CN112786232A - N-type solar cell silver paste doped with organic gallium and preparation method thereof - Google Patents
N-type solar cell silver paste doped with organic gallium and preparation method thereof Download PDFInfo
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- CN112786232A CN112786232A CN201911099042.4A CN201911099042A CN112786232A CN 112786232 A CN112786232 A CN 112786232A CN 201911099042 A CN201911099042 A CN 201911099042A CN 112786232 A CN112786232 A CN 112786232A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 104
- 239000004332 silver Substances 0.000 title claims abstract description 104
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims description 56
- 229910052733 gallium Inorganic materials 0.000 title claims description 56
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000000843 powder Substances 0.000 claims description 95
- 239000011521 glass Substances 0.000 claims description 73
- 238000002156 mixing Methods 0.000 claims description 59
- 239000011230 binding agent Substances 0.000 claims description 53
- 239000006185 dispersion Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 42
- 238000005303 weighing Methods 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 22
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 21
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 14
- 229920000193 polymethacrylate Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000000787 lecithin Substances 0.000 claims description 6
- 235000010445 lecithin Nutrition 0.000 claims description 6
- 229940067606 lecithin Drugs 0.000 claims description 6
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000896 Ethulose Polymers 0.000 claims description 5
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 5
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 5
- JHUXFIPODALNAN-UHFFFAOYSA-N tris(2-methylpropyl)gallane Chemical compound CC(C)C[Ga](CC(C)C)CC(C)C JHUXFIPODALNAN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 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 description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 3
- -1 alcohol ester Chemical class 0.000 claims description 3
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 52
- 229910052710 silicon Inorganic materials 0.000 description 52
- 239000010703 silicon Substances 0.000 description 52
- 238000005245 sintering Methods 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 13
- 238000011068 loading method Methods 0.000 description 13
- 238000007650 screen-printing Methods 0.000 description 13
- 238000007873 sieving Methods 0.000 description 13
- 238000003466 welding Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 150000002259 gallium compounds Chemical class 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VTGARNNDLOTBET-UHFFFAOYSA-N gallium antimonide Chemical compound [Sb]#[Ga] VTGARNNDLOTBET-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001052 transient effect Effects 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
- H01B1/14—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
- 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
- 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
- H01L31/022408—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
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides an organic gallium-doped N-type solar cell silver paste and a preparation method thereof.
Description
Technical Field
The invention relates to solar cell silver paste and a preparation method thereof, in particular to N-type solar cell silver paste doped with organic gallium and a preparation method thereof, and belongs to the technical field of solar cell silver paste.
Background
Solar energy is a renewable clean energy source and is increasingly favored by people. Silicon-based solar cells have always taken on the predominance of the photovoltaic market. Most silicon-based solar cells in the market are still p-type cells at present, but the space for improving the efficiency of the existing p-type cells to date is very limited; the N-type silicon has higher minority carrier lifetime (generally 1-2 orders of magnitude higher than that of p-type silicon), excellent weak illumination response and stronger tolerance to metal impurities, so that the N-type cell can obtain higher efficiency, the power attenuation of the N-type cell is far lower than that of a conventional p-type cell, the market is gradually expanded, and the N-type cell is likely to gradually replace a p-type solar cell to occupy the leading position of a photovoltaic market in the future.
And n+Emitter comparison, p+The emitter and metallic silver interface potential field (barrier) is larger. This makes the metallization of the P-emitter electrode face a serious challenge, i.e. the existing P-type silver paste is difficult to satisfy the contact problem of N-type silicon, and how to prepare a silver paste matching N-type silicon to maximally guide its energy out is urgent.
The research reports of domestic and foreign patents and literature on the silver paste of the N-type solar cell mainly lie in the improvement of reducing ohmic contact by introducing aluminum powder, aluminum-silicon alloy and other aluminum alloy substances, but the research reports and the existing product test use conditions show that: the content and the grain diameter of the aluminum powder have great influence on the compounding of the silicon wafer surface. If the content of aluminum powder is increased by some means, the VOC is correspondingly reduced under the condition of reducing Rs, which is mainly caused by the condition that Al reacts with silicon on the surface of a battery in the reaction process to form Al nails, the integrity of PN-junctions is damaged, even the PN-junctions are burnt through, the surface recombination is increased, and the VOC is reduced; and aluminum powder is inferior to silver powder in conductivity, so that the line resistance of the grid line is increased, and the like, wherein the main problem is the contradiction between ohmic contact and open voltage.
Disclosure of Invention
The invention provides an organic gallium-doped N-type solar cell silver paste and a preparation method thereof, aiming at the problems in the prior art, the N-type solar cell silver paste is prepared by doping organic gallium, combining glass powder component design and nano silver powder addition, optimizing a paste formula and the like, the damage of aluminum powder to PN junctions is reduced, and simultaneously, the introduction of organic gallium improves the doping concentration, reduces contact and keeps higher open voltage, so that a high-efficiency solar cell silver paste raw material is obtained, and the purpose of improving the conversion efficiency of a solar cell is achieved.
According to the first embodiment provided by the invention, an N-type solar cell silver paste doped with organic gallium is provided.
An N-type solar cell silver paste doped with organic gallium comprises the following components or consists of the following components:
0.1 to 10 parts by weight of organic gallium, preferably 0.2 to 8 parts by weight, more preferably 0.3 to 5 parts by weight;
55 to 150 parts by weight of silver powder, preferably 65 to 120 parts by weight, more preferably 75 to 100 parts by weight;
1-25 parts by weight of binder, preferably 3-20 parts by weight, more preferably 5-15 parts by weight;
the glass frit is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.
Preferably, the silver paste further comprises:
0.1 to 10 parts by weight of an auxiliary, preferably 0.2 to 8 parts by weight, and more preferably 0.3 to 5 parts by weight.
In the invention, the organic gallium is one or more of tricyclopentyl gallium, trimethyl gallium, triethyl gallium and triisobutyl gallium
In the invention, the silver powder is micron-spherical silver powder and/or nano silver powder.
Preferably, the silver powder is a mixture of micro-sphere type silver powder and nano silver powder.
More preferably, the silver powder is a mixture of 70-99% by weight of micrometer spherical silver powder and 1-30% by weight of nanometer silver powder.
In the present invention, the binder is an organic binder.
Preferably, the binder is composed of 0.1-30% by weight of high molecular polymer and 70-99% by weight of organic solvent.
In the invention, the high molecular polymer is selected from one or more of polymethacrylate, ethyl cellulose and ethyl hydroxyethyl cellulose.
In the present invention, the organic solvent is selected from one or more of butyl carbitol, terpineol, tributyl citrate, propylene glycol butyl ether, diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, butyl carbitol acetate, dibasic ester, and alcohol ester.
In the invention, the glass powder consists of the following raw materials: 5-40% of B2O30-5% of Al2O30-60% of PbO, 2-20% of ZnO, 5-50% of BaO, 0-30% of V2O5 and 0-25% of Sb2O3、0-20％SiO2And 0 to 40% of Bi2O3。
Preferably, the particle size of the glass frit is 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.3 to 3 μm.
In the invention, the auxiliary agent is methyl silicone oil and/or lecithin.
In the invention, the particle diameter of the micrometer spherical silver powder is D50-1-2 μm.
In the invention, the particle size of the nano silver powder is D50-100-800 nm.
According to a second embodiment provided by the invention, a method for preparing an organic gallium-doped N-type solar cell silver paste is provided.
A method of making an organogallium doped N-type solar cell silver paste or a method of making the organogallium doped N-type solar cell silver paste of the first embodiment, comprising the steps of:
(1) mixing and dispersing organic gallium, a binder, glass powder and an auxiliary agent to obtain a dispersed mixed solution;
(2) adding silver powder into the dispersion mixed solution, dispersing and grinding;
(3) and after grinding, adding an organic solvent, and uniformly dispersing to obtain the N-type solar cell silver paste doped with the organic gallium.
In the present invention, a disperser, preferably a high-speed disperser, is used for the dispersion.
Preferably, the rotation speed of the dispersion machine in the step (1) is 200-600rpm, and the dispersion time is 0.5-30 min.
Preferably, the rotation speed of the dispersion machine in the step (2) is 600-2000rpm, and the dispersion time is 0.5-30 min.
Preferably, the rotation speed of the dispersion machine in the step (3) is 600-1000rpm, and the dispersion time is 0.1-20 min.
Preferably, the weight of the organic solvent added in the step (3) is 0.1-10% of the total weight of the raw materials.
In the invention, the binder is prepared by adopting the following method: mixing the high molecular polymer and the organic solvent, dispersing and dissolving to obtain the binder.
Preferably, the weight ratio of the high molecular polymer to the organic solvent is 1:3 to 20, preferably 1:5 to 15.
In the invention, the glass powder is prepared by the following method: weighing 5-40% of B2O30-5% of Al2O30-60% of PbO, 2-20% of ZnO, 5-50% of BaO and 0-30% of V2O50-25% of Sb2O3、0-20％SiO2And 0 to 40% of Bi2O3Mixing evenly, heating and preserving heat, quenching, ball milling and screening to obtain the glass powder with the grain diameter of 0.1-10 mu m.
Preferably, the temperature of the heating and heat preservation is 800-1500 ℃, and the time of the heating and heat preservation is 30-120 min; deionized water is adopted for quenching; the ball milling time is 1-12 h.
In the invention, the heating and heat preservation adopt a high-temperature muffle furnace.
The invention provides a method for preparing organic gallium-doped N-type solar cell silver paste, which specifically comprises the following steps:
(1) mixing the batch materials according to 0.1-5% of organic gallium, 5-15% of organic binder, 0.5-5% of glass powder and 0.1-5% of auxiliary agent by mass of the prepared slurry, and dispersing for 1-10 min at the rotating speed of 500rpm of 300-;
(2) then adding 75-90% of silver powder into the mixture obtained in the step (1), dispersing for 1-10 min by adopting a dispersion machine at the rotating speed of 800-;
(3) after grinding, adding an organic solvent accounting for 1-3% of the total amount of the raw materials, and dispersing for 1-5min by adopting a high-speed dispersion machine to obtain the N-type solar cell silver paste doped with the organic gallium.
According to the invention, the gallium compound is added into the N-type solar cell silver paste, so that the influence on VOC caused by introducing aluminum powder, aluminum-silicon alloy and other aluminum alloy substances into the N-type solar cell silver paste in the prior art is avoided. The integrity of PN-junction can not be damaged by adding gallium compound, and the structure of silicon on the surface of the battery can not be influenced; meanwhile, the gallium has better conductivity, the line resistance of the grid line on the solar cell is weakened, and the contradiction between ohmic contact and open voltage is perfectly solved.
Experimental research shows that the organic gallium is added into the silver paste of the solar cell, and compared with an inorganic compound added with gallium, the organic gallium-containing silver paste has the following effects and effects:
1. gallium is used as a trivalent dopant, has a doping effect on P-type materials, reduces contact potential energy, and is beneficial to contact of silver paste and silicon; 2. the organic gallium is an organic matter, and compared with an inorganic compound of gallium, the organic gallium can be well dispersed into an organic solvent or an organic carrier due to the principle of similar compatibility, so that the organic gallium is more uniformly contacted with the surface of a silicon wafer printed with the organic gallium; meanwhile, gallium or gallium compounds with high surface activity are generated in the sintering process, and can be diffused to the silicon surface more quickly in the short sintering process, so that the doping solubility of the silicon surface is improved.
Experiments prove that the problem of contradiction between ohmic contact and open voltage can be well solved by adding the tricyclopentyl gallium, the trimethyl gallium, the triethyl gallium or the triisobutyl gallium into the silver paste of the N-type solar cell doped with the organic gallium, the contact and compounding problem between slurry and a silicon wafer in the process of preparing the solar cell is improved, the contact resistance between silver and silicon is reduced, the open voltage of the solar cell is improved, and the photoelectric conversion efficiency is improved.
In the invention, the silver powder is a mixture of micron-spherical silver powder and nano silver powder. By adopting the mixture of silver powders with different particle sizes, the following effects and effects are achieved:
1. the nano silver powder has high surface activation energy and a lower melting point, and can be compacted and dissolved in glass at a lower temperature, so that the conductivity of the micron spherical silver powder can be reached at a lower sintering temperature; 2. meanwhile, as the nano silver powder particles are smaller, the nano silver powder particles can be well filled into gaps of the micron spherical silver powder, so that the compactness of the grid line is improved, and the resistance of the grid line is reduced.
In the present invention, the glass frit is prepared from glass frit having a particle size of 0.1 to 10 μm (preferably 0.2 to 5 μm, and more preferably 0.3 to 3 μm) using a specific raw material, and has the following actions and effects:
the softening temperature of the glass is reduced by controlling the components and the particle size of the glass, and the silver is fully dissolved and the passivation layer is corroded; the proportion of components with strong corrosivity, such as lead or bismuth, is optimized, and passivation layers, such as silicon nitride, silicon oxide or aluminum oxide, on the surface of the silicon battery are well corroded, so that the silver and the silicon are in good ohmic contact, an electron transfer channel is formed, and the conductive effect is achieved; meanwhile, other oxides (such as ZnO/V2O5/SiO2) are introduced to control the structure and the expansion coefficient of the glass, so that the adhesive force between the slurry and silicon is improved, and the reliability of the battery is improved.
In the preparation of the glass powder, the softening temperature Tg of the glass powder is controlled to be 200-480 ℃.
The method mainly aims at the contradiction between ohmic contact and open voltage of the current N-type solar cell silicon wafer, well solves the contact and compounding problem between the slurry and the silicon wafer by doping organic gallium, combining glass component adjustment, nano silver powder and the like, reduces the contact resistance between silver and silicon, improves the open voltage of the solar cell, and achieves the aim of improving the photoelectric conversion efficiency.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. according to the invention, the organic gallium compound is added into the silver paste of the N-type solar cell doped with the organic gallium, so that the P-type material is doped, the contact potential energy is reduced, the silver paste is favorably contacted with silicon to generate gallium or gallium compound with high surface activity in the sintering process, the gallium or gallium compound can be more quickly diffused to the silicon surface in the transient sintering process, and the doping solubility of the silicon surface is improved.
2. The silver powder adopted in the silver paste of the N-type solar cell doped with the organic gallium is a mixture of the micron spherical silver powder and the nanometer silver powder, and can be compacted and dissolved in glass at a lower temperature, so that the micron spherical silver powder can be well filled in gaps of the micron spherical silver powder at a lower sintering temperature, the compactness of grid lines is improved, and the resistance of the grid lines is reduced.
3. According to the N-type solar cell silver paste doped with the organic gallium, the glass powder with a specific particle size is prepared from specific raw materials, the softening temperature of glass is reduced, silver is fully dissolved, and a passivation layer is corroded; the proportion of the components with high corrosivity, such as lead or bismuth, is optimized, and the passivation layers, such as silicon nitride, silicon oxide or aluminum oxide, on the surface of the silicon battery are well corroded, so that the silver and the silicon are in good ohmic contact, an electron transfer channel is formed, and the conductive effect is achieved.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
An N-type solar cell silver paste doped with organic gallium comprises the following components or consists of the following components:
0.1 to 10 parts by weight of organic gallium, preferably 0.2 to 8 parts by weight, more preferably 0.3 to 5 parts by weight;
55 to 150 parts by weight of silver powder, preferably 65 to 120 parts by weight, more preferably 75 to 100 parts by weight;
1-25 parts by weight of binder, preferably 3-20 parts by weight, more preferably 5-15 parts by weight;
the glass frit is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.
Preferably, the silver paste further comprises:
0.1 to 10 parts by weight of an auxiliary, preferably 0.2 to 8 parts by weight, and more preferably 0.3 to 5 parts by weight.
In the invention, the organic gallium is one or more of tricyclopentyl gallium, trimethyl gallium, triethyl gallium and triisobutyl gallium
In the invention, the silver powder is micron-spherical silver powder and/or nano silver powder.
Preferably, the silver powder is a mixture of micro-sphere type silver powder and nano silver powder.
More preferably, the silver powder is a mixture of 70-99% by weight of micrometer spherical silver powder and 1-30% by weight of nanometer silver powder.
In the present invention, the binder is an organic binder.
Preferably, the binder is composed of 0.1-30% by weight of high molecular polymer and 70-99% by weight of organic solvent.
In the invention, the high molecular polymer is selected from one or more of polymethacrylate, ethyl cellulose and ethyl hydroxyethyl cellulose.
In the present invention, the organic solvent is selected from one or more of butyl carbitol, terpineol, tributyl citrate, propylene glycol butyl ether, diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, butyl carbitol acetate, dibasic ester, and alcohol ester.
In the invention, the glass powder consists of the following raw materials: 5-40% of B2O30-5% of Al2O30-60% of PbO, 2-20% of ZnO, 5-50% of BaO, 0-30% of V2O5 and 0-25% of Sb2O3、0-20％SiO2And 0 to 40% of Bi2O3。
Preferably, the particle size of the glass frit is 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.3 to 3 μm.
In the present invention, in the case of the present invention,
the auxiliary agent is methyl silicone oil and/or lecithin.
In the invention, the particle diameter of the micrometer spherical silver powder is D50-1-2 μm.
In the invention, the particle size of the nano silver powder is D50-100-800 nm.
Example 1
A preparation method of an N-type solar cell silver paste doped with organic gallium comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of tricyclopentyl gallium and 0.5 part of methyl silicone oil according to the mass parts, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short-circuit current is 9.9A, open-circuit voltage is 686.4mv, and series resistance (silver and silicon contact resistance) is 3.01 milliohm m omega; the photoelectric conversion efficiency is 22.41%, and the welding tension is 2.5N.
Example 2
A preparation method of an N-type solar cell silver paste doped with organic gallium comprises the following steps:
(1) preparing glass powder: weighing 15 parts of B by mass2O32 parts of Al2O310 parts of Sb2O313 parts of Bi2O320 parts of V2O5And 40 parts of BaO; uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 900 ℃ for a period of time: quenching the melted glass powder particles by using ionized water for 90 minutes, ball-milling for 5 hours, and sieving by a 400-mesh sieve to obtain the glass powder particlesGlass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 11 parts of ethyl cellulose and 89 parts of terpineol according to the mass parts, mixing, and dispersing for 60min on a dispersion machine to obtain a transparent and uniform organic adhesive;
(3) preparing the battery front silver paste: the mixed silver powder is 90 percent of micron silver powder and 10 percent of nano silver powder in percentage by weight; weighing 1 part of the glass powder prepared in the step (1), 8.5 parts of the organic binder prepared in the step (2), 4.5 parts of trimethyl gallium and 1 part of methyl silicone oil according to parts by mass; and (3) uniformly mixing by using a dispersion machine, adding 85 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding terpineol accounting for 3% of the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.882A, open circuit voltage 687.4mv, series resistance (silver to silicon contact resistance) 3.05 milliohm m omega; the photoelectric conversion efficiency is 22.45%, and the welding tension is 2.37N.
Example 3
A preparation method of an N-type solar cell silver paste doped with organic gallium comprises the following steps:
(1) preparing glass powder: weighing 15 parts of B by mass2O32 parts of Al2O310 parts of Sb2O310 parts of ZnO, 13 parts of Bi2O320 parts of V2O5And 30 parts of BaO; uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1200 ℃ for a period of time: quenching the melted glass powder particles by using ionized water for 45 minutes, ball-milling for 6 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 13 parts of ethyl hydroxyethyl cellulose and 87 parts of tributyl citrate according to the mass parts, mixing, and dispersing for 60min on a dispersion machine to obtain a transparent and uniform organic adhesive;
(3) preparing the battery front silver paste: the mixed silver powder is 90 percent of micron silver powder and 10 percent of nano silver powder in percentage by weight; weighing 1.5 parts of the glass powder prepared in the step (1), 10.5 parts of the organic binder prepared in the step (2), 0.5 part of triethyl gallium and 2 parts of lecithin according to parts by mass; and (3) uniformly mixing by using a dispersion machine, adding 85 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding tributyl citrate accounting for 5% of the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.894A, open circuit voltage 683.2mv, series resistance (silver and silicon contact resistance) 3.53 milliohm m omega; the photoelectric conversion efficiency is 22.23%, and the welding tension is 2.42N.
Example 4
A preparation method of an N-type solar cell silver paste doped with organic gallium comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O31 part of Al2O315 parts of Sb2O310 parts of ZnO, 13 parts of PbO and 15 parts of V2O5And 36 parts of BaO; uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 850 ℃ for a period of time: quenching the melted glass powder particles by using ionized water for 120 minutes, ball-milling for 4 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 20 parts of polymethacrylate and 80 parts of propylene glycol butyl ether according to the mass parts, mixing, and dispersing for 60min on a dispersion machine to obtain a transparent and uniform organic adhesive;
(3) preparing the battery front silver paste: the mixed silver powder is 98 percent of micron silver powder and 2 percent of nano silver powder in percentage by weight; weighing 1 part of glass powder prepared in the step (1), 9.7 parts of organic binder prepared in the step (2), 2 parts of triisobutyl gallium and 0.3 part of lecithin in parts by mass; and (3) uniformly mixing by using a dispersion machine, adding 86 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding propylene glycol butyl ether accounting for 5% of the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.890A, open circuit voltage 685.3mv, series resistance (silver and silicon contact resistance) 3.12 milliohm m omega; the photoelectric conversion efficiency is 22.41%, and the welding tension is 2.53N.
Example 5
A preparation method of an N-type solar cell silver paste doped with organic gallium comprises the following steps:
(1) preparing glass powder: 25 parts of B2O31 part of Al2O315 parts of Sb2O310 parts of ZnO, 23 parts of PbO and 10 parts of V2O5And 16 parts of BaO; uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 850 ℃ for a period of time: quenching the melted glass powder particles by using ionized water for 120 minutes, ball-milling for 4 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 16 parts of ethyl hydroxyethyl cellulose and 84 parts of butyl carbitol acetate according to the mass parts, mixing, and dispersing for 60min on a dispersion machine to obtain a transparent and uniform organic adhesive;
(3) preparing the battery front silver paste: the mixed silver powder is 95 percent of micron silver powder and 5 percent of nano silver powder in percentage by weight; weighing 1 part of glass powder prepared in the step (1), 7.5 parts of organic binder prepared in the step (2), 2.5 parts of tricyclopentyl gallium, 2 parts of methyl silicone oil and 2 parts of lecithin in parts by mass; and (3) uniformly mixing by using a dispersion machine, adding 86 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding butyl carbitol acetate accounting for 2% of the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.895A, open circuit voltage 685.8mv, series resistance (silver to silicon contact resistance) 3.08 milliohm m omega; the photoelectric conversion efficiency is 22.48%, and the welding tension is 2.19N.
Comparative example 1
A preparation method of an aluminum oxide doped N-type solar cell silver paste comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of aluminum oxide and 0.5 part of methyl silicone oil according to the mass parts, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.865A, open circuit voltage 679.7mv, series resistance (silver to silicon contact resistance) 5.24 milliohm m omega; the photoelectric conversion efficiency is 22.08%, and the welding tension is 1.9N.
Comparative example 2
A preparation method of aluminum powder doped N-type solar cell silver paste comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of aluminum powder and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.784A, open circuit voltage 672.6mv, series resistance (silver and silicon contact resistance) 3.98 milliohm m omega; the photoelectric conversion efficiency is 22.23%, and the welding tension is 1.93N.
Comparative example 3
The method for preparing the organic gallium-doped N-type solar cell silver paste comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of tricyclopentyl gallium and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of micron silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 microns, and adding 3% of butyl carbitol based on the total weight of raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.692A, open circuit voltage 675.7mv, series resistance (silver to silicon contact resistance) 3.77 milliohm m omega; the photoelectric conversion efficiency is 22.31%, and the welding tension is 2.03N.
Comparative example 4
A preparation method of an N-type solar cell silver paste doped with a gallium compound comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of gallium nitride and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.829A, open circuit voltage 681.3mv, series resistance (silver to silicon contact resistance) 5.17 milliohm m omega; the photoelectric conversion efficiency is 22.09%, and the welding tension is 1.5N.
Comparative example 5
A preparation method of an N-type solar cell silver paste doped with a gallium compound comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of gallium-lead alloy and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.814A, open circuit voltage 682.0mv, series resistance (silver to silicon contact resistance) 5.21 milliohm m omega; the photoelectric conversion efficiency is 22.18%, and the welding tension is 2.71N.
Comparative example 6
A preparation method of an N-type solar cell silver paste doped with a gallium compound comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the melted glass powder particles by using deionized water for 60 minutes, ball-milling for 2.5 hours, and sieving by using a 400-mesh sieveTaking glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of gallium selenide and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.783A, open circuit voltage 678.9mv, series resistance (silver to silicon contact resistance) 5.33 milliohm m omega; the photoelectric conversion efficiency is 21.98%, and the welding tension is 2.48N.
Comparative example 7
A preparation method of an N-type solar cell silver paste doped with a gallium compound comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of gallium antimonide and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of the raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.803A, open circuit voltage 684.2mv, series resistance (silver to silicon contact resistance) 5.56 milliohm m omega; the photoelectric conversion efficiency is 22.08%, and the welding tension is 1.8N.
Comparative example 8
A preparation method of an N-type solar cell silver paste doped with a gallium compound comprises the following steps:
(1) preparing glass powder: weighing 10 parts of B by mass2O35 parts of SiO220 parts of Bi2O35 parts of ZnO257 parts of PbO and 3 parts of Sb2O3Uniformly mixing by using a mixer, loading into a crucible, putting into a muffle furnace, and keeping the temperature at 1000 ℃ for a period of time: quenching the molten glass powder particles by using deionized water for 60 minutes, carrying out ball milling for 2.5 hours, and sieving by using a 400-mesh sieve to obtain glass sticky powder with the particle size D50 being 0.3-3 microns;
(2) preparation of organic binder: weighing 8 parts of polymethacrylate and 92 parts of butyl carbitol according to the mass parts, mixing, dispersing for 60min on a dispersion machine, and dispersing and dissolving to obtain a transparent and uniform organic binder;
(3) preparing battery silver paste: the weight percentage of the mixed silver powder is 85 percent of micron silver powder and 15 percent of nano silver powder; weighing 2 parts of glass powder prepared in the step (1), 11 parts of organic binder prepared in the step (2), 3 parts of gallium-bismuth alloy and 0.5 part of methyl silicone oil according to parts by mass, uniformly mixing by using a dispersion machine, adding 83.5 parts of the mixed silver powder, mixing, grinding by using a three-roll grinder until the fineness is below 8 micrometers, and adding 3% of butyl carbitol based on the total weight of raw materials to obtain the N-type solar cell silver paste.
By using the prepared sample, electrode films are formed on an N-type silicon wafer with the specification of 156mm multiplied by 156mm by 430-mesh screen printing, the width of a main gate is 0.7 micron, and the electrode films are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 700-.
The electrical data after sintering are tested as follows: short circuit current 9.794A, open circuit voltage 680.1mv, series resistance (silver to silicon contact resistance) 5.45 milliohm m omega; the photoelectric conversion efficiency is 22.28%, and the welding tension is 2.98N.
Claims (10)
1. An N-type solar cell silver paste doped with organic gallium is characterized in that: the silver paste comprises the following components or consists of the following components:
0.1 to 10 parts by weight of organic gallium, preferably 0.2 to 8 parts by weight, more preferably 0.3 to 5 parts by weight;
55 to 150 parts by weight of silver powder, preferably 65 to 120 parts by weight, more preferably 75 to 100 parts by weight;
1-25 parts by weight of binder, preferably 3-20 parts by weight, more preferably 5-15 parts by weight;
the glass frit is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.
2. The organic gallium doped N-type solar cell silver paste of claim 1, wherein: the silver paste also comprises:
0.1 to 10 parts by weight of an auxiliary, preferably 0.2 to 8 parts by weight, and more preferably 0.3 to 5 parts by weight.
3. The organic gallium doped N-type solar cell silver paste of claim 1 or 2, wherein: the organic gallium is one or more of tricyclopentyl gallium, trimethyl gallium, triethyl gallium and triisobutyl gallium.
4. The organic gallium doped N-type solar cell silver paste of any one of claims 1-3, wherein: the silver powder is micron spherical silver powder and/or nano silver powder; preferably, the silver powder is a mixture of micron-spherical silver powder and nano-silver powder; more preferably, the silver powder is a mixture of 70-99% by weight of micrometer spherical silver powder and 1-30% by weight of nanometer silver powder.
5. The organic gallium doped N-type solar cell silver paste of any one of claims 1-4, wherein: the binder is an organic binder; preferably, the binder consists of 0.1 to 30 weight percent of high molecular polymer and 70 to 99 weight percent of organic solvent;
wherein: the high molecular polymer is selected from one or more of polymethacrylate, ethyl cellulose and ethyl hydroxyethyl cellulose; the organic solvent is selected from one or more of butyl carbitol, terpineol, tributyl citrate, propylene glycol butyl ether, diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, butyl carbitol acetate, dibasic ester and alcohol ester.
6. The organogallium doped N-type solar cell silver paste of any one of claims 1-5, wherein: the glass powder is prepared from the following raw materials: 5-40% of B2O30-5% of Al2O30-60% of PbO, 2-20% of ZnO, 5-50% of BaO, 0-30% of V2O5 and 0-25% of Sb2O3、0-20％SiO2And 0 to 40% of Bi2O3；
Preferably, the particle size of the glass frit is 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.3 to 3 μm.
7. The organic gallium doped N-type solar cell silver paste of any one of claims 2-6, wherein: the auxiliary agent is methyl silicone oil and/or lecithin;
the particle size of the micrometer spherical silver powder is D50-1-2 μm; the particle size of the nano silver powder is D50-100-800 nm.
8. A method of making an organogallium doped N-type solar cell silver paste according to any one of claims 1 to 7, comprising the steps of:
(1) mixing and dispersing organic gallium, a binder, glass powder and an auxiliary agent to obtain a dispersed mixed solution;
(2) adding silver powder into the dispersion mixed solution, dispersing and grinding;
(3) and after grinding, adding an organic solvent, and uniformly dispersing to obtain the N-type solar cell silver paste doped with the organic gallium.
9. The method of claim 8, wherein: the dispersion adopts a dispersion machine, preferably a high-speed dispersion machine;
preferably, the rotation speed of a dispersion machine in the step (1) is 200-600rpm, and the dispersion time is 0.5-30 min; in the step (2), the rotating speed of a dispersion machine is 600-2000rpm, and the dispersion time is 0.5-30 min; in the step (3), the rotating speed of a dispersion machine is 600-1000rpm, and the dispersion time is 0.1-20 min; the weight of the organic solvent added in the step (3) is 0.1-10% of the total weight of the raw materials.
10. The method according to claim 8 or 9, characterized in that: the adhesive is prepared by adopting the following method: mixing a high molecular polymer and an organic solvent, and dispersing and dissolving to obtain a binder; preferably, the weight ratio of the high molecular polymer to the organic solvent is 1:3-20, preferably 1: 5-15; and/or
The glass powder is prepared by the following method: weighing 5-40% of B2O30-5% of Al2O30-60% of PbO, 2-20% of ZnO, 5-50% of BaO and 0-30% of V2O50-25% of Sb2O3、0-20％SiO2And 0 to 40% of Bi2O3Uniformly mixing, heating and preserving heat, quenching, ball-milling and screening to obtain the particle size of 0.1-10 μm glass powder; preferably, the temperature of the heating and heat preservation is 800-1500 ℃, and the time of the heating and heat preservation is 30-120 min; deionized water is adopted for quenching; the ball milling time is 1-12 h.
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