subject matter is not limited to the specific details described in the examples and comparative examples.
TABLE 1
As shown in Table 1, the solar cell electrodes manufactured from the compositions prepared in examples 1 to 11 exhibited high adhesive strength with solder ribbons and excellent conversion efficiency as compared to the other comparative examples 1 to 7. While comparative examples 1-7 show either lower cell efficiency or lower tensile force, or both.
Comparative example 1 shows that the efficiency and tensile strength of the solar electrode made with the glass composition containing a lower content of PbO are lower than those of the inventive examples. Comparative example 2 shows that the efficiency of the solar cell is lower when the glass composition contains a higher content of PbO. Similarly, comparative example 3 has no group i oxide and the resulting solar cell has a lower efficiency. Comparative examples 4 and 5 have no group ii oxide and the solar electrodes produced have lower efficiency and lower tensile strength than the inventive examples. Comparative examples 6, 7 show that group II oxides are not within the scope of the invention and that the resulting solar cells have either lower efficiency or lower tensile force or both.
The invention example shows that the glass powder comprises 20-50 wt% of PbO and 31-70 wt% of TeO20.1-7 wt% of IA group metal oxide, 0.1-7 wt% of IIA group metal oxide and other oxides, wherein the mass ratio of the IA group metal oxide to the IIA group metal oxide is 0.1-7: 1, the total addition amount of the IA group metal oxide, the IIA group metal oxide and the other oxides in the glass powder is 1-25 wt%, and the prepared solar cell has higher performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The glass powder for preparing the solar cell electrode is characterized by comprising 20-50 wt% of PbO and 65-70 wt% of TeO20.1-7 wt% of IA group metal oxide, 0.1-7 wt% of IIA group metal oxide and other oxides, wherein the total content of the components is 100%, the mass ratio of the IA group metal oxide to the IIA group metal oxide is 0.1-7: 1, and the total addition amount of the IA group metal oxide, the IIA group metal oxide and the other oxides in the glass powder is 1-25 wt%; the IA group metal oxide is selected from Li2O、Na2O and K2One or more of the group consisting of O; the group IIA metal oxide is one or more selected from the group consisting of MgO, CaO, SrO and BaO; the other oxide is selected from P2O5、B2O3、TiO2、WO3、NiO、SiO2And ZnO.
2. The glass frit according to claim 1, wherein the average particle diameter D50 of the glass frit is 0.1 to 10 μm.
3. A paste composition for preparing a solar cell electrode, comprising 60 to 95 wt% of a conductive powder, 1.0 to 20 wt% of an organic vehicle, 0.1 to 5 wt% of the glass frit according to any one of claims 1 to 2, and the balance of additives.
4. The paste composition of claim 3, wherein the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
5. The paste composition of claim 3, wherein the conductive powder is silver powder.
6. A solar cell electrode prepared from the paste composition according to any one of claims 3 to 5.
7. A solar cell comprising an electrode, wherein the electrode is the solar cell electrode of claim 6.
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| CN108321224A (en) * | 2017-10-30 | 2018-07-24 | 无锡帝科电子材料科技有限公司 | It is used to prepare the polynary nanometer material including its paste composition and electrode of solar battery and battery of electrode of solar battery |
| WO2021159499A1 (en) * | 2020-02-14 | 2021-08-19 | 硕禾电子材料股份有限公司 | Conductive paste for heterojunction solar cell, heterojunction solar cell, and electrode structure |
| CN114538782A (en) * | 2020-11-26 | 2022-05-27 | 无锡帝科电子材料股份有限公司 | Glass frit for preparing solar cell electrode, paste composition comprising same, solar cell electrode and solar cell |
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| CN103594140A (en) * | 2012-08-13 | 2014-02-19 | 第一毛织株式会社 | Paste composition for solar cell electrode, and electrode prepared using the same |
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| CN104751935A (en) * | 2013-12-26 | 2015-07-01 | 湖南利德电子浆料有限公司 | High-sheet-resistance efficient solar cell front silver paste and preparation method thereof |
| CN106007389B (en) * | 2016-05-13 | 2019-04-30 | 浙江光达电子科技有限公司 | A kind of crystal silicon solar batteries front side silver paste glass powder and preparation method thereof |
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| CN103958429A (en) * | 2011-12-06 | 2014-07-30 | E.I.内穆尔杜邦公司 | Conductive silver paste for a metal-wrap-through silicon solar cell |
| CN103594140A (en) * | 2012-08-13 | 2014-02-19 | 第一毛织株式会社 | Paste composition for solar cell electrode, and electrode prepared using the same |
| CN103811098A (en) * | 2012-11-12 | 2014-05-21 | 第一毛织株式会社 | Electrode paste for solar cell and electrode prepared thereof |
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