CN111875254A - Lead-free glass powder suitable for front silver paste of black silicon + perc battery and preparation method thereof - Google Patents
Lead-free glass powder suitable for front silver paste of black silicon + perc battery and preparation method thereof Download PDFInfo
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- CN111875254A CN111875254A CN202010732893.4A CN202010732893A CN111875254A CN 111875254 A CN111875254 A CN 111875254A CN 202010732893 A CN202010732893 A CN 202010732893A CN 111875254 A CN111875254 A CN 111875254A
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different 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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Abstract
The invention discloses lead-free glass powder for front silver paste suitable for a black silicon + perc battery, which is prepared by mixing two types of glass powder with different sizes according to mass fraction; the lead-free glass powder for the front silver paste of the black silicon + perc battery, provided by the invention, has the advantages that the two glass powders can be mixed according to a certain proportion, different combination effects can be generated by different proportions, and therefore, the optimal proportion can be matched, and the optimal tension value can be obtained. The prepared double-component glass powder with different particle sizes can obtain higher photoelectric conversion efficiency by improving the combination state of the silver electrode and the aggregate.
Description
Technical Field
The invention relates to the field of new materials, in particular to lead-free glass powder suitable for black silicon + perc battery front silver paste and a preparation method thereof.
Background
The industrial production of crystalline silicon solar cell electrode metallization adopts a screen printing process, and the slurry used for the screen printing of the crystalline silicon solar cell front silver electrode is prepared by matching superfine high-purity silver powder serving as a main body filler with a certain proportion of a glass powder organic carrier. In the crystalline silicon solar cell, the average efficiency of the black silicon is generally 18.8-19.0% due to the higher conversion efficiency of the black silicon solar cell, the efficiency of the black silicon solar cell is improved by 0.2-0.4% compared with the conventional cell, and the power of the module can reach 275W. The black silicon technology can form a nano-scale pit to improve the capture of incident light, so that the cost reduction of a silicon wafer end and the efficiency improvement of a battery piece end are both considered simultaneously.
Among the many factors affecting the performance of the black silicon + perc cell, the glass frit is a key factor, and directly affects the electrical performance of the solar cell, particularly the series resistance of the solar cell, and further affects the photoelectric conversion efficiency of the cell. Therefore, there is a great demand for producing a glass powder having a low melting point and glass transition temperature, good wettability to a silicon substrate and silver powder in a high-temperature molten state, good ohmic contact, and a large tensile value.
Aiming at the key problems, the invention provides the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery. This glass powder has the glass powder of two kinds of different components and particle diameter to mix according to the proportion of difference and forms, and glass powder A can see through the SiN rete in the use, forms good contact with black silicon-perc battery, and glass powder B is bigger because the size, can see through the rete and form strong rivet effect on collective, lets form a very strong combination effect between silver thick liquid and the base member, has obtained great pulling force value to high energy conversion efficiency has been obtained.
Through retrieval, the application number CN201210474531.5 is named as a technical scheme of lead-free low-melting-point glass powder for silver paste on the front surface of a silicon solar cell and a preparation method thereof, and the technical problem to be solved is that a glass semiconductor can be formed, after an electrode is formed by preparing slurry, the reflection of a printed grid line and an electrode to sunlight can be reduced, the influence of contact grid line and electrode shadow to light is reduced, the absorption of the grid line and the electrode to light is increased, and meanwhile, the glass powder has a lower softening point, a low thermal expansion coefficient and good fluidity. The lead-free low-melting-point glass powder for the front silver paste of the silicon solar cell is prepared and processed from Bi2O 330-60%, B2O 31.5-18%, ZnO 1-13%, Al2O 31-15%, BaO 0.1-6%, TeO 210-45% and SiO 23-25% in percentage by weight, is a glass semiconductor, and has the softening temperature of 410-540 ℃, the thermal expansion coefficient of 56-75 multiplied by 10 < -7 >/DEG C, the particle size range of 0.3-4 mu m and the particle size span of less than 1.3. In summary, the solution of the present application, whether solving the technical problem or being a specific solution, is significantly different from the above-mentioned search document.
Disclosure of Invention
The invention adopts the technical scheme that the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery and the preparation method thereof are provided to solve the technical problems, and the two-phase lead-free glass powder which is lead-free, environment-friendly, high in adhesive force, contact resistance and high in tensile value is obtained by mixing two kinds of glass powder with different components and particle sizes.
In order to achieve the purpose, the invention adopts the technical scheme that:
is prepared by mixing two kinds of glass powder with different grain diameters according to a certain proportion;
the formula of one of the glass powder A is as follows: bi2O325～45％、TeO230～40％、SiO 21～5％、WO35～15％、Nb2O51～5％、SrCO32～7％、P2O50～6％、CaCO30～5％、MgO 0～4％、La2O30～2％；
The formula of another glass powder B is as follows: 360-75% of Bi2O and H3BO315～20％、ZnO 0.1～4％、Al2O30～3％、CeO22～8％、MoO30.1～5％、Y2O35～10％、Na2CO30～5％、Nd2O30～5％。
And mixing the two kinds of glass powder according to a certain proportion, wherein the specific range is x glass powder A: (1-x) glass powder B, wherein x is in the range of 0.6-0.9.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: the preparation process of the glass powder A comprises the following steps:
1) firstly, raw materials used for the glass powder A, analytically pure bismuth trioxide, tellurium dioxide, silicon dioxide, tungsten trioxide, niobium pentoxide, strontium carbonate, phosphorus pentoxide, calcium carbonate, magnesium oxide and lanthanum trioxide are weighed according to a certain proportion and are uniformly mixed;
2) then the mixture is put into a corundum crucible with the purity of 99.9 percent;
3) putting the crucible filled with the mixture into a muffle furnace;
4) taking the crucible out of the muffle furnace by using crucible tongs, pouring the molten glass liquid on a double-roller machine rotating at a high speed, cooling the molten glass liquid and rolling the molten glass liquid into a glass sheet;
5) putting the glass sheet into a polyurethane ball milling tank for primary crushing;
6) and crushing the dried glass powder by a high-speed jet mill.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: and 3) in the step 3), heating to 1000-1040 ℃ according to the temperature of 10 ℃/. min, and preserving the heat for 60-90min to enable the mixture in the crucible to be fully melted and reacted.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: in the step 5), according to the glass material: ball grinding stone: setting the rotation speed of a planetary ball mill to 380 r/min, ball-milling for 2.5h until the particle size of glass powder is within the range of 80-120 mu m, and drying the ball-milled glass powder.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: and 6), until the particle size range of the glass powder reaches D10-0.2-0.5 μm, D50-2.5 μm and D100 is less than 5 μm.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: the preparation process of the glass powder B comprises the following steps:
1) firstly, raw materials used by the glass powder B, analytically pure bismuth trioxide, boric acid, zinc oxide, aluminum oxide, cerium dioxide, molybdenum trioxide, yttrium trioxide, sodium carbonate and neodymium trioxide are weighed according to a certain proportion and are uniformly mixed;
2) then the mixture is put into a corundum crucible with the purity of 99.9 percent;
3) putting the crucible filled with the mixture into a muffle furnace;
4) taking the crucible out of the muffle furnace by using crucible tongs, pouring the molten glass liquid on a double-roller machine rotating at a high speed, cooling the molten glass liquid and rolling the molten glass liquid into a glass sheet;
5) putting the glass sheet into a polyurethane ball milling tank for primary crushing;
6) crushing the dried glass powder by a high-speed jet mill;
7) and mixing the two prepared glass powders according to a certain proportion to obtain the finished glass powder.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: in the step 3), the temperature is increased to 1070-.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: in the step 5), according to the glass material: ball grinding stone: setting the rotation speed of a planetary ball mill to 380 r/min, ball-milling for 2.5h until the particle size of glass powder is within the range of 80-120 mu m, and drying the ball-milled glass powder.
The preparation method of the lead-free glass powder suitable for the front silver paste of the black silicon + perc battery comprises the following steps: and 6), until the particle size range of the glass powder reaches D10-0.2-0.5 μm, D50-1.8 μm and D100 is less than 5 μm.
Compared with the prior art, the invention has the following beneficial effects:
1) the prepared two-component glass powder with different particle sizes is prepared from lead-free environment-friendly raw materials, belongs to environment-friendly materials, and is safe and non-toxic to human bodies;
2) according to the two-component glass powder with different particle sizes, the two glass powders can be mixed according to a certain proportion, and different proportions can produce different combination effects, so that the optimal proportion can be matched, and the optimal tension value can be obtained;
3) the prepared double-component glass powder with different particle sizes can obtain higher photoelectric conversion efficiency by improving the combination state of the silver electrode and the aggregate.
Drawings
Fig. 1 is qualitative or quantitative experimental data for realizing technical effects of the lead-free glass powder for the front silver paste of the black silicon + perc battery provided by the invention.
Detailed Description
The invention provides the lead-free environment-friendly double-component glass powder with different particle sizes, good adhesion, large tensile force value and high energy conversion efficiency. The key points of the technology of the invention are as follows: firstly, two components of glass powder with different particle sizes are matched for use; and secondly, the jet mill is adopted to finely crush the glass powder, and the particle size is controlled in a very stable range, so that the stability of a slurry viscosity system is ensured, and the expected effect of the glass powder in the slurry performance is ensured.
According to the formula of the glass powder A, Bi is in mass ratio2O340％、TeO235％、SiO24％、WO38％、Nb2O54％、SrCO34％、P2O52％、CaCO 31％、MgO 1％、La2O31 percent; and then preparing the finished glass powder according to the preparation process of the glass powder A. According to the formula of the glass powder B, Bi is added according to the mass ratio2O365％、H3BO318％、ZnO2％、Al2O31％、CeO23％、MoO32％、Y2O36％、Na2CO32％、Nd2O31 percent of the raw materials are mixed and then prepared into finished glass according to the preparation process of the glass powder BAnd (3) pulverizing.
Example one
The two prepared glass powders are uniformly mixed according to 60% of glass powder A and 40% of glass powder B, then the mixed two-component glass powder with different particle diameters is prepared into finished slurry according to 2%, 90% of silver powder and 8% of organic carrier, and printing, sintering and terminal performance testing are carried out according to the application process of the slurry. The final data are shown in the following table:
example two
And uniformly mixing the two prepared glass powders according to 70% of glass powder A and 30% of glass powder B, preparing finished slurry from the mixed two-component glass powder with different particle sizes according to 2%, 90% of silver powder and 8% of organic carrier, and printing, sintering and testing the terminal performance according to the application process of the slurry. The final data are shown in the following table:
the final battery efficiency of the double-component glass powder with different particle sizes is 0.37% higher than that of a main stream competitive product, the adhesion force is 1N higher than that of the main stream competitive product, and the use requirement is far met. Therefore, the two-component glass powder in this example is in the best ratio.
EXAMPLE III
And uniformly mixing the two prepared glass powders according to 80% of glass powder A and 20% of glass powder B, preparing finished slurry from the mixed two-component glass powder with different particle sizes according to 2%, 90% of silver powder and 8% of organic carrier, and printing, sintering and testing the terminal performance according to the application process of the slurry. The final data are shown in the following table:
example four
And uniformly mixing the two prepared glass powders according to 90% of glass powder A and 10% of glass powder B, preparing finished slurry from the mixed two-component glass powder with different particle sizes according to 2%, 90% of silver powder and 8% of organic carrier, and printing, sintering and testing the terminal performance according to the application process of the slurry. The final data are shown in the following table:
although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The lead-free glass powder for the front silver paste suitable for the black silicon + perc battery is characterized in that: mixing two kinds of glass powder with different sizes according to mass fraction:
the formula of one of the glass powder A is as follows: bi2O325～45％、TeO230～40％、SiO21～5％、WO35～15％、Nb2O51～5％、SrCO32～7％、P2O50～6％、CaCO30～5％、MgO 0～4％、La2O30～2％；
The formula of another glass powder B is as follows: bi2O360～75％、H3BO315～20％、ZnO 0.1～4％、Al2O30～3％、CeO22～8％、MoO30.1～5％、Y2O35～10％、Na2CO30～5％、Nd2O30～5％；
And mixing the two kinds of glass powder according to a certain proportion, wherein the specific range is x glass powder A: (1-x) glass powder B, wherein x is in the range of 0.6-0.9.
2. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery according to claim 1, wherein the preparation process of the glass powder A comprises the following steps:
1) firstly, raw materials used for the glass powder A, analytically pure bismuth trioxide, tellurium dioxide, silicon dioxide, tungsten trioxide, niobium pentoxide, strontium carbonate, phosphorus pentoxide, calcium carbonate, magnesium oxide and lanthanum trioxide are weighed according to a certain proportion and are uniformly mixed;
2) then the mixture is put into a corundum crucible with the purity of 99.9 percent;
3) putting the crucible filled with the mixture into a muffle furnace;
4) taking the crucible out of the muffle furnace by using crucible tongs, pouring the molten glass liquid on a double-roller machine rotating at a high speed, cooling the molten glass liquid and rolling the molten glass liquid into a glass sheet;
5) putting the glass sheet into a polyurethane ball milling tank for primary crushing;
6) and crushing the dried glass powder by a high-speed jet mill.
3. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 2, wherein the method comprises the following steps: and 3) in the step 3), heating to 1000-1040 ℃ at the temperature of 10 ℃/min, and preserving the heat for 60-90min to ensure that the mixture in the crucible is fully melted and reacted.
4. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 2, wherein the method comprises the following steps: in the step 5), according to the glass material: ball grinding stone: setting the rotation speed of a planetary ball mill to 300 r/min, ball-milling for 2h until the particle size of glass powder is within the range of 80-120 mu m, and drying the ball-milled glass powder.
5. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 2, wherein the method comprises the following steps: and 6), until the particle size ranges of the glass powder reach D10-0.5 μm, D50-2.5-3 μm and D100 is less than 6 μm.
6. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 1, wherein the method comprises the following steps: the preparation process of the glass powder B comprises the following steps:
1) firstly, raw materials used by the glass powder B are analyzed and pure-grade bismuth trioxide, boric acid, zinc oxide, aluminum oxide, cerium dioxide, molybdenum trioxide, yttrium trioxide, sodium carbonate and neodymium trioxide are weighed according to a certain proportion and are uniformly mixed;
2) then the mixture is put into a corundum crucible with the purity of 99.9 percent;
3) putting the crucible filled with the mixture into a muffle furnace;
4) taking the crucible out of the muffle furnace by using crucible tongs, pouring the molten glass liquid on a double-roller machine rotating at a high speed, cooling the molten glass liquid and rolling the molten glass liquid into a glass sheet;
5) putting the glass sheet into a polyurethane ball milling tank for primary crushing;
6) crushing the dried glass powder by a high-speed jet mill;
7) and mixing the two prepared glass powders according to a certain proportion to obtain the finished glass powder.
7. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 6, wherein the method comprises the following steps: in the step 3), the temperature is increased to 1070-.
8. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 6, wherein the method comprises the following steps: in the step 5), according to the glass material: ball grinding stone: setting the rotation speed of a planetary ball mill to 300 r/min, ball-milling for 2h until the particle size of glass powder is within the range of 80-120 mu m, and drying the ball-milled glass powder.
9. The method for preparing the lead-free glass powder for the front silver paste of the black silicon + perc battery as claimed in claim 6, wherein the method comprises the following steps: and 6), until the particle size range of the glass powder reaches D10-0.2-0.5 μm, D50-1.5-1.8 μm and D100 is less than 6 μm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910828A (en) * | 2012-11-21 | 2013-02-06 | 贵州威顿晶磷电子材料有限公司 | Low-melting point glass powder for silver pastes on fronts of silicon solar cells and preparation method of glass powder |
| TW201638036A (en) * | 2015-02-19 | 2016-11-01 | Central Glass Co Ltd | BiO-TeO-SiO-WO-based glass |
| CN107265872A (en) * | 2017-07-10 | 2017-10-20 | 上海银浆科技有限公司 | One kind is applied to crystal silicon battery front side silver paste two-component lead-free glass powder |
| KR20190028038A (en) * | 2017-09-08 | 2019-03-18 | 대주전자재료 주식회사 | Paste composition of solar cell front electrode and manufacturing method thereof |
| CN110950540A (en) * | 2019-11-11 | 2020-04-03 | 上海银浆科技有限公司 | Surface modification method of glass for front silver paste of solar cell |
| CN111268915A (en) * | 2018-12-04 | 2020-06-12 | 上海银浆科技有限公司 | Bi-component high-contact glass powder for solar front silver paste |
-
2020
- 2020-07-27 CN CN202010732893.4A patent/CN111875254A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910828A (en) * | 2012-11-21 | 2013-02-06 | 贵州威顿晶磷电子材料有限公司 | Low-melting point glass powder for silver pastes on fronts of silicon solar cells and preparation method of glass powder |
| TW201638036A (en) * | 2015-02-19 | 2016-11-01 | Central Glass Co Ltd | BiO-TeO-SiO-WO-based glass |
| CN107265872A (en) * | 2017-07-10 | 2017-10-20 | 上海银浆科技有限公司 | One kind is applied to crystal silicon battery front side silver paste two-component lead-free glass powder |
| KR20190028038A (en) * | 2017-09-08 | 2019-03-18 | 대주전자재료 주식회사 | Paste composition of solar cell front electrode and manufacturing method thereof |
| CN111268915A (en) * | 2018-12-04 | 2020-06-12 | 上海银浆科技有限公司 | Bi-component high-contact glass powder for solar front silver paste |
| CN110950540A (en) * | 2019-11-11 | 2020-04-03 | 上海银浆科技有限公司 | Surface modification method of glass for front silver paste of solar cell |
Non-Patent Citations (1)
| Title |
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| 云斯宁主编: "《新型能源材料与器件》", 31 May 2019, 北京：中国建材工业出版社 * |
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