CN111540502A - Graphene-doped front silver paste and preparation method and application thereof - Google Patents
Graphene-doped front silver paste and preparation method and application thereof Download PDFInfo
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- CN111540502A CN111540502A CN202010374041.2A CN202010374041A CN111540502A CN 111540502 A CN111540502 A CN 111540502A CN 202010374041 A CN202010374041 A CN 202010374041A CN 111540502 A CN111540502 A CN 111540502A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000004332 silver Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 42
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- 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 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000013008 thixotropic agent Substances 0.000 claims description 6
- 239000003981 vehicle Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- -1 fatty acid ester Chemical class 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229950011392 sorbitan stearate Drugs 0.000 claims description 3
- IVGZFMVIHQRCHJ-UHFFFAOYSA-N [Zn].[Bi].[B] Chemical compound [Zn].[Bi].[B] IVGZFMVIHQRCHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000007639 printing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 10
- 238000005245 sintering Methods 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007650 screen-printing Methods 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
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a graphene-doped front silver paste and a preparation method and application thereof, wherein the front silver paste comprises 90-98% of silver powder, 1-8% of glass powder, 0.5-1% of graphene, 1-10% of organic carrier, 0.1-5% of auxiliary agent and 0.1-1% of solvent by taking the total mass of the front silver paste as a reference; wherein the sheet diameter of the graphene is 50 nm-300 nm. According to the invention, by utilizing the sheet structure and the ultrahigh conductivity of the nano-scale small-size graphene, the gaps among the silver powder can be communicated when the front silver paste is printed and sintered, so that a complete conductive path is constructed, the photoelectric conversion efficiency of the solar cell is improved, and the solar cell has a good application prospect.
Description
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to a graphene-doped front silver paste and a preparation method and application thereof.
Background
A solar cell, also called a "solar chip" or a "photovoltaic cell", is a photoelectric semiconductor sheet that directly generates electricity from sunlight, and is a device that can output voltage instantaneously and generate current in the presence of a circuit as long as it is illuminated by light satisfying a certain illumination condition, and directly converts light energy into electrical energy through a photoelectric effect or a photochemical effect. The solar light irradiates on a semiconductor P-n junction to form a new hole-electron pair, under the action of an electric field built in the P-n junction, a photoproduction hole flows to a P area, a photoproduction electron flows to an n area, and a circuit is switched on to generate current, so that the working principle of the photoelectric effect solar cell is realized.
The crystal silicon solar cell which works by the photovoltaic effect is taken as the mainstream, and the front silver paste is taken as an important component of the solar cell and is one of the main factors influencing the photoelectric conversion efficiency of the solar cell. The front silver paste generally uses spherical silver powder, and the existing sintering process cannot solve the problem of gaps among the silver powder, so that the conductive network is not smooth, and the conductivity of the conductive network is influenced.
The graphene is composed of a layer of dense carbon atoms wrapped on a honeycomb crystal lattice, namely a planar hexagonal honeycomb net-shaped carbon atom thin layer with a two-dimensional structure. It is composed of carbon atoms and SP2Composed of hybrid orbitals, each of the internal carbon atomsThe carbon atoms all have an unbound electron on the Pz orbital, and the Pz orbital adjacent to the carbon atom can form a delocalized big pi bond in the vertical direction, so the carbon atoms have excellent electrical and optical properties. Its carrier mobility at room temperature is about 15000cm2V · S is twice or more as high as the material having the highest carrier mobility known so far. Graphene is a semi-metal/semiconductor material with a forbidden band width of almost zero, and has the characteristic of semi-metal. Graphene is an ideal material for nano-circuits and has a resistivity of 10-6Omega cm, lower than metallic copper or silver, is the material with the lowest resistance at room temperature among all the known materials at present, and has a conduction density one million times that of copper. Therefore, graphene is expected to solve various problems of the solar cell.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention mainly aims to overcome at least one defect in the prior art, and provides the graphene-doped front silver paste and the preparation method and application thereof, so as to solve the problems that gaps exist among silver powders in the existing front silver paste, so that a conductive network is not smooth, and the conductivity is influenced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a graphene-doped front silver paste, which comprises 90-98% of silver powder, 1-8% of glass powder, 0.5-1% of graphene, 1-10% of organic carrier, 0.1-5% of auxiliary agent and 0.1-1% of solvent by taking the total mass of the front silver paste as a reference; wherein the sheet diameter of the graphene is 50 nm-300 nm.
According to one embodiment of the invention, the graphene has 1-3 layers of sheets and a specific surface area of 250m2/g～400m2/g。
According to one embodiment of the present invention, the silver powder is a spherical silver powder, and the silver powder D50 is 1.5 μm to 2.5 μm.
According to one embodiment of the present invention, the glass frit is selected from one or more of tellurium-lead-boron system, tellurium-lead-bismuth system and bismuth-zinc-boron system.
According to one embodiment of the invention, the solvent is selected from one or more of terpineol, N-methylpyrrolidone, N-dimethylformamide, ethylene glycol butyl ether; the auxiliary agent comprises a defoaming agent and an adhesive, wherein the defoaming agent is a silicone defoaming agent, and the adhesive is selected from one or more of ethyl cellulose, polyvinyl alcohol and sorbitan stearate.
According to one embodiment of the present invention, the organic vehicle comprises 60% to 80% of an organic solvent, 1% to 20% of a plasticizer, 1% to 10% of a thixotropic agent, and 1% to 10% of a thickener, based on the total mass of the organic vehicle.
According to one embodiment of the present invention, the organic solvent is selected from one or more of tributyl citrate, butyl carbitol acetate, N-methyl pyrrolidone; the plasticizer is selected from one or more of phthalate, phosphate and fatty acid ester; the thixotropic agent is selected from one or more of organic bentonite, polyamide wax and castor oil; the thickening agent is selected from one or more of ethyl cellulose and sodium hydroxymethyl cellulose.
The invention also provides a preparation method of the front silver paste, which comprises the following steps: mixing the silver powder, the glass powder, the graphene, the organic carrier, the auxiliary agent and the solvent to obtain a mixture; after the mixture is uniformly dispersed, obtaining a pre-dispersion body; and rolling the pre-dispersion to obtain the front silver paste.
According to one embodiment of the invention, the front-side silver paste is obtained by rolling the pre-dispersion for 3-8 times by using a three-roll mill.
The invention also provides application of the front silver paste in a solar cell.
According to the technical scheme, the invention has the beneficial effects that:
according to the graphene-doped front silver paste provided by the invention, the graphene with the small size of a nanometer level is added into the front silver paste, so that gaps among the silver powders in the front silver paste are effectively communicated, and a smooth conductive network is constructed. And the nano-graphene has small size, so that the printing and screening capability of the nano-graphene is not influenced. The obtained front silver paste can effectively improve the photoelectric conversion efficiency of the solar cell, and has wide application prospect.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a graphene-doped front silver paste, which comprises 90-98% of silver powder, 1-8% of glass powder, 0.5-1% of graphene, 1-10% of organic carrier, 0.1-5% of auxiliary agent and 0.1-1% of solvent by taking the total mass of the front silver paste as a reference; wherein the graphene has a sheet diameter of 50nm to 300nm, for example, 50nm, 70nm, 100nm, 150nm, 176nm, 210nm, 230nm, 270nm, 280nm, 300nm, and the like. Preferably, the size of the plate diameter is 50nm to 150 nm.
According to the invention, the electrodes on the surface of the existing silicon solar cell mainly comprise a back electrode and a front silver electrode, and the electrodes are usually formed by printing conductive silver paste on the surface of a silicon wafer by adopting a screen printing mode. The front silver paste has the capability of penetrating through a silicon nitride (SiNx) antireflection film, and whether good ohmic contact can be formed with a silicon wafer after sintering is the key for improving the efficiency of the solar cell. However, the front silver paste generally uses spherical silver powder, and the existing sintering process cannot solve the problem of gaps among the silver powder, so that the conductive network is not smooth, and the conductivity of the conductive network is influenced. The inventor of the invention finds that by adding the nano-scale graphene into the front silver paste, when the front silver paste is sintered at high temperature, the glass powder is etched and penetrated to firstly penetrate through the silicon nitride antireflection film, and the molten silver powder and the graphene enter the silicon substrate along with the glass powder to form good ohmic contact. The nanoscale small size can effectively communicate the gaps among the silver powder, increase the contact area, construct a smooth conductive network, and the printing screening capability of the nano-graphene is not affected due to the small size of the nano-graphene.
Specifically, the graphene sheet layer is 1-3 layers, and the specific surface area is 250m2/g～400m2G, e.g. 250m2/g、260m2/g、300m2/g、320m2/g、370m2/g、400m2And/g, etc. The silver powder is generally spherical silver powder, and the silver powder D50 is 1.5 to 2.5 μm, for example, 1.5, 1.65, 1.7, 1.78, 2, 2.3 μm or the like.
In some embodiments, the foregoing glass frit is selected from one or more of tellurium (Te) -lead (Pb) -boron (B) system, tellurium (Te) -lead (Pb) -bismuth (Bi) system, bismuth (Bi) -zinc (Zn) -boron (B) system.
In some embodiments, the aforementioned solvent is selected from one or more of terpineol, N-methylpyrrolidone, N-dimethylformamide, butyl cellosolve; the auxiliary agent comprises a defoaming agent and an adhesive, wherein the defoaming agent is a silicone defoaming agent, and the adhesive is selected from one or more of ethyl cellulose, polyvinyl alcohol and sorbitan stearate.
In some embodiments, the organic vehicle comprises 60% to 80% organic solvent, 1% to 20% plasticizer, 1% to 10% thixotropic agent, and 1% to 10% thickening agent, based on the total mass of the organic vehicle. Wherein the organic solvent is selected from one or more of tributyl citrate, butyl carbitol acetate and N-methyl pyrrolidone; the plasticizer is selected from one or more of phthalate, phosphate and fatty acid ester; the thixotropic agent is selected from one or more of organic bentonite, polyamide wax and castor oil; the thickening agent is selected from one or more of ethyl cellulose and sodium hydroxymethyl cellulose. The organic carrier has an important influence on the aspect ratio of the grid lines during printing, and the aspect ratio of the grid lines finally influences the photoelectric conversion efficiency of the solar cell.
The invention also provides a preparation method of the front silver paste, which comprises the following steps: mixing the silver powder, the glass powder, the graphene, the organic carrier, the auxiliary agent and the solvent to obtain a mixture; uniformly dispersing the mixture to obtain a pre-dispersion body; and rolling the pre-dispersion to obtain the front silver paste. The front-side silver paste is obtained by rolling the pre-dispersion for 3-8 times by using a three-roll mill, but the invention is not limited thereto, and the rolling times can be adjusted according to actual needs.
In conclusion, the nano-scale graphene is added into the front silver paste, so that the nano-scale small-size graphene can effectively communicate with gaps among the silver powder, the contact area is increased, a smooth conductive network is constructed, and the printing and screening capability of the nano-scale graphene is not influenced due to the small size of the nano-scale graphene. The obtained front silver paste can effectively improve the photoelectric conversion efficiency of the solar cell, and has wide application prospect.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
1) 0.5 percent of graphene (with the sheet diameter of 80 nm-120 nm and the specific surface area of 300 m) is added by mass percentage2Per gram), 5.4% of organic carrier, 91.2% of silver powder (particle size 2.0 μm), 2.1% of bismuth (Bi) -zinc (Zn) -boron (B) system glass powder (BYB0876, Baibo, Guizhou), 0.1% of defoaming agent BYK-066N, 0.2% of adhesive polyvinyl alcohol, 0.2% of ethylene glycol butyl ether, 0.2% of terpineol and 0.1% of N-methyl pyrrolidone solvent are added into a material barrel and uniformly mixed, wherein the organic carrier comprises 3.4% of butyl carbitol, 1% of polyamide wax and 1% of phthalate.
2) Uniformly dispersing the mixture obtained in the step 1) by using a high-speed dispersion machine at the rotating speed of 2000rpm, and then carrying out gadolinium pressing for 5 times by using a three-roll machine to obtain the graphene-doped front silver paste.
And printing a 360-mesh screen plate on the monocrystalline silicon piece, sintering at multiple temperature intervals of 280-880 ℃ to obtain the monocrystalline silicon battery piece, and testing the electrical property of the battery piece, wherein the results are shown in table 1.
Example 2
1) 0.4 percent of graphene (the sheet diameter is 80 nm-120 nm, the specific surface area is 300 m)2Per gram), 5.4% of organic carrier, 91.3% of silver powder (particle size 2.0 μm), 2.1% of bismuth (Bi) -zinc (Zn) -boron (B) system glass powder (BYB0876, Baibo, Guizhou), 0.1% of defoaming agent BYK-066N, 0.2% of adhesive polyvinyl alcohol, 0.2% of ethylene glycol butyl ether, 0.2% of terpineol and 0.1% of N-methyl pyrrolidone solvent are added into a material barrel and uniformly mixed, wherein the organic carrier comprises 3.4% of butyl carbitol, 1% of polyamide wax and 1% of phthalate.
2) Uniformly dispersing the mixture obtained in the step 1) by using a high-speed dispersion machine at the rotating speed of 2000rpm, and then carrying out gadolinium pressing for 5 times by using a three-roll machine to obtain the graphene-doped front silver paste.
And printing a 360-mesh screen plate on the monocrystalline silicon piece, sintering at multiple temperature intervals of 280-880 ℃ to obtain the monocrystalline silicon battery piece, and testing the electrical property of the battery piece, wherein the results are shown in table 1.
Comparative example 1
1) Adding 5.4% of organic carrier, 91.7% of silver powder (the particle size is 2.0 mu m), 2.1% of bismuth (Bi) -zinc (Zn) -boron (B) system glass powder (BYB0876, Baibo, Guizhou), 0.1% of defoaming agent BYK-066N, 0.2% of adhesive polyvinyl alcohol, 0.2% of ethylene glycol butyl ether, 0.2% of terpineol and 0.1% of N-methyl pyrrolidone solvent into a material barrel, and uniformly mixing, wherein the organic carrier comprises 3.4% of butyl carbitol, 1% of polyamide wax and 1% of phthalate.
2) Uniformly dispersing the mixture obtained in the step 1) by using a high-speed dispersion machine at the rotating speed of 2000rpm, and then pressing gadolinium for 5 times by using a three-roll machine to obtain front silver paste.
And printing a 360-mesh screen plate on the monocrystalline silicon piece, sintering at multiple temperature intervals of 280-880 ℃ to obtain the monocrystalline silicon battery piece, and testing the electrical property of the battery piece, wherein the results are shown in table 1.
Comparative example 2
1) 0.5 percent of graphene (the sheet diameter is 1-5 mu m, the specific surface area is 300 m)2Per gram), 5.4% of organic carrier, 91.2% of silver powder (particle size 2.0 μm), 2.1% of bismuth (Bi) -zinc (Zn) -boron (B) system glass powder (BYB0876, Baibo, Guizhou), 0.1% of defoaming agent BYK-066N, 0.2% of adhesive polyvinyl alcohol, 0.2% of ethylene glycol butyl ether, 0.2% of terpineol and 0.1% of N-methyl pyrrolidone solvent are added into a material barrel and uniformly mixed, wherein the organic carrier comprises 3.4% of butyl carbitol, 1% of polyamide wax and 1% of phthalate.
2) Uniformly dispersing the mixture obtained in the step 1) by using a high-speed dispersion machine at the rotating speed of 2000rpm, and then carrying out gadolinium pressing for 5 times by using a three-roll machine to obtain the graphene-doped front silver paste. And printing a 360-mesh screen plate on the monocrystalline silicon piece, sintering at multiple temperature intervals of 280-880 ℃ to obtain the monocrystalline silicon battery piece, and testing the electrical property of the battery piece, wherein the results are shown in table 1.
Comparative example 3
1) 0.5 percent of modified graphene (with the sheet diameter of 80 nm-120 nm and the specific surface area of 300 m) is added by mass percentage2The modifier is polyvinylpyrrolidone, the mass of the modifier is 0.1 percent of graphene, 5.4 percent of organic carrier, 91.2 percent of silver powder (the particle size is 2.0 mu m), 2.1 percent of bismuth (Bi) -zinc (Zn) -boron (B) system glass powder (Bybo, BYB0876, Guizhou), 0.1 percent of defoaming agent BYK-066N, 0.2 percent of adhesive polyvinyl alcohol, 0.2 percent of ethylene glycol monobutyl ether, 0.2 percent of terpineol and 0.1 percent of N-methyl pyrrolidone solvent are added into a material barrel and evenly mixed, wherein the organic carrier comprises 3.4 percent of butyl carbitol, 1 percent of polyamide wax and 1 percent of phthalate.
2) Uniformly dispersing the mixture obtained in the step 1) by using a high-speed dispersion machine at the rotating speed of 2000rpm, and then carrying out gadolinium pressing for 5 times by using a three-roll machine to obtain the graphene-doped front silver paste.
And printing a 360-mesh screen plate on the monocrystalline silicon piece, sintering at multiple temperature intervals of 280-880 ℃ to obtain the monocrystalline silicon battery piece, and testing the electrical property of the battery piece, wherein the results are shown in table 1.
TABLE 1
As can be seen from table 1 above, the photoelectric conversion efficiency of the large-sized graphene and the modified graphene is lower than that of the small-sized graphene, and the small-sized graphene has a small particle size, so that the screen printing plate is not easily blocked during printing, and smooth and continuous grid lines can be printed; the modified graphene is wrapped on the surface of graphene because of the addition of the dispersing agent, so that the electronic migration of the modified graphene is influenced, and the conductivity of the modified graphene is reduced by a little compared with that of pure graphene.
In conclusion, the graphene with the small nanoscale size is added into the front silver paste, so that gaps among the silver powder in the front silver paste are effectively communicated, and a smooth conductive network is constructed. And the nano-graphene has small size, so that the printing and screening capability of the nano-graphene is not influenced. The obtained front silver paste can effectively improve the photoelectric conversion efficiency of the solar cell, and has wide application prospect.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. The graphene-doped front silver paste is characterized by comprising 90-98% of silver powder, 1-8% of glass powder, 0.5-1% of graphene, 1-10% of organic carrier, 0.1-5% of auxiliary agent and 0.1-1% of solvent by taking the total mass of the front silver paste as a reference; wherein the sheet diameter of the graphene is 50 nm-300 nm.
2. The graphene-doped front silver paste according to claim 1, wherein the graphene has 1-3 layers of sheet layers and a specific surface area of 250m2/g～400m2/g。
3. The graphene-doped front silver paste according to claim 1, wherein the silver powder is spherical silver powder, and the silver powder D50 is 1.5-2.5 μm.
4. The graphene-doped front silver paste of claim 1, wherein the glass frit is selected from one or more of a tellurium-lead-boron system, a tellurium-lead-bismuth system, and a bismuth-zinc-boron system.
5. The graphene-doped front side silver paste according to claim 1, wherein the solvent is selected from one or more of terpineol, N-methylpyrrolidone, N-dimethylformamide, ethylene glycol monobutyl ether; the auxiliary agent comprises a defoaming agent and an adhesive, wherein the defoaming agent is a silicone defoaming agent, and the adhesive is selected from one or more of ethyl cellulose, polyvinyl alcohol and sorbitan stearate.
6. The graphene-doped front silver paste according to claim 1, wherein the organic vehicle comprises 60-80% of an organic solvent, 1-20% of a plasticizer, 1-10% of a thixotropic agent and 1-10% of a thickening agent, based on the total mass of the organic vehicle.
7. The graphene-doped front silver paste according to claim 6, wherein the organic solvent is selected from one or more of tributyl citrate, butyl carbitol acetate, and N-methylpyrrolidone; the plasticizer is selected from one or more of phthalate, phosphate and fatty acid ester; the thixotropic agent is selected from one or more of organic bentonite, polyamide wax and castor oil; the thickening agent is selected from one or more of ethyl cellulose and sodium hydroxymethyl cellulose.
8. The preparation method of the graphene-doped front silver paste according to any one of claims 1 to 7, which is characterized by comprising the following steps:
mixing the silver powder, the glass powder, the graphene, the organic carrier, the auxiliary agent and the solvent to obtain a mixture;
after the mixture is uniformly dispersed, obtaining a pre-dispersion body; and
and rolling the pre-dispersion to obtain the graphene-doped front silver paste.
9. The preparation method of claim 8, wherein the pre-dispersion is rolled by a three-roll mill for 3-8 times to obtain the graphene-doped front silver paste.
10. The application of the graphene-doped front-side silver paste according to any one of claims 1 to 7 in a solar cell.
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