CN113087390B - Composite glass powder and electrode silver paste prepared from same - Google Patents

Composite glass powder and electrode silver paste prepared from same Download PDF

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CN113087390B
CN113087390B CN202110404347.2A CN202110404347A CN113087390B CN 113087390 B CN113087390 B CN 113087390B CN 202110404347 A CN202110404347 A CN 202110404347A CN 113087390 B CN113087390 B CN 113087390B
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oxide
glass powder
composite glass
silver paste
weight ratio
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CN113087390A (en
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刘国民
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Jiangsu Riyu Photovoltaic New Materials Co ltd
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Jiangsu Riyu Photovoltaic New Material Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/14Compositions for glass with special properties for electro-conductive glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C12/00Powdered glass; Bead compositions
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14Conductive material dispersed in non-conductive inorganic material
    • H01B1/16Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

The invention relates to the technical field of solar cells, in particular to composite glass powder and electrode silver paste prepared from the composite glass powder, wherein the composite glass powder comprises 44-74wt% of Bi oxide, 10-20wt% of B oxide, 3-7wt% of Zn oxide, 10-20wt% of Si oxide, 1-5wt% of V oxide and 2-4wt% of Mo oxide. The composite glass powder provided by the invention adopts oxides of specific elements, particularly V and Mo, which are matched with other elements, so that the composite glass powder can play a role in synergy, and is high in photoelectric conversion efficiency when used in a solar cell.

Description

Composite glass powder and electrode silver paste prepared from same
Technical Field
The invention relates to the technical field of solar cells, in particular to composite glass powder and electrode silver paste prepared from the composite glass powder.
Background
The crystalline silicon solar cell is a semiconductor device capable of converting solar energy into electric energy, and the solar cell can generate current under the condition of illumination, collect the electricity through a grid line and an electrode and transmit the electricity. The front surface electrode and the grid line of the crystalline silicon solar cell are both made of conductive silver paste by the processes of high-speed high-precision screen printing, low-temperature drying, high-temperature sintering and the like. The conductive silver paste is generally prepared from silver powder, glass frit, and an organic vehicle.
The glass powder is liquefied during rapid sintering, plays a role in bonding between the silver powder and the silicon substrate, and simultaneously plays a role in penetrating through the antireflection film, so that good ohmic contact is formed between the silver powder and the silicon substrate. The components, content, particle size and softening temperature of the glass powder directly influence the contact resistance, the ability of penetrating through the antireflection film, the conductivity of the electrode, the adhesion between the electrode and the substrate and the like, thereby influencing the photoelectric conversion efficiency and the service life of the solar cell.
CN102992632A relates to lead-free glass powder for solar cell aluminum paste and a preparation method thereof. The lead-free glass powder comprises the following components in percentage by weight: 20-29% of bismuth oxide, 5-15% of boron oxide, 21-39% of silicon oxide, 5-30% of zinc oxide, 1-10% of calcium oxide, 1-10% of antimony oxide and 0.5-5% of tin oxide; wherein the sum of the weight percentages of the components is 100 percent, the median particle size of the glass powder is less than 2 mu m, the maximum particle size is less than 5 mu m, and the softening temperature of the glass powder is 400-550 ℃. However, the photoelectric conversion efficiency thereof for use in solar cells is still to be further improved.
Disclosure of Invention
The invention aims to overcome the defect that the photoelectric conversion efficiency of glass powder used in a solar cell is still to be further improved in the prior art, and provides composite glass powder and electrode silver paste prepared from the composite glass powder.
In order to achieve the above object, a first aspect of the present invention provides a composite glass frit comprising 44 to 74wt% of a Bi oxide, 10 to 20wt% of a B oxide, 3 to 7wt% of a Zn oxide, 10 to 20wt% of a Si oxide, 1 to 5wt% of a V oxide, and 2 to 4wt% of a Mo oxide.
Preferably, 59-74wt% of Bi oxide, 10-15wt% of B oxide, 3-5wt% of Zn oxide, 10-15wt% of Si oxide, 1-3wt% of V oxide, 2-3wt% of Mo oxide are included.
Preferably, the weight ratio of the V oxide to the Mo oxide is 1.2-2:1.
Preferably, the weight ratio of the V oxide to the Mo oxide is 1.2 to 1.5.
Preferably, the weight ratio of the B oxide, the Si oxide and the Zn oxide is 2-3.5.
Preferably, it comprises 65-74wt% of Bi oxide, 10-13wt% of B oxide, 3-4wt% of Zn oxide, 10-13wt% of Si oxide, 1-2wt% of V oxide, 2-3wt% of Mo oxide.
The second aspect of the present invention provides an electrode silver paste, including: 50-65wt% of silver powder, 10-20wt% of glass powder, 1-5wt% of assistant and 10-39wt% of organic carrier, wherein the glass powder is the composite glass powder in the first aspect.
Preferably, the aid is Ti oxide.
Preferably, the organic carrier is at least one of carboxymethyl cellulose, ethyl cellulose and terpineol.
Preferably, the organic carrier is carboxymethyl cellulose, ethyl cellulose and terpineol, and the weight ratio of the carboxymethyl cellulose to the ethyl cellulose to the terpineol is 1.
Compared with the prior art, the composite glass powder provided by the invention has the advantages that the oxide of a plurality of specific elements, particularly V and Mo, is matched with other elements, so that the synergistic effect can be achieved, and the photoelectric conversion efficiency of the composite glass powder used in the solar cell is high. Furthermore, the inventor further researches and discovers that the photoelectric conversion efficiency of the obtained composite glass powder for the solar cell is higher by adopting a preferable scheme of V and Mo with a specific ratio; by adopting the preferable scheme of B, si and Zn with specific ratio, the obtained composite glass powder has higher photoelectric conversion efficiency when used in a solar cell. The composite glass powder is used in electrode silver paste, and the photoelectric conversion efficiency is high.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The first aspect of the present invention provides a composite glass frit comprising 44 to 74wt% of a Bi oxide, 10 to 20wt% of a B oxide, 3 to 7wt% of a Zn oxide, 10 to 20wt% of a Si oxide, 1 to 5wt% of a V oxide, and 2 to 4wt% of a Mo oxide.
In the present invention, the a oxide means an oxide containing an element a, and for example, the Bi oxide means an oxide containing a Bi element, that is, bismuth oxide.
According to the present invention, it is preferable to include 59-74wt% of Bi oxide, 10-15wt% of B oxide, 3-5wt% of Zn oxide, 10-15wt% of Si oxide, 1-3wt% of V oxide, 2-3wt% of Mo oxide.
More preferably, it comprises 65-74wt% of Bi oxide, 10-13wt% of B oxide, 3-4wt% of Zn oxide, 10-13wt% of Si oxide, 1-2wt% of V oxide, 2-3wt% of Mo oxide.
The inventor further researches to find that the photoelectric conversion efficiency of the obtained composite glass powder for the solar cell is higher by adopting a preferable scheme of V and Mo with a specific ratio; preferably, the weight ratio of the V oxide to the Mo oxide is 1.2-2:1.
Further preferably, the weight ratio of the V oxide to the Mo oxide is 1.2 to 1.5.
The inventor further researches to find that the photoelectric conversion efficiency of the obtained composite glass powder used in the solar cell is higher by adopting a preferable scheme of B oxide, si oxide and Zn oxide with specific proportions; preferably, the weight ratio of the B oxide, the Si oxide and the Zn oxide is 2-3.5.
The inventor further researches to find that when each element has specific content and relative proportion, the synergistic effect is optimal; preferably, the composite glass frit comprises 44-74wt% of Bi oxide, 10-20wt% of B oxide, 3-7wt% of Zn oxide, 10-20wt% of Si oxide, 1-5wt% of V oxide, 2-4wt% of Mo oxide; the weight ratio of the V oxide to the Mo oxide is 1.2-2:1, and the weight ratio of the B oxide, the Si oxide and the Zn oxide is 2-3.5.
The preparation method of the glass powder is not limited at all, and can be carried out by adopting the method existing in the field, such as: weighing the raw materials to prepare a mixture; (2) Putting the mixture into a crucible for smelting (the temperature is preferably 1200-1500 ℃, and the heat preservation time is 10-30 min); (3) water quenching the melted glass liquid; (4) drying; (5) then ball-milling and crushing into powder; (6) Sieving (preferably to obtain 0.5-6 μm glass powder).
The second aspect of the present invention provides an electrode silver paste, including: 50-65wt% of silver powder, 10-20wt% of glass powder, 1-5wt% of assistant and 10-39wt% of organic carrier, wherein the glass powder is the composite glass powder in the first aspect.
According to the invention, preferably, the promoter is Ti oxide.
According to the present invention, preferably, the organic vehicle is at least one of carboxymethyl cellulose, ethyl cellulose and terpineol.
Preferably, the organic carrier is carboxymethyl cellulose, ethyl cellulose and terpineol, and the weight ratio of the carboxymethyl cellulose to the ethyl cellulose to the terpineol is 1.
According to a preferred embodiment of the present invention, the electrode silver paste includes: 50-65wt% of silver powder, 10-20wt% of glass frit, 1-5wt% of an assistant and 10-39wt% of an organic vehicle, the glass frit comprising 44-74wt% of a Bi oxide, 10-20wt% of a B oxide, 3-7wt% of a Zn oxide, 10-20wt% of a Si oxide, 1-5wt% of a V oxide, 2-4wt% of a Mo oxide; the weight ratio of the V oxide to the Mo oxide is 1.2-2:1, and the weight ratio of the B oxide, the Si oxide and the Zn oxide is 2-3.5; the auxiliary agent is Ti oxide; the organic carrier is carboxymethyl cellulose, ethyl cellulose and terpineol, and the weight ratio of the carboxymethyl cellulose to the ethyl cellulose to the terpineol is 1.
The preparation method of the electrode silver paste is not limited at all, and can be any existing preparation method, for example, the raw materials are mixed according to the weight percentage and stirred uniformly, and then a three-roll grinder is used for rolling for 10-30 times.
The present invention will be described in detail below by way of examples. In the following examples, the starting materials were all commercially available products unless otherwise specified.
Example 1
(1) Preparing a Bi oxide, a B oxide, a Zn oxide, a Si oxide, a V oxide and a Mo oxide (the dosage of each raw material is shown in table 1) into a mixture; putting the mixture into a crucible for smelting (the temperature is 1300 ℃, and the heat preservation time is 20 min); water quenching the molten glass; drying; then ball milling and crushing into powder; sieving to obtain 0.5-6 μm composite glass powder;
(2) The silver powder, the composite glass powder, the auxiliary agent and the organic carrier are mixed and stirred uniformly according to the weight percentage shown in the table 1, and then a three-roll grinder is used for rolling for 20 times to obtain the electrode silver paste.
Then, electrode silver paste was printed on a P-type single crystal silicon substrate having a diameter of 100mm, and the substrate was placed in an infrared tunnel furnace and sintered at 800 ℃ to obtain a solar cell, and the photoelectric conversion efficiency of the solar cell was measured by a JT-1 transistor characteristic graph instrument as shown in table 2.
Examples 2 to 3
The procedure is as in example 1, except that the amounts of the starting materials and the process parameters indicated in Table 1 are used.
Examples 4 to 5
The procedure is as in example 1, except that the amounts of the starting materials and the process parameters indicated in Table 1 are used.
TABLE 1
Figure GDA0004046691070000061
Example 6
The procedure is as in example 1, except that the weight ratio of V oxide to Mo oxide is 1:3. The photoelectric conversion efficiency was measured as shown in table 2.
Example 7
The procedure of example 1 was followed, except that the weight ratio of the B oxide, si oxide and Zn oxide was 4. The photoelectric conversion efficiency was measured as shown in table 2.
Example 8
The procedure is as in example 1, except that the weight ratio of carboxymethyl cellulose, ethyl cellulose and terpineol is 1. The photoelectric conversion efficiency was measured as shown in table 2.
Example 9
The procedure is as in example 1 except that the organic vehicle is carboxymethylcellulose and terpineol, the weight ratio of carboxymethylcellulose to terpineol is 1:2 and the total amount of organic vehicle is the same as in example 1. The photoelectric conversion efficiency was measured as shown in table 2.
Comparative example 1
The procedure is as in example 1, except that no promoter Ti oxide is introduced in step (2). The photoelectric conversion efficiency was measured as shown in table 2.
Comparative example 2
The procedure of example 1 was followed except that no Mo oxide was introduced in step (1). The photoelectric conversion efficiency was measured as shown in table 2.
TABLE 2
Figure GDA0004046691070000071
Figure GDA0004046691070000081
As can be seen from the results in Table 2, the examples of the present invention have significantly better effects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (1)

1. An electrode silver paste, comprising: 60wt% of silver powder, 2wt% of an auxiliary agent, 20wt% of an organic carrier and the balance of glass powder, wherein the auxiliary agent is Ti oxide, the organic carrier is carboxymethyl cellulose, ethyl cellulose and terpineol, and the weight ratio of the carboxymethyl cellulose, the ethyl cellulose and the terpineol is 1; the glass powder is a composite glass powder consisting of Bi oxide, B oxide, si oxide, V oxide, 5wt% of Zn oxide and 2wt% of Mo oxide, and the weight ratio of the V oxide to the Mo oxide is 1.2; the weight ratio of the B oxide to the Si oxide to the Zn oxide is 2.
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CN102592703B (en) * 2012-02-13 2014-04-16 江苏瑞德新能源科技有限公司 Silver conductor slurry for back electrodes of solar energy battery
CN102718989B (en) * 2012-06-11 2015-02-25 洛阳理工学院 Organic carrier for electronic silver paste and preparation method of organic carrier
CN105825913B (en) * 2016-05-16 2017-11-24 南通天盛新能源股份有限公司 A kind of ageing-resistant crystal silicon solar energy battery back silver paste and preparation method thereof
CN108198648A (en) * 2017-12-27 2018-06-22 乐凯胶片股份有限公司 A kind of back of the body passivation rear surface of solar cell silver paste
CN109384393A (en) * 2018-10-15 2019-02-26 海宁市瑞银科技有限公司 PERC crystal silicon solar battery back silver paste lead-free glass powder and preparation method thereof

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