CN113443833A - Glass composition for front silver paste of crystalline silicon PERC battery and preparation method thereof - Google Patents
Glass composition for front silver paste of crystalline silicon PERC battery and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 179
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 72
- 239000004332 silver Substances 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title claims abstract description 26
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title claims abstract description 26
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title claims abstract description 26
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 114
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 229910003069 TeO2 Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 238000007496 glass forming Methods 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 22
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000002844 melting Methods 0.000 abstract description 11
- 230000008018 melting Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 238000005245 sintering Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- -1 silver ions Chemical class 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- 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
- H01B1/16—Conductive material dispersed in non-conductive inorganic 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
Abstract
The invention provides a glass composition for a front silver paste of a crystalline silicon PERC battery, which comprises lead-containing system glass powder and lead-free system glass powder; wherein the lead-containing glass powder is PbO-Bi2O3‑SiO2‑Li2O, lead-free glass powder is TeO2‑V2O5‑Li2O-ZnO, and the mixing ratio of the lead-containing glass powder to the lead-free glass powder is 1-10: 1. The glass composition for the front silver paste of the crystalline silicon PERC battery provided by the invention adopts two kinds of glass powder for combined use, one kind of glass powder is used for etching silicon nitride, and good ohmic contact is obtained; a silver melting method for melting silver, which can reduce the recombination of silicon surface by adjusting the size of silver crystal grains to obtain high open voltage and reduce contact resistance, thereby achieving higher conversion efficiency. The invention also provides a preparation method of the glass composition for the front silver paste of the crystalline silicon PERC battery.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a glass composition for a front silver paste of a crystalline silicon PERC cell and a preparation method thereof.
Background
Currently, the mainstream cell technology in the photovoltaic market is crystalline silicon PERC cell technology, which means passivated emitter back contact technology. In recent years, the technology of the PERC battery is rapidly developed, and after the technology of the SE selective emitter is matched, the efficiency is greatly improved to more than 23%. The intense competition in the photovoltaic market has made the demand for this enhancement increasingly high. In terms of the matching materials of the battery, the slurry occupies a higher proportion in the cost of the battery and plays a great role in improving the efficiency all the time. Therefore, the continuous improvement of the performance of the slurry is an important way for reducing the cost and improving the efficiency of the battery.
The front-side battery slurry is printed on the front side of the crystalline silicon PERC battery, and plays an important role in leading out photo-generated electrons generated in crystalline silicon. The front silver paste mainly comprises conductive phase silver powder, inorganic phase glass powder, an organic carrier and an additive. The silver powder mainly plays a role in conducting electricity, and the glass powder plays a role in etching silicon nitride and melting silver and promoting the sintering of the silver powder. And in the sintering process, the glass powder gradually softens and flows along with the increase of the sintering temperature, reacts with the silicon nitride of the antireflection film, and etches the silicon nitride to enable the silver powder to be contacted with the glass powder. During this process silver is dissolved in the liquid phase of the glass in the form of ions and reacts with silicon nitride to form silver. The generated silver is deposited on the surface of the silicon to form silver crystals which are channels for photo-generated electrons generated in the battery to flow to an external circuit, so that the more silver grains, the lower the contact resistance. However, a problem arises in that the more silicon nitride is etched, the more silver grains are formed, and the more metal compounds are formed on the silicon surface, which affects the open circuit voltage Voc.
In existing glass systems, a tradeoff is often made between open circuit voltage and contact resistance. When the open circuit voltage is high, the contact resistance is low; and when the contact is good and the contact resistance is low, the surface metal recombination is high and the open-circuit voltage is reduced due to more etching of silicon nitride and larger and deeper silver crystal grains.
In view of the above, the present invention aims to provide a new material to solve the above technical problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a glass composition for the front silver paste of a crystal silicon PERC battery, which adopts two kinds of glass powder to be used in combination, wherein one kind of glass powder is used for etching silicon nitride to obtain good ohmic contact; a silver melting method for melting silver, which can reduce the recombination of silicon surface by adjusting the size of silver crystal grains to obtain high open voltage and reduce contact resistance, thereby achieving higher conversion efficiency.
In order to solve the problems, the technical scheme of the invention is as follows:
a glass composition for a front silver paste of a crystal silicon PERC battery comprises lead-containing system glass powder and lead-free system glass powder; wherein the lead-containing glass powder is PbO-Bi2O3-SiO2-Li2O, lead-free glass powder is TeO2-V2O5-Li2O-ZnO, and the mixing ratio of the lead-containing glass powder to the lead-free glass powder is 1-10: 1.
Further, PbO-Bi2O3-SiO2-Li2In the O system, the contents of the components are as follows by weight percent:
PbO：40-70wt％，Bi2O3：10-30wt％，SiO2：10-20wt％，Li2O：10-20wt％。
further, PbO-Bi2O3-SiO2-Li2In the O system, alkali metal oxide Na is also included2O、K2O or its carbonate, or at least one of the alkaline earth metal oxides MgO, CaO, SrO, BaO or its carbonate, for adjusting the softening temperature and high-temperature viscosity of the glass; the addition amount of the PbO-Bi is PbO-Bi2O3-SiO2-Li20 to 5 wt% of the total amount of the O-system glass powder.
Further, PbO-Bi2O3-SiO2-Li2In the O system, a glass forming compound B is also included2O3And Al2O3For adjusting the glass transition temperature and the glass softening temperature; the addition amount of the PbO-Bi is PbO-Bi2O3-SiO2-Li20 to 5 wt% of the total amount of the O-system glass powder.
Further, PbO-Bi2O3-SiO2-Li2The particle size D50 of the O-system glass powder is 0.5-1.2 μm.
Further, TeO2-V2O5-Li2In the O-ZnO system, the contents of the components are as follows by weight percent:
TeO2and V2O5Sum of contents of (A): 60-80 wt%, Li2O：10-20wt％，ZnO：5-20wt％；
Wherein, TeO2And V2O5In a mass ratio of 1-5: 1.
Further, TeO2-V2O5-Li2In the O-ZnO system, SiO is also included2、WO3、B2O3、Al2O3At least one of the above components is beneficial to the oxidation of a glass former, the improvement of glass network connection and the adjustment of glass transition temperature; the addition amount of the additive is TeO2-V2O5-Li20-5 wt% of the total amount of the O-ZnO glass powder.
Further, TeO2-V2O5-Li2The particle size D50 of the O-ZnO glass powder is 1.2-2 μm.
PbO-Bi2O3-SiO2-Li2O-system glass powder and TeO2-V2O5-Li2The O-ZnO glass powder has smaller granularity and can soften and flow at lower temperature. Wherein, PbO-Bi2O3-SiO2-Li2The grain size of the O is smaller, and TeO with larger grain size penetrates through the antireflection film by softening and flowing preferentially along with the increase of the sintering temperature in the sintering stage2-V2O5-Li2The O-ZnO lead-free glass powder starts to melt silver, and the silver is along with the temperature riseThe glass flows down the silicon surface and then forms silver grains in the cooling stage.
Furthermore, the adding weight of the lead-containing glass powder and the lead-free glass powder in the slurry is 1.5-5%.
The process for preparing the front silver paste by the glass powder composition comprises the following steps:
the paste contains 82 to 92 wt% of silver powder, 1.5 to 5 wt% of the low temperature glass composition, and 5 to 15 wt% of the organic vehicle, based on the total weight of the paste. Accurately weighing the components, uniformly mixing, and then grinding by using a three-roll grinder, namely, fully mixing the slurry by utilizing shearing force. The fineness after grinding is less than 5 mu m, and the method is suitable for the printing requirement of a high-mesh screen plate.
The invention also provides a preparation method of the glass composition for the front silver paste of the crystalline silicon PERC battery, which comprises the following steps:
mixing PbO-Bi2O3-SiO2-Li2Drying each raw material of the O lead-containing system glass powder, uniformly mixing the raw materials in proportion, smelting at the smelting temperature of 1000-1200 ℃, keeping the temperature at the temperature of 20-60min, quenching, and then grinding to obtain the lead-containing system glass powder;
adding TeO2-V2O5-Li2Drying each raw material of the O-ZnO lead-free system glass powder, uniformly mixing the raw materials in proportion, smelting at the smelting temperature of 900-1100 ℃, preserving heat for 20-60min, quenching, and then grinding to obtain the lead-free system glass powder;
mixing the lead-containing glass powder and the lead-free glass powder according to the weight ratio of 1-10:1 to obtain the glass composition.
Compared with the prior art, the glass composition for the front silver paste of the crystalline silicon PERC battery has the beneficial effects that:
the invention provides a glass composition for crystalline silicon PERC battery front silver paste, which comprises lead-containing glass powder and lead-free glass powder, wherein the lead-containing glass powder is PbO-Bi2O3-SiO2-Li2O, lead-free glass powder is TeO2-V2O5-Li2O-ZnO. Wherein, PbO-Bi2O3-SiO2-Li2The function of the lead-containing glass powder is to etch the silicon nitride antireflection layer, so that silver and glass phases are in contact with silicon, and an interface is provided for the formation of silver crystal grains; TeO2-V2O5-Li2The O-ZnO lead-free system glass powder mainly has the functions of dissolving silver to enable the silver to exist in a glass system in an ion form, and then silver ions are separated out due to supersaturation in a sintering and cooling stage to form silver grains on the silicon surface; meanwhile, silver ions can also partially participate in the reaction with silicon nitride, and the effect of improving contact is achieved. Using PbO-Bi2O3-SiO2-Li2O lead-containing glass powder and TeO2-V2O5-Li2The O-ZnO lead-free glass powder combination can obtain better ohmic contact and simultaneously ensure lower metal composition on the silicon surface, thereby obtaining high open voltage and further ensuring higher photoelectric conversion efficiency.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
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 ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The glass composition for the front silver paste of the crystal silicon PERC battery comprises PbO-Bi2O3-SiO2-Li2O-system glass powder and TeO2-V2O5-Li2O-ZnO glass powder.
PbO-Bi2O3-SiO2-Li2The function of the lead-containing O-based glass powder is to etch the silicon nitride antireflection layerThe silver and glassy phase are brought into contact with the silicon to provide an interface for silver grain formation. The technical conception is as follows: the PbO can react with the silicon nitride and the silicon substrate in the sintering process and has stronger reaction, so that the invention can reduce the metallization composition of the silicon surface while utilizing the reaction of the PbO with the silicon and the silicon nitride, namely the reaction can not be too strong, thus the PbO can not flow to the surface of the silicon wafer prematurely, and one of the ways for realizing the purpose is to improve the softening point of the PbO glass, thereby reducing the glass amount flowing to the silicon substrate, reducing the damage of a glass layer to an emitter and enabling a battery to obtain high open voltage.
Specifically, PbO and Bi2O3Can react with the silicon nitride of the antireflection film to play a role of penetrating the silicon nitride. Adding PbO and Bi simultaneously2O3Then, the glass-transition temperature can be reduced, so that the glass starts to soften and flow at a lower temperature and reacts with silicon nitride; SiO 22The oxide is a glass forming body, and can increase the chemical stability of the glass and improve the corrosion resistance of the glass after being added. Li2Although O is an oxide outside the glass network, the lithium ion has small radius and strong accumulation effect, and the crystallization performance of the glass can be improved and the high-temperature fluidity of the glass can be controlled when the addition amount is more than 10wt percent.
PbO-Bi2O3-SiO2-Li2The lead-containing O-based glass powder may further contain an alkali metal oxide Na2O、K2O or its carbonate, or at least one of the alkaline earth metal oxides MgO, CaO, SrO, BaO or its carbonate, for adjusting the softening temperature and high-temperature viscosity of the glass; b may also be added2O3And Al2O3For adjusting the glass transition temperature and the glass softening temperature.
TeO2-V2O5-Li2The O-ZnO lead-free system glass powder mainly has the functions of dissolving silver to enable the silver to exist in a glass system in an ion form, and then silver ions are separated out due to supersaturation in a sintering and cooling stage to form silver grains on the silicon surface; meanwhile, silver ions can also partially participate in the reaction with silicon nitride, and the effect of improving contact is achieved. The design concept is as follows: TeO2-V2O5-Li2The O-ZnO system glass powder has a lower softening point, can ensure that the glass has better low-temperature fluidity, and promotes the sintering of silver powder. Wherein TeO2And V2O5The glass is an oxide with strong oxidizability and has strong solubility to silver, and the solubility of the glass to silver is increased after the oxide is added, so that more silver is dissolved in the glass in a sintering stage, and more silver grains are formed in a cooling stage, thereby increasing contact; and TeO2The glass flows more uniformly, the wettability of the silicon nitride antireflection film is better, the contact area of the glass and the silicon nitride layer can be increased, the corrosion of the silicon nitride layer is more uniform, and therefore a battery with uniform contact is obtained, and the requirement of wide sintering window is met; li is added into the system glass powder2O and ZnO can adjust the crystallization performance of the glass and control the fluidity of the glass at a high temperature stage, thereby achieving the purposes of controlling the tendency of overlarge silver crystal grain growth, reducing the metal recombination on the silicon surface and improving the open-circuit voltage.
TeO2-V2O5-Li2The O-ZnO lead-free glass powder can also be added with a glass forming compound SiO2、WO3、B2O3、Al2O3At least one of the above components is favorable for the oxidation of a glass former, the improvement of glass network connection and the adjustment of glass transition temperature.
The glass composition for the front silver paste of the crystalline silicon PERC battery provided by the invention is explained in detail by specific examples.
Example 1
Firstly, the oxides constituting the glass powder were dried, then 100g of the oxides were accurately weighed in the composition ratios shown in tables 1 and 2 in example 1, and the weighed oxides were put into a mixer to be mixed uniformly, and then transferred into a platinum crucible to be put into a melting furnace to be melted. PbO-Bi2O3-SiO2-Li2The melting temperature of the lead-containing O-based glass powder is 1000 ℃, and the heat preservation time is 60 minutes. TeO2-V2O5-Li2The melting temperature of the O-ZnO lead-free system glass powder is 900 ℃. The incubation time was 60 minutes. Then poured in quicklyQuenching is carried out in deionized water. The resulting glass frit was ground in a ball mill. PbO-Bi2O3-SiO2-Li2The granularity D50 of the ball-milled O lead-containing glass powder is 0.5 mu m, and the granularity of the ball-milled O lead-containing glass powder is TeO2-V2O5-Li2The particle size D50 of the O-ZnO lead-free glass powder after ball milling is 1.2 mu m.
Then taking PbO-Bi2O3-SiO2-Li2Lead-containing O glass powder 7.5g, TeO2-V2O5-Li27.5g of O-ZnO lead-free glass powder, 410g of silver powder and 75g of organic carrier are mixed, and then the mixture is ground and dispersed by a three-roll mill, and the obtained front electrode silver paste is numbered P1, and the fineness of the front electrode silver paste is less than 5 um.
Example 2
Example 2 and example 1 were formulated differently, and the compositions of oxides in the two glass powders were as shown in tables 1 and 2. The preparation method is the same as example 1, except that PbO-Bi2O3-SiO2-Li2The melting temperature of the lead-containing system glass powder is 1200 ℃, and the heat preservation time is 20 minutes; TeO2-V2O5-Li2The melting temperature of the O-ZnO lead-free glass powder is 1100 ℃. The incubation time was 20 minutes.
Ball milling to obtain PbO-Bi2O3-SiO2-Li2The granularity D50 of the ball-milled O lead-containing glass powder is 1.2 mu m, and the granularity of the ball-milled O lead-containing glass powder is TeO2-V2O5-Li2The particle size D50 of the O-ZnO lead-free glass powder after ball milling is 2 μm.
Then taking PbO-Bi2O3-SiO2-Li210g of lead-containing glass powder of O, TeO2-V2O5-Li25g of O-ZnO lead-free glass powder, 460g of silver powder and 25g of organic carrier are mixed, and then a three-roll mill is used for grinding and dispersing, wherein the number of the obtained front electrode silver paste is P2, and the fineness of the front electrode silver paste is less than 5 um.
Example 3
Example 3 and example 2 were formulated differently, and the compositions of oxides in the two glass powders were as shown in tables 1 and 2. The preparation method is the same as example 2, except that the slurry ratio is different, in this example, PbO-Bi is taken2O3-SiO2-Li2Lead-containing O glass powder 22.75g, TeO2-V2O5-Li22.25g of O-ZnO lead-free glass powder, 425g of silver powder and 50g of organic carrier are mixed, and then grinding and dispersing are carried out by a three-roll mill, the number of the obtained front electrode silver paste is P3, and the fineness of the front electrode silver paste is less than 5 um.
Example 4
Example 4 and example 3 were formulated differently, and the compositions of the oxides in the two glass powders are shown in tables 1 and 2. The preparation method is the same as example 3, except that the slurry ratio is different, in this example, PbO-Bi is taken2O3-SiO2-Li25g of lead-containing glass powder of O, TeO2-V2O5-Li22.5g of O-ZnO lead-free glass powder, 440g of silver powder and 52.5g of organic carrier are mixed, and then grinding and dispersing are carried out by a three-roll mill, and the obtained front electrode silver paste is numbered P4, and the fineness is less than 5 um.
Example 5
Different formulations were used for example 5 and example 4, and the compositions of oxides in the two glass powders were as shown in tables 1 and 2. The preparation method is the same as example 3, except that the slurry ratio is different, in this example, PbO-Bi is taken2O3-SiO2-Li2Lead-containing O glass powder 7.5g, TeO2-V2O5-Li22.5g of O-ZnO lead-free glass powder, 450g of silver powder and 40g of organic carrier are mixed, and then grinding and dispersing are carried out by a three-roll mill, and the obtained front electrode silver paste is numbered P5, and the fineness of the front electrode silver paste is less than 5 um.
Example 6
Different formulations were used for example 6 and example 5, and the compositions of oxides in the two glass powders were as shown in tables 1 and 2. The preparation method is the same as example 5, the proportions of the glass powder, the silver powder and the organic vehicle in the paste are the same as example 5, and the obtained paste is numbered P6.
Example 7
Different formulations were used for example 7 and example 6, and the compositions of oxides in the two glass powders were as shown in tables 1 and 2. The preparation method was the same as example 6, and the proportions of the glass frit, the silver powder and the organic vehicle in the paste were the same as example 6, and the obtained paste was numbered P7.
Example 8
Different formulations were used for example 8 and example 6, and the compositions of oxides in the two glass powders were as shown in tables 1 and 2. The preparation method was the same as example 6, and the proportions of the glass frit, the silver powder and the organic vehicle in the paste were the same as example 6, and the obtained paste was numbered P8.
Comparative example 1
The compositions of oxides in the glass frit of comparative example 1 are shown in tables 1 and 2. The preparation process is the same as example 5, except that only PbO-Bi is contained in the slurry2O3-SiO2-Li2Lead-containing O glass powder in an amount of 10g and containing no TeO2-V2O5-Li2O-ZnO lead-free glass powder. The resulting slurry was numbered P9.
Comparative example 2
The compositions of oxides in the glass frit of comparative example 2 are shown in tables 1 and 2. The preparation process is the same as example 5, except that only TeO is contained in the slurry2-V2O5-Li2O-ZnO leadless glass powder with content of 10g and no PbO-Bi2O3-SiO2-Li2O is a lead-containing glass powder. The resulting slurry was numbered P10.
The glass frits of examples 1 to 8 and comparative examples 1 to 2 had the following oxide compositions:
table 1: PbO-Bi2O3-SiO2-Li2O containing lead system glass powder composition (in percentage by weight)
TABLE 2 TeO2-V2O5-Li2O-ZnO leadless glass powder (by weight percentage)
| TeO2 | V2O5 | Li2O | ZnO | SiO2 | B2O3 | Al2O3 | |
| Example 1 | 35 | 35 | 10 | 20 | 0 | 0 | 0 |
| Example 2 | 62.5 | 12.5 | 20 | 5 | 0 | 0 | 0 |
| Example 3 | 50 | 25 | 10 | 15 | 0 | 0 | 0 |
| Example 4 | 50 | 20 | 12 | 13 | 5 | 0 | 0 |
| Example 5 | 30 | 30 | 20 | 15 | 2.5 | 2.5 | 0 |
| Example 6 | 40 | 20 | 20 | 15 | 0 | 2.5 | 2.5 |
| Example 7 | 40 | 20 | 20 | 15 | 0 | 2.5 | 2.5 |
| Example 8 | 30 | 30 | 20 | 15 | 2.5 | 2.5 | 0 |
| Comparative example 1 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Comparative example 2 | 30 | 30 | 20 | 15 | 2.5 | 2.5 | 0 |
The pastes obtained in examples 1 to 8 and comparative examples 1 to 2 were printed on the front surface of an SE-PERC cell, followed by sintering, and then the cell pieces were tested for I-V characteristics using a hall tester with the main parameters of open circuit voltage (Voc), short circuit current (Isc), Fill Factor (FF) and photoelectric conversion efficiency (Eta), and the test results are shown in table 3.
Table 3: I-V Properties of slurries of examples 1 to 8 and comparative examples 1 to 2
| Isc[A] | Uoc[v] | FF[％] | Eta[％] | Rser[Ohm] | Rshunt[Ohm] | |
| Example 1 | 10.0140 | 0.6876 | 81.5354 | 22.2781 | 0.0041 | 322.8980 |
| Example 2 | 10.0154 | 0.6876 | 81.3814 | 22.2405 | 0.0041 | 265.0182 |
| Example 3 | 9.9911 | 0.6874 | 81.4620 | 22.2008 | 0.0042 | 459.9136 |
| Example 4 | 10.0230 | 0.6878 | 81.4493 | 22.2838 | 0.0043 | 286.8999 |
| Example 5 | 10.0108 | 0.6876 | 81.3963 | 22.2359 | 0.0042 | 434.3351 |
| Example 6 | 10.0221 | 0.6872 | 81.4085 | 22.2497 | 0.0042 | 470.3484 |
| Example 7 | 10.0160 | 0.6871 | 81.6548 | 22.2990 | 0.0039 | 318.0551 |
| Example 8 | 10.0340 | 0.6872 | 81.2151 | 22.2228 | 0.0045 | 517.7003 |
| Comparative example 1 | 9.9440 | 0.6815 | 81.4823 | 21.9127 | 0.0043 | 275.4071 |
| Comparative example 2 | 10.0040 | 0.6839 | 80.0313 | 21.7297 | 0.0050 | 364.9683 |
As can be seen from the I-V performance test data of Table 3, examples 1-8 achieved higher photoelectric conversion efficiencies, ranging from 22.2% to 22.3%.
Comparative examples 1 and 2 have significantly low photoelectric conversion efficiency due to the addition of only one of the glass frits. In the comparative example 1, only the lead-containing glass powder is added, so that the glass powder has strong corrosivity and can well corrode a silicon nitride antireflection layer, and therefore, lower series resistance can be obtained, but the glass powder also has a destructive effect on silicon due to the strong corrosivity, so that the open-circuit voltage is lower, and the photoelectric conversion efficiency is low; in comparative example 2, since only the lead-free glass powder was added, the corrosion of the glass powder was weak, and the etching effect on silicon nitride was weak, the series resistance was high.
The slurry of the embodiments 1 to 8 is added with two kinds of system glass powders at the same time, the lead-containing system glass powder can help to form good contact resistance, and the silver melting effect of the lead-free system glass powder makes the number of silver crystal grains generated on the silicon surface more and tend to be small in size, so that the damage to silicon is small, the metal composition on the silicon surface is small, a small open-circuit voltage can be realized, and finally high photoelectric conversion efficiency is obtained.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. The glass composition for the front silver paste of the crystal silicon PERC battery is characterized by comprising lead-containing system glass powder and lead-free system glass powder; wherein the lead-containing glass powder is PbO-Bi2O3-SiO2-Li2O, lead-free glass powder is TeO2-V2O5-Li2O-ZnO and lead-containing systemsThe mixing ratio of the glass powder to the lead-free glass powder is 1-10: 1.
2. The glass composition for crystalline silicon PERC battery front silver paste of claim 1, wherein PbO-Bi2O3-SiO2-Li2In the O system, the contents of the components are as follows by weight percent:
PbO：40-70wt％，Bi2O3：10-30wt％，SiO2：10-20wt％，Li2O：10-20wt％。
3. the glass composition for crystalline silicon PERC battery front silver paste of claim 2, wherein PbO-Bi2O3-SiO2-Li2In the O system, alkali metal oxide Na is also included2O、K2O or carbonate thereof, or at least one of alkaline earth metal oxides MgO, CaO, SrO, BaO or carbonate thereof; the addition amount of the PbO-Bi is PbO-Bi2O3-SiO2-Li20 to 5 wt% of the total amount of the O-system glass powder.
4. The glass composition for crystalline silicon PERC battery front silver paste of claim 2, wherein PbO-Bi2O3-SiO2-Li2In the O system, a glass forming compound B is also included2O3And Al2O3The addition amount of the PbO-Bi is PbO-Bi2O3-SiO2-Li20 to 5 wt% of the total amount of the O-system glass powder.
5. The glass composition for crystalline silicon PERC battery front silver paste of claim 2, wherein PbO-Bi2O3-SiO2-Li2The particle size D50 of the O-system glass powder is 0.5-1.2 μm.
6. The glass composition for crystalline silicon PERC cell front side silver paste of claim 1, wherein TeO2-V2O5-Li2In the O-ZnO system, the contents of the components are as follows by weight percent:
TeO2and V2O5Sum of contents of (A): 60-80 wt%, Li2O：10-20wt％，ZnO：5-20wt％；
Wherein, TeO2And V2O5In a mass ratio of 1-5: 1.
7. The glass composition for crystalline silicon PERC cell front side silver paste of claim 5, wherein TeO2-V2O5-Li2In the O-ZnO system, SiO is also included2、WO3、B2O3、Al2O3At least one of (1) in an amount of TeO2-V2O5-Li20-5 wt% of the total amount of the O-ZnO glass powder.
8. The glass composition for crystalline silicon PERC cell front side silver paste of claim 6, wherein TeO2-V2O5-Li2The particle size D50 of the O-ZnO glass powder is 1.2-2 μm.
9. The glass composition for crystalline silicon PERC cell front silver paste according to any one of claims 1 to 8, wherein the weight of the lead-containing glass powder and the lead-free glass powder added in the paste is 1.5 to 5%.
10. A preparation method of a glass composition for a front silver paste of a crystalline silicon PERC battery is characterized by comprising the following steps:
mixing PbO-Bi2O3-SiO2-Li2Drying each raw material of the O lead-containing system glass powder, uniformly mixing the raw materials in proportion, smelting at the smelting temperature of 1000-1200 ℃, keeping the temperature at the temperature of 20-60min, quenching, and then grinding to obtain the lead-containing system glass powder;
adding TeO2-V2O5-Li2Baking each raw material of O-ZnO lead-free system glass powderDrying, uniformly mixing the materials in proportion, smelting at the smelting temperature of 900-1100 ℃, preserving heat for 20-60min, quenching, and then grinding to obtain lead-free system glass powder;
mixing the lead-containing glass powder and the lead-free glass powder according to the weight ratio of 1-10:1 to obtain the glass composition.
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