CN115504674B - Glass powder for front surface sizing agent of N-type solar cell and preparation method thereof - Google Patents
Glass powder for front surface sizing agent of N-type solar cell and preparation method thereof Download PDFInfo
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- CN115504674B CN115504674B CN202211172752.7A CN202211172752A CN115504674B CN 115504674 B CN115504674 B CN 115504674B CN 202211172752 A CN202211172752 A CN 202211172752A CN 115504674 B CN115504674 B CN 115504674B
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- 239000011521 glass Substances 0.000 title claims abstract description 149
- 239000000843 powder Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 title description 4
- 238000004513 sizing Methods 0.000 title description 4
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 19
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 10
- OTZGYUUQQRXJMY-UHFFFAOYSA-N $l^{2}-bismuthanylidenesilicon Chemical compound [Bi]=[Si] OTZGYUUQQRXJMY-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005097 cold rolling Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052709 silver Inorganic materials 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002161 passivation Methods 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000000156 glass melt Substances 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000005355 lead glass Substances 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 235000019325 ethyl cellulose Nutrition 0.000 description 5
- 229920001249 ethyl cellulose Polymers 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 229940116411 terpineol Drugs 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 4
- -1 silver-aluminum Chemical compound 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- 229910017982 Ag—Si Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910017107 AlOx Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZGUQQOOKFJPJRS-UHFFFAOYSA-N lead silicon Chemical group [Si].[Pb] ZGUQQOOKFJPJRS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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
- 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 application discloses glass powder for front slurry of an N-type solar cell and a preparation method thereof, wherein the glass powder is formed by mixing and collocating two types of glass powder, and the first type of glass powder is lead boron glass series glass which does not contain tellurium, zinc and bismuth and takes lead and boron as essential components; the second glass powder is tellurium glass which does not contain lead and takes tellurium bismuth silicon as an essential component. The glass powder of the first type can be quickly melted and etched through the anti-reflection layer in the sintering process, and the high-content lead active groups can quickly form a conductive contact window to form a good inverted pyramid structure, so that the silver melting efficiency is greatly improved, and a good contact resistance is obtained. The second type of glass frit is capable of controlling the inhibition of the glass melt by the silica-alumina content, producing a suitable passivation effect, balancing the corrosion ability of high lead glass, while providing proper fluidity. The two types of glass powders are matched to prepare slurry, so that the open-circuit voltage can be well improved, and good contact resistance, filling factor and conversion efficiency are obtained.
Description
Technical Field
The application relates to the technical field of conductive silver paste of solar cells, in particular to glass powder for front paste of TOPCON N-type solar cells and a preparation method thereof, and belongs to the technical field of TOPCON N-type solar cells.
Background
With the rapid development of economy of various countries, the energy consumption speed of human beings is increased, and the dependence requirement of human beings on emerging energy sources is gradually increased due to the over exploitation of traditional resources. In recent years, the solar photovoltaic power generation technology and application development are rapid, and the continuous cost reduction and efficiency improvement are very important for the whole industry. Among the solar cell technologies, crystalline silicon solar cells are rapidly developed due to low cost and high photoelectric conversion efficiency. Wherein high conversion efficiency cell structures such as tunnel oxide passivation contacts (tunnel oxide passivated contact, TOPCon). The TOPCON battery is used as one of the most promising high-efficiency solar cells at present, can realize the surface passivation effect equivalent to the HIT battery result, is compatible with a high-temperature sintering process, and can avoid the high recombination problem caused by electrode contact points.
The TOPCON battery technology front emitter mainly adopts silver-aluminum slurry, the pure silver slurry is difficult to form a good contact effect on the N-type battery emitter, and after aluminum powder is introduced, ag-Al-Si phases can be formed on the surface of the emitter, so that the resistance is reduced. At present, the silver aluminum paste glass powder of the N-type TOPCO battery is generally commonly used glass powder, so that damage to a PN junction is easily caused, a SiNx layer is excessively corroded, and the PN junction is broken down.
Disclosure of Invention
Aiming at the problems, the application provides the front-side slurry glass powder for the N-type solar cell and the preparation method thereof, which can be effectively applied to the front-side metallization technology of the N-type TOPCON cell, wherein the front-side slurry glass powder for the N-type solar cell contains high Pb and Bi contents, can well corrode a passivation layer, provides good silver melting, well infiltrates a solar cell silicon wafer, obtains better ohmic contact, and simultaneously provides good corrosion control contact effect and improves the photoelectric conversion efficiency of the cell.
The technical scheme of the application is as follows:
glass frit for N-type solar cell front side paste comprising two glass frit compositions. Wherein, the first glass powder is lead silicon glass which does not contain tellurium, zinc and bismuth and takes lead and boron as essential components; the second glass powder is tellurium glass which does not contain lead and takes tellurium bismuth silicon as an essential component. The first glass powder is mainly used as a three-dimensional corrosion silicon wafer AlOx passivation layer, is melted firstly in a high-temperature sintering process, wets the surface of the silicon wafer, and after reaching the limit of Ag atoms in the dissolving process, silver microcrystals appear and an Ag-Si conductive contact window is opened; however, after excessive quantity, the softening point is lower, the duration of the glass liquid state is longer, and PN junction breakdown is easy to cause; the second glass powder is mainly used for selectively inhibiting corrosion of glass melt on the surface of Si, and can be spread on the surface of Si, so that Ag-Si sintering is blocked, and the composite loss is effectively reduced;
the application is implemented by the following technical scheme:
the two glass powder compositions of the application, wherein, the first glass powder is lead boron glass which does not contain tellurium, zinc and bismuth and takes lead boron as an essential component; the second glass powder is tellurium glass which does not contain lead and takes tellurium bismuth silicon as an essential component.
The first glass powder is prepared from the following raw materials in parts by weight: 25 to 70mol% of PbO,1 to 50mol% of B 2 O 3 ，1～10mol％R 2 O and others.
The second glass powder is prepared from the following raw materials in parts by weight: 1 to 30mol% ZnO and 1 to 40mol% Bi 2 O 3 ，1～30mol％TeO 2 ，1～20mol％B 2 O 3 ，1～30mol％SiO 2 ，1～10mol％R 2 O and others.
The two glass powders are matched according to the proportion, wherein the first glass powder accounts for 30-80% of the total mass ratio of the mixed glass powder, and the second glass powder accounts for 20-70% of the total mass ratio of the mixed glass powder.
The alkali metal oxide R of the application 2 O is Na 2 O、Li 2 O、K 2 One or more of O.
The first glass powder also contains one or more of oxides of titanium, magnesium, aluminum and calcium or salts thereof, wherein the content of the oxides of titanium, magnesium, aluminum and calcium or salts thereof is 1-20mol%; the second glass powder also contains one or more of titanium, magnesium, aluminum, calcium, barium and tungsten oxides or salts thereof, wherein the content of the titanium, magnesium, aluminum, calcium, barium and tungsten oxides or salts thereof is 1-30mol%.
The particle size D50 of the glass powder is smaller than 10um, and the softening point of the glass powder is 300-400 ℃.
The application relates to a preparation method of front slurry glass powder for an N-type solar cell, which is a high-temperature melting water quenching method or a cold rolling method.
The application relates to a preparation method of glass powder for front slurry of an N-type solar cell, wherein the weight ratio of the mixed glass powder prepared by the preparation method in the front slurry of the N-type solar cell is controlled to be 2-8%.
The method for preparing the first glass powder and the second glass powder comprises the following steps:
(1) Proportioning according to the proportion of glass materials, weighing the components by calculating the weight of the components according to mole percentages, and fully and uniformly mixing the components in a mixer;
(2) Putting the materials into a platinum crucible, melting the materials by using a lifting furnace at the temperature of 1000-1300 ℃, preserving the heat for 1h, homogenizing the glass state, and preparing the glass material by using a melting water quenching method or a cold rolling method;
(3) The glass material is ground by adopting a horizontal or vertical ball mill, the rotating speed of the ball mill is 350-400r/min, the solvent is alcohol, the grinding time is 12h, the D50 is less than 10um material after drying, and further, the D50 is less than or equal to 5um material.
Compared with the prior art, the application provides the glass powder for the front slurry of the N-type solar cell, and the glass powder is prepared by mixing a lead-boron system and tellurium glass. Further, the lead-boron system and the tellurium-bismuth-silicon system are adopted. The action mode of the glass frit has larger difference with that of the traditional glass frit, and the lead-boron system can have better silver melting corrosion capability, provide more silver melting precipitation and open a conductive contact window. The tellurium bismuth silicon system can provide better control and selection contact capability, and simultaneously, the function is beneficial to improving the open pressure and the efficiency of the battery piece.
The first glass powder is lead boron glass which does not contain tellurium, zinc and bismuth and takes lead boron as an essential component; in the high-temperature sintering process, borate can be melted and etched through the anti-reflection layer at a lower temperature, an Ag-Si interface is opened, a conductive contact window can be formed rapidly by high-content lead active groups in glass, a good inverted pyramid structure is formed, silver melting efficiency is greatly improved, good contact resistance and filling factor are obtained, and cell efficiency is improved.
The second glass powder is tellurium glass which does not contain lead and takes tellurium bismuth silicon as an essential component. The glass contains high-content silicon, has lower glass fluidity, inhibits the corrosion of glass melt on the silicon surface in the high-temperature sintering process, and has a proper passivation effect. The bismuth telluride powder contains a proper amount of bismuth telluride, can ensure the adaptation with the first glass powder, keeps proper erosion capacity and spreads the silicon surface. The inhibiting capability of the glass melt is controlled by adjusting the content of silicon and aluminum, and the tellurium and bismuth can ensure proper fluidity and silver melting capability of the glass.
The technical scheme of the application has the following beneficial effects: the front-side slurry glass powder for the N-type solar cell provided by the application can be effectively applied to the front-side metallization technology of the N-type TOPCON cell, and the front-side slurry glass powder for the N-type solar cell contains high Pb and Bi contents, can well corrode a passivation layer, provides good silver melting, well infiltrates a solar cell silicon wafer, obtains good ohmic contact, and simultaneously can provide good corrosion control contact effect, and improves the photoelectric conversion efficiency of the cell.
Compared with single glass powder for other N-type solar cell front surface sizing agents, the application adopts the mixture of two types of glass powder, and the erosion of an inorganic system to different film layers and the control of ultra-thin SiO are realized through the combination of the two types of glass powder 2 The layer interface is coordinated with the performance of the silver-aluminum paste, so that the open pressure can be effectively improved, and the series resistance can be reduced.
Detailed Description
The lead boron glass system is prepared from the following raw materials in parts by weight: 25 to 70mol% of PbO,1 to 50mol% of B 2 O 3 ，1～10mol％R 2 O and others.
The tellurium-based glass is prepared from the following raw materials in parts by weight: 1 to 30mol% ZnO and 1 to 40mol% Bi 2 O 3 ，1～30mol％TeO 2 ，1～20mol％B 2 O 3 ，1～30mol％SiO 2 ，1～10mol％R 2 O and others.
According to the application, the two glass powders are matched in proportion, wherein the first glass powder accounts for 30-80% of the total mass ratio of the mixed glass powder, and the second glass powder accounts for 20-70% of the total mass ratio of the mixed glass powder.
Alkali metal R of the application 2 O is Na 2 O、Li 2 O、K 2 One or more of O.
The first glass powder also contains one or more of oxides of titanium, magnesium, aluminum and calcium or salts thereof, wherein the content of the oxides of titanium, magnesium, aluminum and calcium or salts thereof is 1-20mol%; the second glass powder also contains one or more of titanium, magnesium, aluminum, calcium, barium and tungsten oxides or salts thereof, wherein the content of the titanium, magnesium, aluminum, calcium, barium and tungsten oxides or salts thereof is 1-30mol%.
The particle size D50 of the glass powder is smaller than 10um, and the softening point of the glass powder is 300-400 ℃.
The application relates to a preparation method of front slurry glass powder of an N-type solar cell, which is a high-temperature melting water quenching method or a cold rolling method.
According to the preparation method of the front slurry glass powder of the N-type solar cell, the weight ratio of the mixed glass in the slurry is controlled to be 2-8%.
The method for preparing the first glass powder and the second glass powder comprises the following steps:
(1) Proportioning glass materials in tables 1 and 2, weighing the components by calculation according to mole percentages, and fully and uniformly mixing the components in a mixer;
(2) Putting the materials into a platinum crucible, melting the materials by using a lifting furnace at the temperature of 1000-1300 ℃, preserving the heat for 1h, homogenizing the glass state, and preparing the glass material by using a melting water quenching method or a cold rolling method;
(3) The glass material is ground by adopting a horizontal or vertical ball mill, the rotating speed of the ball mill is 400r/min, the solvent is alcohol, the grinding time is 12h, the D50 is less than 10um material after drying, and further, the D50 is less than or equal to 5um material.
List one
Watch II
Preparation examples and comparative examples of silver aluminum paste:
example 1
82wt% of conductive silver powder, 1wt% of conductive aluminum powder, 3wt% of first type glass powder GA-1,3wt% of second type glass powder GB-1 and 10wt% of organic phase are weighed. Wherein the organic phase is an activated mixture of terpineol, ethylcellulose, polyurethane, epoxy resin and silane coupling agent. The conductive silver powder, the conductive aluminum powder and the glass powder are premixed by a V-shaped mixer or a homogenizing mixer, and after the materials are uniform, the materials are mixed with an organic phase and centrifuged to be mixed fully. The slurry was sequentially ground 6 times using a three-roll grinder, and the fineness of grinding was measured using a scraper fineness meter. And the fineness test of the slurry is less than or equal to 8um. The slurry was prepared with the name NP-01.
Example 2
82wt% of conductive silver powder, 1wt% of conductive aluminum powder, 4wt% of first type glass powder GA-2,2wt% of second type glass powder GB-2 and 10wt% of organic phase are weighed. Wherein the organic phase is an activated mixture of terpineol, ethylcellulose, polyurethane, epoxy resin and silane coupling agent. The conductive silver powder, the conductive aluminum powder and the glass powder are premixed by a V-shaped mixer or a homogenizing mixer, and after the materials are uniform, the materials are mixed with an organic phase and centrifuged to be mixed fully. The slurry was sequentially ground 6 times using a three-roll grinder, and the fineness of grinding was measured using a scraper fineness meter. And the fineness test of the slurry is less than or equal to 8um. The slurry was prepared under the name NP-02.
Example 3
82wt% of conductive silver powder, 1wt% of conductive aluminum powder, 5wt% of first type glass powder GA-3,1wt% of second type glass powder GB-3 and 10wt% of organic phase are weighed. Wherein the organic phase is an activated mixture of terpineol, ethylcellulose, polyurethane, epoxy resin and silane coupling agent. The conductive silver powder, the conductive aluminum powder and the glass powder are premixed by a V-shaped mixer or a homogenizing mixer, and after the materials are uniform, the materials are mixed with an organic phase and centrifuged to be mixed fully. The slurry was sequentially ground 6 times using a three-roll grinder, and the fineness of grinding was measured using a scraper fineness meter. And the fineness test of the slurry is less than or equal to 8um. The slurry was prepared under the name NP-03.
Comparative example 1
82wt% of conductive silver powder, 1wt% of conductive aluminum powder, 6wt% of glass frit G-1,10wt% of organic phase were weighed. Wherein the organic phase is an activated mixture of terpineol, ethylcellulose, polyurethane, epoxy resin and silane coupling agent. Wherein the G-1 glass powder is single glass and is conventional commercial glass. Mainly comprises lead bismuth. The conductive silver powder, the conductive aluminum powder and the glass powder are premixed by a V-shaped mixer or a homogenizing mixer, and after the materials are uniform, the materials are mixed with an organic phase and centrifuged to be mixed fully. The slurry was sequentially ground 6 times using a three-roll grinder, and the fineness of grinding was measured using a scraper fineness meter. And the fineness test of the slurry is less than or equal to 8um. The slurry was prepared with the name NL-01.
Comparative example 2
82wt% of conductive silver powder, 1wt% of conductive aluminum powder, 6wt% of glass frit G-2,10wt% of organic phase were weighed. Wherein the organic phase is an activated mixture of terpineol, ethylcellulose, polyurethane, epoxy resin and silane coupling agent. Wherein the G-2 glass powder is single glass and is conventional commercial glass. Mainly comprises lead bismuth. The conductive silver powder, the conductive aluminum powder and the glass powder are premixed by a V-shaped mixer or a homogenizing mixer, and after the materials are uniform, the materials are mixed with an organic phase and centrifuged to be mixed fully. The slurry was sequentially ground 6 times using a three-roll grinder, and the fineness of grinding was measured using a scraper fineness meter. And the fineness test of the slurry is less than or equal to 8um. The slurry was prepared under the name NL-02.
The pastes prepared in examples 1-3 and comparative examples 1-2 were printed on N-type 164 silicon wafers using a mewei automatic printer, 40 sheets were printed on each paste, sintered using a destatch sintering furnace at 810 c peak temperature, and the battery sheet IV test was performed and the data recorded.
Table 3 shows a summary of the electrical performance data of the battery cells
| Sizing agent | Open circuit voltage | Series resistor | Fill factor | Conversion efficiency |
| NP-01 | 0.714 | 2.0 | 82.81 | 24.41 |
| NP-02 | 0.713 | 1.6 | 82.63 | 24.32 |
| NP-03 | 0.709 | 1.9 | 82.11 | 24.07 |
| NL-01 | 0.707 | 2.6 | 81.09 | 23.76 |
| NL-02 | 0.702 | 4.4 | 79.54 | 23.16 |
As shown in Table 3, the N-type slurries NP-01, NP-02 and NP-03 of the examples all had better electrical properties than the comparative examples. In the embodiment, the first glass powder and the second glass powder are mixed according to a certain proportion to prepare the N-type front slurry, so that better open-circuit voltage can be obtained, the composite loss is small, and the conversion is improved. From the data of the slurries of the numbers NP-01, NP-02 and NP-03, it can be seen that, along with the doping of the glass powder of the second type, the coordination effect of the two glass powders is obviously improved by 2-12mv compared with the slurry prepared by single glass, the filling factor is improved by 1.02-3.27%, and the conversion efficiency is improved by 0.31-1.25%. The proportion of the second glass type is properly increased, which is beneficial to controlling proper glass melt erosion and can obtain a better contact interface.
In summary, the glass powder of the first type can be quickly melted and etched through the anti-reflection layer in the sintering process, and the high-content lead active groups can quickly form a conductive contact window to form a good inverted pyramid structure, so that the silver melting efficiency is greatly improved, and a good contact resistance is obtained. The second type of glass frit is capable of controlling the inhibition of the glass melt by the silica-alumina content, producing a suitable passivation effect, balancing the corrosion ability of high lead glass, while providing proper fluidity. The two types of glass powders are matched to prepare slurry, so that the open-circuit voltage can be well improved, and good contact resistance, filling factor and conversion efficiency are obtained.
The application includes the illustrative items, principles of action and structures of the above examples, but not limited to the above description, the scope of the application being defined only by the claims. The embodiments can be modified, modified and replaced in multiple layers without departing from the illustrative principles and conditions of the application, and all the embodiments with the same or similar technical schemes and applications are within the scope of the application.
Claims (7)
1. Glass frit for front-side paste of N-type solar cell, characterized in that it comprises two glass frit compositions, wherein the first glass frit is lead boron glass system glass without tellurium, zinc and bismuth and with lead and boron as essential components; the second glass powder is tellurium glass which does not contain lead and takes tellurium bismuth silicon as an essential component;
the raw material components of the first glass powder comprise: 35 to 70mol percent of PbO,35～50mol％B 2 O 3 ，1～10mol％R 2 o, said R 2 O is an alkali metal oxide;
the raw material components of the second glass powder comprise: 1 to 30mol% of ZnO,26 to 40mol% of Bi 2 O 3 ，22～30mol％TeO 2 ，1～20mol％B 2 O 3 ，15～30mol％SiO 2 ，1～10mol％R 2 O, said R 2 O is an alkali metal oxide;
the ratio of the two glass powders is 50-80% of the total mass ratio of the mixed glass powder, and the ratio of the second glass powder to the mixed glass powder is 20-50%.
2. The glass frit for N-type solar cell front surface paste according to claim 1, wherein the alkali metal oxide R 2 O is Na 2 O、Li 2 O、K 2 One or more of O.
3. The glass powder for the front surface slurry of the N-type solar cell according to claim 1, wherein the first glass powder further contains one or more of oxides of titanium, magnesium, aluminum and calcium or salts thereof, and the contents of the oxides of titanium, magnesium, aluminum and calcium or salts thereof are as follows: 1 to 20mol%; the second glass powder also contains one or more of oxides of titanium, magnesium, aluminum, calcium, barium and tungsten or salts thereof, wherein the contents of the oxides of titanium, magnesium, aluminum, calcium, barium and tungsten or the salts thereof are as follows: 1 to 30mol percent.
4. The glass frit for N-type solar cell front surface paste according to claim 1, wherein the particle size D50 of the glass frit is less than 10um, and the softening point of the glass frit is 300-400 ℃.
5. A method for preparing the front-side paste glass powder for the N-type solar cells according to any one of claims 1 to 4, which comprises the following steps:
(1) The first glass powder or the second glass powder is singly proportioned according to the proportion of glass materials, and the components materials are weighed according to mole percent, and are fully and uniformly mixed in a mixer by calculating the weight of each component;
(2) Putting the materials into a platinum crucible, melting the materials by using a lifting furnace at the temperature of 1000-1300 ℃, preserving the heat for 1h, homogenizing the glass state, and preparing the glass material by using a melting water quenching method or a cold rolling method;
(3) The glass material is ground by adopting a horizontal or vertical ball mill, the rotating speed of the ball mill is 350-400r/min, the solvent is alcohol, the grinding time is 12h, and the D50 < 10um material is obtained after drying.
6. The method for preparing front-side paste glass powder for N-type solar cells according to claim 5, wherein the material obtained in the step (3) is D50.ltoreq.5um.
7. The method for preparing glass frit for N-type solar cell front surface paste according to claim 5, wherein the weight ratio of the mixed glass frit prepared by the preparation method in the N-type solar cell front surface paste is controlled to be 2-8%.
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| KR20150027652A (en) * | 2013-09-04 | 2015-03-12 | 제일모직주식회사 | The composition for forming solar cell electrode comprising the same, and electrode prepared using the same |
| US10040717B1 (en) * | 2017-09-18 | 2018-08-07 | Jiangxi Jiayin Science and Technology, Ltd. | Thick-film paste with multiple discrete frits and methods for contacting crystalline silicon solar cell emitter surfaces |
| CN111599506A (en) * | 2020-04-08 | 2020-08-28 | 常州聚和新材料股份有限公司 | Solar cell conductive paste, glass material and solar cell |
| CN113380439A (en) * | 2020-03-02 | 2021-09-10 | 常州聚和新材料股份有限公司 | Composition for forming solar cell electrode and solar cell electrode formed therefrom |
| CN114999704A (en) * | 2022-04-01 | 2022-09-02 | 广东南海启明光大科技有限公司 | Auxiliary glass powder additive for silver paste and preparation method thereof |
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| KR20150027652A (en) * | 2013-09-04 | 2015-03-12 | 제일모직주식회사 | The composition for forming solar cell electrode comprising the same, and electrode prepared using the same |
| US10040717B1 (en) * | 2017-09-18 | 2018-08-07 | Jiangxi Jiayin Science and Technology, Ltd. | Thick-film paste with multiple discrete frits and methods for contacting crystalline silicon solar cell emitter surfaces |
| CN113380439A (en) * | 2020-03-02 | 2021-09-10 | 常州聚和新材料股份有限公司 | Composition for forming solar cell electrode and solar cell electrode formed therefrom |
| CN111599506A (en) * | 2020-04-08 | 2020-08-28 | 常州聚和新材料股份有限公司 | Solar cell conductive paste, glass material and solar cell |
| CN114999704A (en) * | 2022-04-01 | 2022-09-02 | 广东南海启明光大科技有限公司 | Auxiliary glass powder additive for silver paste and preparation method thereof |
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