CN111009334A - Conductive silver paste for solar cell and preparation method thereof - Google Patents
Conductive silver paste for solar cell and preparation method thereof Download PDFInfo
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- CN111009334A CN111009334A CN201911378148.8A CN201911378148A CN111009334A CN 111009334 A CN111009334 A CN 111009334A CN 201911378148 A CN201911378148 A CN 201911378148A CN 111009334 A CN111009334 A CN 111009334A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 98
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 17
- 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 claims abstract description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 17
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 17
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940116411 terpineol Drugs 0.000 claims abstract description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims abstract description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 55
- 229910052593 corundum Inorganic materials 0.000 claims description 36
- 239000010431 corundum Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 12
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001780 ECTFE Polymers 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 6
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010344 co-firing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- 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
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a conductive silver paste for a solar cell and a preparation method thereof, the conductive silver paste for the solar cell comprises 1-10 parts by weight of an organic carrier, 70-90 parts by weight of a conductive metal phase, 2-3 parts by weight of a binder and 0-1 part by weight of an additive, wherein the binder is Bi-B-Si glass powder, and the softening temperature of the glass powder is low, so that the sintering temperature is lowered, the influence of high temperature on a solar cell substrate is reduced, and the thermal expansion coefficient can be effectively reduced by adopting at least one organic system selected from terpineol, benzyl alcohol, ethyl cellulose, butyl carbitol, tributyl citrate and tributyl phthalate, so that the problem of warping of a silicon crystal solar cell after high-temperature sintering is reduced.
Description
Technical Field
The invention belongs to the field of conductive base materials for solar cells, and particularly relates to conductive silver paste for a solar cell and a preparation method thereof.
Background
With the continuous development of the photovoltaic industry, the product types of the solar cell are increasing, and the solar cell comprises a crystalline silicon solar cell, a multi-compound thin-film solar cell, a quantum dot solar cell, an organic solar cell and the like. Among these solar cell products, the crystalline silicon solar cell has been developed most mature, wide in application range and high in conversion efficiency due to industrial technology, and thus has a dominant position in the global photovoltaic market.
In the crystalline silicon solar cell, the most basic structure is a P-N junction diode, and the P-N junction is the most basic utilization form for realizing photoelectric conversion on the crystalline silicon solar cell and is also the core component for realizing a conductive path of a plurality of semiconductor devices. Because the migration speed of electrons in Si is obviously higher than that of holes, the former is about 3 times of that of the latter, so that P-type silicon is usually selected as a substrate, an N-type layer is formed on the P-type silicon substrate through diffusion, and forms a P-N junction together with the P-type layer to form the basic structure of the crystalline silicon solar cell.
The main flow of the industrial production of the crystalline silicon solar cell comprises silicon slicing; cleaning and removing the damaged layer; preparing a suede structure; preparing a P-N junction; etching the periphery; plating SiN and an anti-reflection film by PECVD; preparing an aluminum back surface field: screen printing to prepare front and back electrodes; drying and sintering; testing, sorting, packaging and the like.
Silver paste plays a critical role in the preparation of various raw materials of crystalline silicon solar cells. The glass powder is used as the most important raw material in the silver paste of the solar cell, and the quality of the performance of the glass powder directly influences the quality of the paste of the solar cell, so that the photoelectric conversion efficiency of the cell is influenced, and therefore, the preparation of the glass powder for the silver paste with excellent performance is the key for preparing the high-efficiency solar cell. Because the research and development of the silver paste for the solar cell in China are late, the quality of the glass powder for the silver paste produced in China is still not high. The existing silver paste manufacturing often affects the manufacturing yield of the battery and the battery module because the silver paste causes the battery to warp. Secondly, when the silver paste is manufactured by applying the traditional screen printing process, a high-temperature co-firing process is used for firing the conductive paste into a solidified electrode, and certain damage can be caused to the battery piece by high-temperature sintering. Thirdly, in the cooling process after co-firing, the battery warps due to the difference of the thermal expansion coefficients of the silicon substrate and the electrode. The solar cell with the warpage exceeding 2mm is easy to break in the subsequent packaging process, and the production yield is affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a conductive silver paste for a solar cell and a preparation method thereof, wherein the conductive silver paste does not warp in the process of preparing the solar cell and has low sintering temperature, and the specific contents of the conductive silver paste are as follows:
the invention aims to provide a conductive silver paste for a solar cell, which has the technical points that: the conductive silver paste for the solar cell comprises, by weight, 1-10 parts of an organic carrier, 70-90 parts of a conductive metal phase, 2-3 parts of a binder and 0-1 part of an additive;
the conductive metal phase is formed by mixing silver powder A and silver powder B, and the weight ratio of the silver powder A to the silver powder B is (80-90): (10-20);
the silver powder A is spherical silver powder, the median particle diameter of the silver powder A is 1.2-2 mu m, and the specific surface area of the silver powder A is 0.4-0.5 m2The apparent density of the silver powder A is 2.5-3.5 g/cm3The tap density of the silver powder A is 5.5-6.2 g/cm3；
The silver powder B is flake silver powder, the median particle diameter of the silver powder B is 2-2.5 mu m, and the specific surface area of the silver powder B is 0.3-0.5 m2The apparent density of the silver powder B is 2.5-3.5 g/cm3The tap density of the B silver powder is 6.0-6.4 g/cm3；
The binding agent is Bi-B-Si glass powder, and the mass ratio of Bi element to B element to Si element is (75-80): (8-9): 3.
in some embodiments of the invention, the organic vehicle is at least one of terpineol, benzyl alcohol, ethyl cellulose, butyl carbitol, tributyl citrate, and tributyl phthalate.
In some embodiments of the present invention, the ethyl cellulose has an ethoxy content of 49 to 55wt%, and the ethyl cellulose has a viscosity of 1 to 100mPa · s.
In some embodiments of the present invention, the Bi-B-Si based glass powder is formed of BiO3、B2O3、Al2O3、SiO2、ZnO、Na2O and CeO2Mixing, melting and grinding.
In some embodiments of the present invention, the softening temperature of the Bi-B-Si based glass frit is 480 to 510 ℃.
In some embodiments of the present invention, the method for preparing the Bi-B-Si based glass frit comprises:
step 1: weighing the materials required by the Bi-B-Si series glass powder by using an electronic balance, finely grinding the weighed glass materials in an agate grinding bowl and uniformly mixing the glass materials;
step 2: preheating the corundum crucible in a box type resistance furnace, slowly raising the temperature from room temperature to 900-1300 ℃, clamping the corundum crucible by using a crucible clamp, transferring the glass material which is fully mixed in the step 1 into the preheated corundum crucible, then placing the corundum crucible back into the box type resistance furnace, heating the corundum crucible to 900-1300 ℃, and preserving the heat for 30-90 min at the temperature;
and step 3: and (3) rapidly transferring the glass material treated in the step (2) into an annealing furnace at 200-400 ℃, annealing the glass material, then pouring the glass material into deionized water for water quenching, transferring the water quenched glass particles into a drying box for drying, then transferring the completely dried glass material into an air flow mill, and introducing high-pressure gas to crush the glass material into glass powder with the median particle size of 5-6 microns.
In some embodiments of the invention, the additive is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), and fluoroolefin-vinyl ether copolymer (FEVE).
Another object of the present invention is to provide a method for preparing a conductive silver paste for a solar cell, which comprises the following steps: the preparation method of the conductive silver paste for the solar cell comprises the following steps: and dispersing the conductive metal phase, the binder and the additive in an organic carrier, and then grinding for 3-5 times by using a three-roll grinder until the fineness of the slurry is 6-9 microns to obtain the conductive silver paste for the solar cell.
Compared with the prior art, the invention has the beneficial effects that:
1. the conductive silver paste for the solar cell comprises 1-10 parts by weight of an organic carrier, 70-90 parts by weight of a conductive metal phase, 2-3 parts by weight of a binder and 0-1 part by weight of an additive, wherein the binder is Bi-B-Si glass powder, and the softening temperature of the glass powder is low, so that the sintering temperature is lowered, and the influence of high temperature on a solar cell substrate is reduced.
2. According to the conductive silver paste for the solar cell, the thermal expansion coefficient can be effectively reduced due to the adoption of the organic system of at least one of terpineol, benzyl alcohol, ethyl cellulose, butyl carbitol, tributyl citrate and tributyl phthalate, so that the problem of warping of the silicon crystal solar cell after high-temperature sintering is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1
The invention relates to a conductive silver paste for a solar cell, which is prepared from 5 parts by weight of an organic carrier, 80 parts by weight of a conductive metal phase, 2.5 parts by weight of a binder and 0.5 part by weight of an additive;
the conductive metal phase is formed by mixing silver powder A and silver powder B, and the weight ratio of the silver powder A to the silver powder B is 85: 15;
the silver powder A is spherical silver powder, the median particle diameter of the silver powder A is 1.1 mu m, and the specific surface area of the silver powder A is 0.45m2The apparent density of the silver powder A is 3g/cm3The tap density of the silver powder A is 5.85g/cm3；
The silver powder B is flake silver powder, the median particle diameter of the silver powder B is 2.25 mu m, and the specific surface area of the silver powder B is 0.4m2G, said B silverThe bulk density of the powder was 3g/cm3The tap density of the B silver powder is 6.2g/cm3；
The binding agent is Bi-B-Si glass powder, and the mass ratio of Bi element to B element to Si element is 77.5: 8.5: 3.
wherein the organic carrier is a mixture of terpineol, benzyl alcohol and ethyl cellulose.
Wherein the ethoxy content of the ethyl cellulose is 52wt%, and the viscosity of the ethyl cellulose is 50 mPa.
Wherein the Bi-B-Si based glass powder is composed of BiO3、B2O3、Al2O3、SiO2、ZnO、Na2O and CeO2Mixing, melting and grinding.
Wherein the softening temperature of the Bi-B-Si based glass powder is 495 ℃.
Wherein the preparation method of the Bi-B-Si glass powder comprises the following steps:
step 1: weighing the materials required by the Bi-B-Si series glass powder by using an electronic balance, finely grinding the weighed glass materials in an agate grinding bowl and uniformly mixing the glass materials;
step 2: placing the corundum crucible into a box type resistance furnace for preheating, slowly raising the temperature from room temperature to 1100 ℃, clamping the corundum crucible by using a crucible clamp, transferring the glass material which is fully mixed in the step 1 into the preheated corundum crucible, then placing the corundum crucible back into the box type resistance furnace, heating the corundum crucible to 1100 ℃, and preserving the heat for 45min at the temperature;
and step 3: and (3) rapidly moving the glass material treated in the step (2) into an annealing furnace at 300 ℃, annealing the glass material, then pouring the glass material into deionized water for water quenching, moving the water quenched glass particles into a drying box for drying, then moving the completely dried glass material into an air flow mill, and introducing high-pressure gas to crush the glass material into glass powder with the median particle size of 5.5 microns.
Wherein the additive is polychlorotrifluoroethylene PCTFE.
According to the formula, the preparation method of the conductive silver paste for the solar cell comprises the following steps: and dispersing the conductive metal phase, the binder and the additive in an organic carrier, and then grinding for 4 times by using a three-roll grinder until the fineness of the slurry is 7.5 mu m to obtain the conductive silver paste for the solar cell.
The prepared silver paste is printed on a solar cell, a silver electrode is obtained after drying and sintering, and the printed silver electrode is observed by naked eyes, so that the appearance is smooth and flat, and no warping phenomenon occurs. The photoelectric conversion efficiency was tested to be 23.45%.
Example 2
The conductive silver paste for the solar cell comprises, by weight, 1 part of an organic carrier, 90 parts of a conductive metal phase, 2 parts of a binder and 0.1 part of an additive, wherein the organic carrier is in a solid-liquid state;
the conductive metal phase is formed by mixing silver powder A and silver powder B, and the weight ratio of the silver powder A to the silver powder B is 90: 10;
the silver powder A is spherical silver powder, the median particle diameter of the silver powder A is 1.2 mu m, and the specific surface area of the silver powder A is 0.4m2The apparent density of the silver powder A is 2.5g/cm3The tap density of the silver powder A is 5.5g/cm3；
The silver powder B is flake silver powder, the median particle diameter of the silver powder B is 2 mu m, and the specific surface area of the silver powder B is 0.3m2The apparent density of the silver powder B is 2.5g/cm3The tap density of the B silver powder is 6.0g/cm3；
The binding agent is Bi-B-Si glass powder, and the mass ratio of Bi element to B element to Si element is 75: 9: 3.
wherein the organic carrier is a mixture of terpineol, ethyl cellulose and butyl carbitol.
Wherein the ethyl cellulose has an ethoxy content of 49wt% and a viscosity of 100 mPas.
Wherein the Bi-B-Si based glass powder is composed of BiO3、B2O3、Al2O3、SiO2、ZnO、Na2O andCeO2mixing, melting and grinding.
Wherein the softening temperature of the Bi-B-Si based glass powder is 480 ℃.
Wherein the preparation method of the Bi-B-Si glass powder comprises the following steps:
step 1: weighing the materials required by the Bi-B-Si series glass powder by using an electronic balance, finely grinding the weighed glass materials in an agate grinding bowl and uniformly mixing the glass materials;
step 2: putting the corundum crucible into a box-type resistance furnace for preheating, slowly raising the temperature from room temperature to 900 ℃, clamping the corundum crucible by using a crucible clamp, transferring the glass material which is fully mixed in the step 1 into the preheated corundum crucible, putting the corundum crucible back into the box-type resistance furnace, heating the corundum crucible to 900 ℃ all the time, and preserving the heat for 30min at the temperature;
and step 3: and (3) rapidly moving the glass material treated in the step (2) into an annealing furnace at 200 ℃, annealing the glass material, then pouring the glass material into deionized water for water quenching, moving the water quenched glass particles into a drying box for drying, then moving the completely dried glass material into an air flow mill, and introducing high-pressure air to crush the glass material into glass powder with the median particle size of 5 microns.
Wherein the additive is polytetrafluoroethylene PTFE.
According to the formula, the preparation method of the conductive silver paste for the solar cell comprises the following steps: and dispersing the conductive metal phase, the binder and the additive in an organic carrier, and then grinding for 3 times by using a three-roll grinder until the fineness of the slurry is 9 mu m to obtain the conductive silver paste for the solar cell.
The prepared silver paste is printed on a solar cell, a silver electrode is obtained after drying and sintering, and the printed silver electrode is observed by naked eyes, so that the appearance is smooth and flat, and no warping phenomenon occurs. The photoelectric conversion efficiency was tested to be 22.98%.
Example 3
The conductive silver paste for the solar cell comprises, by weight, 10 parts of an organic carrier, 70 parts of a conductive metal phase, 3 parts of a binder and 1 part of an additive, wherein the organic carrier is in an amount of 10 parts;
the conductive metal phase is formed by mixing silver powder A and silver powder B, and the weight ratio of the silver powder A to the silver powder B is 80: 20;
the silver powder A is spherical silver powder, the median particle diameter of the silver powder A is 2 mu m, and the specific surface area of the silver powder A is 0.5m2The apparent density of the silver powder A is 3.5g/cm3The tap density of the silver powder A is 6.2g/cm3；
The silver powder B is flake silver powder, the median particle diameter of the silver powder B is 2.5 mu m, and the specific surface area of the silver powder B is 0.5m2The apparent density of the silver powder B is 3.5g/cm3The tap density of the B silver powder is 6.4g/cm3；
The binding agent is Bi-B-Si glass powder, and the mass ratio of Bi element to B element to Si element is 80: 8: 3.
wherein the organic carrier is a mixture of ethyl cellulose, butyl carbitol and tributyl citrate.
Wherein the ethyl cellulose has an ethoxy content of 55wt% and a viscosity of 80 mPas.
Wherein the Bi-B-Si based glass powder is composed of BiO3、B2O3、Al2O3、SiO2、ZnO、Na2O and CeO2Mixing, melting and grinding.
Wherein the softening temperature of the Bi-B-Si based glass powder is 480 ℃.
Wherein the preparation method of the Bi-B-Si glass powder comprises the following steps:
step 1: weighing the materials required by the Bi-B-Si series glass powder by using an electronic balance, finely grinding the weighed glass materials in an agate grinding bowl and uniformly mixing the glass materials;
step 2: placing the corundum crucible into a box type resistance furnace for preheating, slowly raising the temperature from room temperature to 1300 ℃, clamping the corundum crucible by using a crucible clamp, transferring the glass material which is fully mixed in the step 1 into the preheated corundum crucible, then placing the corundum crucible back into the box type resistance furnace, heating the corundum crucible to 1300 ℃ all the time, and preserving the heat for 90min at the temperature;
and step 3: and (3) rapidly moving the glass material treated in the step (2) into an annealing furnace at 400 ℃, annealing the glass material, then pouring the glass material into deionized water for water quenching, moving the water quenched glass particles into a drying box for drying, then moving the completely dried glass material into an air flow mill, and introducing high-pressure gas to crush the glass material into glass powder with the median particle size of 6 microns.
Wherein the additive is polyvinylidene fluoride (PVDF).
According to the formula, the preparation method of the conductive silver paste for the solar cell comprises the following steps: and dispersing the conductive metal phase, the binder and the additive in an organic carrier, and then grinding for 4 times by using a three-roll grinder until the fineness of the slurry is 7 mu m to obtain the conductive silver paste for the solar cell.
The prepared silver paste is printed on a solar cell, a silver electrode is obtained after drying and sintering, and the printed silver electrode is observed by naked eyes, so that the appearance is smooth and flat, and no warping phenomenon occurs. The photoelectric conversion efficiency was tested to be 23.16%.
Example 4
The conductive silver paste for the solar cell comprises, by weight, 6 parts of an organic carrier, 85 parts of a conductive metal phase, 2.5 parts of a binder and 0.5 part of an additive, wherein the organic carrier is in an organic-inorganic composite structure;
the conductive metal phase is formed by mixing silver powder A and silver powder B, and the weight ratio of the silver powder A to the silver powder B is 82: 18;
the silver powder A is spherical silver powder, the median particle diameter of the silver powder A is 1.2-2 mu m, and the specific surface area of the silver powder A is 0.42m2The apparent density of the silver powder A is 2.8g/cm3The tap density of the silver powder A is 5.6g/cm3；
The silver powder B is flake silver powder, the median particle diameter of the silver powder B is 2.3 mu m, and the specific surface area of the silver powder B is 0.45m2(g) pine of said B silver powderThe packing density is 3.2g/cm3The tap density of the B silver powder is 6.2g/cm3；
The binding agent is Bi-B-Si glass powder, and the mass ratio of Bi element to B element to Si element is 88: 8.5: 3.
wherein the organic carrier is a mixture of ethyl cellulose, butyl carbitol and tributyl phthalate.
Wherein the ethyl cellulose has an ethoxy content of 50wt% and a viscosity of 100 mPas.
Wherein the Bi-B-Si based glass powder is composed of BiO3、B2O3、Al2O3、SiO2、ZnO、Na2O and CeO2Mixing, melting and grinding.
Wherein the softening temperature of the Bi-B-Si based glass powder is 480 ℃.
Wherein the preparation method of the Bi-B-Si glass powder comprises the following steps:
step 1: weighing the materials required by the Bi-B-Si series glass powder by using an electronic balance, finely grinding the weighed glass materials in an agate grinding bowl and uniformly mixing the glass materials;
step 2: placing the corundum crucible into a box-type resistance furnace for preheating, slowly raising the temperature from room temperature to 1100 ℃, clamping the corundum crucible by using a crucible clamp, transferring the glass material which is fully mixed in the step 1 into the preheated corundum crucible, then placing the corundum crucible back into the box-type resistance furnace, heating the corundum crucible to 1100 ℃, and preserving the heat for 40min at the temperature;
and step 3: and (3) rapidly moving the glass material treated in the step (2) into an annealing furnace at 300 ℃, annealing the glass material, then pouring the glass material into deionized water for water quenching, moving the water quenched glass particles into a drying box for drying, then moving the completely dried glass material into an air flow mill, and introducing high-pressure gas to crush the glass material into glass powder with the median particle size of 5.8 microns.
Wherein the additive is a mixture of ethylene-tetrafluoroethylene copolymer ETFE and ethylene-chlorotrifluoroethylene copolymer ECTFE.
According to the formula, the preparation method of the conductive silver paste for the solar cell comprises the following steps: and dispersing the conductive metal phase, the binder and the additive in an organic carrier, and then grinding for 4 times by using a three-roll grinder until the fineness of the slurry is 6 mu m to obtain the conductive silver paste for the solar cell.
The prepared silver paste is printed on a solar cell, a silver electrode is obtained after drying and sintering, and the printed silver electrode is observed by naked eyes, so that the appearance is smooth and flat, and no warping phenomenon occurs. The photoelectric conversion efficiency was tested to be 23.37%.
The present invention provides only one kind of conductive silver paste for solar cells and a method for preparing the same, and there are many methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, it should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention, and each component not specified in the present embodiment can be implemented by using the existing technology.
Claims (8)
1. The utility model provides a solar cell is with electrically conductive silver thick liquid which characterized in that: the conductive silver paste for the solar cell comprises, by weight, 1-10 parts of an organic carrier, 70-90 parts of a conductive metal phase, 2-3 parts of a binder and 0-1 part of an additive;
the conductive metal phase is formed by mixing silver powder A and silver powder B, and the weight ratio of the silver powder A to the silver powder B is (80-90): (10-20);
the silver powder A is spherical silver powder, the median particle diameter of the silver powder A is 1.2-2 mu m, and the specific surface area of the silver powder A is 0.4-0.5 m2The apparent density of the silver powder A is 2.5-3.5 g/cm3The tap density of the silver powder A is 5.5-6.2 g/cm3；
The silver powder B is flake silver powder, the median particle diameter of the silver powder B is 2-2.5 mu m, and the specific surface area of the silver powder B is 0.3-0.5 m2The apparent density of the silver powder B is 2.5-3.5 g/cm3The tap density of the B silver powder is 6.0-6.4 g/cm3；
The binding agent is Bi-B-Si glass powder, and the mass ratio of Bi element to B element to Si element is (75-80): (8-9): 3.
2. the conductive silver paste for a solar cell according to claim 1, wherein: the organic carrier is at least one of terpineol, benzyl alcohol, ethyl cellulose, butyl carbitol, tributyl citrate and tributyl phthalate.
3. The conductive silver paste for a solar cell according to claim 2, wherein: the ethyl cellulose has an ethoxy content of 49-55 wt%, and the viscosity of the ethyl cellulose is 1-100 mPa & s.
4. The conductive silver paste for a solar cell according to claim 1, wherein: the Bi-B-Si based glass powder is composed of BiO3、B2O3、Al2O3、SiO2、ZnO、Na2O and CeO2Mixing, melting and grinding.
5. The conductive silver paste for a solar cell according to claim 4, wherein: the softening temperature of the Bi-B-Si glass powder is 480-510 ℃.
6. The conductive silver paste for a solar cell according to claim 4, wherein: the preparation method of the Bi-B-Si glass powder comprises the following steps:
step 1: weighing the materials required by the Bi-B-Si series glass powder by using an electronic balance, finely grinding the weighed glass materials in an agate grinding bowl and uniformly mixing the glass materials;
step 2: preheating the corundum crucible in a box type resistance furnace, slowly raising the temperature from room temperature to 900-1300 ℃, clamping the corundum crucible by using a crucible clamp, transferring the glass material which is fully mixed in the step 1 into the preheated corundum crucible, then placing the corundum crucible back into the box type resistance furnace, heating the corundum crucible to 900-1300 ℃, and preserving the heat for 30-90 min at the temperature;
and step 3: and (3) rapidly transferring the glass material treated in the step (2) into an annealing furnace at 200-400 ℃, annealing the glass material, then pouring the glass material into deionized water for water quenching, transferring the water quenched glass particles into a drying box for drying, then transferring the completely dried glass material into an air flow mill, and introducing high-pressure gas to crush the glass material into glass powder with the median particle size of 5-6 microns.
7. The conductive silver paste for a solar cell according to claim 1, wherein: the additive is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF) and fluoroolefin-vinyl ether copolymer (FEVE).
8. A preparation method of conductive silver paste for a solar cell is characterized by comprising the following steps: the preparation method of the conductive silver paste for the solar cell comprises the following steps: and dispersing the conductive metal phase, the binder and the additive in an organic carrier, and then grinding for 3-5 times by using a three-roll grinder until the fineness of the slurry is 6-9 microns to obtain the conductive silver paste for the solar cell.
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| US20120240994A1 (en) * | 2011-03-25 | 2012-09-27 | Samsung Electronics Co., Ltd. | Conductive paste and electronic device, and solar cell including an electrode formed using the conductive paste |
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