CN114267474B - High-performance metalized slurry for solar cell and preparation method thereof - Google Patents
High-performance metalized slurry for solar cell and preparation method thereof Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 110
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000003960 organic solvent Substances 0.000 claims abstract description 72
- 239000011521 glass Substances 0.000 claims abstract description 69
- 229910052709 silver Inorganic materials 0.000 claims abstract description 46
- 239000004332 silver Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 41
- 239000000956 alloy Substances 0.000 claims abstract description 41
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 38
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 32
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 238000001465 metallisation Methods 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 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
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 9
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- 238000004090 dissolution Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 5 to 10 parts of organic resin, 10 to 20 parts of organic solvent, 0.2 to 0.5 part of surfactant, 0.1 to 0.3 part of coupling agent, 0.2 to 0.4 part of maleic anhydride grafting compatilizer, 2 to 5 parts of silver coated glass powder, 5 to 12 parts of glass powder, 70 to 80 parts of silver powder and 1 to 3 parts of nano alloy powder; the high-performance metallized slurry for the solar cell, which is prepared by the invention, is suitable for an ultra-thin line printing process with the thickness of less than 25 mu m, and has the characteristics of good thin line printing property, high conversion efficiency, low composite current, low contact resistivity and the like.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to high-performance metalized slurry for a solar cell and a preparation method thereof.
Background
The technology in the photovoltaic industry is updated and iterated rapidly, the component conversion efficiency determined by first-time runners is currently a market admission threshold, and enterprises actively develop research and development and large-scale application of high-efficiency technologies, which is the root of the maintained competitiveness. The N-type crystalline silicon battery is a necessary choice of a high-efficiency battery technology route due to the natural advantages of high minority carrier lifetime, no light-induced attenuation and the like, and is a new generation battery technology entering mass production in the photovoltaic industry. An ultra-thin tunneling oxide layer and a passivation contact structure of a highly doped polycrystalline silicon thin layer are introduced into an N-type battery to form a tunneling oxide layer passivation contact battery (Tunnel Oxide Passivated Contact, TOPCon), so that the conversion efficiency of the battery can be greatly improved, and the method is an important development direction of a high-efficiency battery.
When the metalized slurry for the P-type photovoltaic cell which is mainstream in the market at present is used for preparing the electrode of TOPCon cells and perovskite laminated cells thereof, the passivation layer structure can be burnt out due to the difference of the cell surface structures, so that the loss of the cell in the Filling Factor (FF) and the open-circuit voltage (Voc) is brought, and the conversion efficiency of the cell is seriously affected. Therefore, the novel metalized slurry is developed, the damage to the passivation layer of the high-efficiency battery including TOPCon and perovskite laminated batteries thereof is reduced in the battery sintering process, the high conversion efficiency is realized, and the development of the high-efficiency battery in the future is very critical.
Patent 201911377189.5 provides a high-efficiency nano silver coated glass powder, a doped nano oxide conductive paste and a preparation method, wherein the conductive paste is prepared by using the nano silver coated glass powder and the nano oxide, compared with the conductive paste prepared without coating and nano oxide, uoc is improved by 0.33%, FF is improved by 0.2%, and conversion efficiency Ncell is improved to 22.76%, so that the requirement of high conversion efficiency cannot be met.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a preparation method of high-performance metalized slurry for a solar cell, and the high-performance metalized slurry for the solar cell prepared by the method is applicable to an ultra-thin line printing process with the thickness of less than 25 mu m and has the characteristics of good thin line printing performance, high conversion efficiency, low composite current, low contact resistivity and the like.
The technical scheme of the invention is as follows:
The invention provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 5 to 10 parts of organic resin, 10 to 20 parts of organic solvent, 0.2 to 0.5 part of surfactant, 0.1 to 0.3 part of coupling agent, 0.2 to 0.4 part of maleic anhydride grafting compatilizer, 2 to 5 parts of silver coated glass powder, 5 to 12 parts of glass powder, 70 to 80 parts of silver powder and 1 to 3 parts of nano alloy powder.
As a further limitation of the present invention, the organic resin is a thermoplastic resin, and the thermoplastic resin is at least one of polyethylene, polypropylene, polystyrene, and polyvinyl butyral.
As a further limitation of the present invention, the organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, the hydrophilic organic solvent is at least one of methanol, ethanol, acetone, formic acid, acetic acid; the lipophilic organic solvent is at least one of dimethyl adipate, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, terpineol and dioctyl phthalate.
As a further limitation of the present invention, the maleic anhydride graft compatibilizer is at least one of a maleic anhydride grafted ethylene-vinyl acetate copolymer, a maleic anhydride grafted polypropylene, and a maleic anhydride grafted polyethylene.
As a further limitation of the present invention, the silver powder is one or a mixture of more of spherical silver powder, plate-like silver powder, irregular silver powder, and linear silver powder; the D50 of the silver powder is 400-600 nm.
As a further limitation of the present invention, the nano alloy powder is at least one of tin-based, lead-based, aluminum-based, copper-based alloy powder; the grain diameter of the nano alloy powder is 100-300 nm.
As a further limitation of the present invention, the silver-coated glass frit is prepared by the following method:
a. Slowly dripping ammonia water with the concentration of 0.01-0.05 mol/L into silver nitrate solution with the concentration of 0.01-0.05 mol/L, and stirring for 1-2 h to obtain silver ammonia solution;
b. Adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution;
c. Adding glass powder into the mixed solution obtained in the step b, performing ultrasonic dispersion for 10-30 min by using a cell ultrasonic pulverizer, and then heating in a water bath at 60-80 ℃ for 2-4 h to obtain a mixed solution containing activated glass powder;
d. Slowly dripping glucose solution with the concentration of 0.01-0.1 mlo/L into the mixed solution obtained in the step c, and reacting for 20-60 min under the conditions of water bath heating and magnetic stirring after 2-3 min of dripping; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; finally, placing the glass powder in an oven with the temperature of 80-90 ℃ and drying for 6-8 hours to obtain the silver coated glass powder.
As a further limitation of the invention, the mass ratio of the silver nitrate solution to the ammonia water in the step a is 1:1-10.
As a further limitation of the present invention, the anhydrous ethanol in the step b accounts for 5 to 15% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1 to 3% of the mass of the silver-ammonia solution.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell, which comprises the following steps:
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolving temperature is 120-140 ℃ for 1-2 h, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotating speed of 2000-3000 RPM, and reacting for 1-2 h at an activating temperature of 60-80 ℃ to obtain an organic carrier with the viscosity of 30-45 Pa.S;
(3) Adding the mixed powder obtained in the step (1) into the organic carrier obtained in the step (2), and stirring for 4-6 hours at the temperature of 40-60 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 150-350 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
The beneficial technical effects of the invention are as follows:
(1) The organic solvent adopts a hydrophilic organic solvent and lipophilic organic solvent composite technology, has different surface tension, contains more active functional groups, and can enhance the bonding effect between organic resin and silver powder in an organic carrier and between silver paste slurry and a battery piece substrate; on one hand, the lipophilic organic solvent can lubricate silver powder, reduce friction among powder, in order to increase the arrangement compactness and stacking compactness of silver powder in silver grating after sintering, solidification, also weaken the friction between paste and screen printing plate while printing at the same time, in order to improve, improve fine grating, high-speed printability of paste; on the other hand, the hydrophilic organic solvent can improve the compatibility and wettability of the silver powder and the resin in the organic carrier, and endow the paste with lower viscosity and better fluidity, so that the paste has excellent printing superfine linearity.
(2) The organic carrier is prepared by two-stage heat treatment and activation, organic resin and organic solvent in the organic carrier are heated and dissolved, then surfactant, coupling agent and maleic anhydride grafting compatilizer are mixed with the organic carrier, and the organic carrier obtained by the heat activation treatment has the characteristics of proper viscosity and high viscosity stability, can effectively reduce the generation probability of silver flakes during silver paste production, and is suitable for rapid printing.
(3) According to the invention, the maleic anhydride grafting compatilizer is added, so that the compatibility of the organic resin with silver powder, glass powder and nano alloy powder can be improved, the organic carrier can better cover conductive particles, and agglomeration, aggregation and precipitation among the particles are prevented, so that conductive particles can form good conductive chains during sintering of the conductive paste, and a continuous and compact conductive silver film is finally obtained.
Detailed Description
The present invention will be specifically described with reference to examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 5 parts of organic resin, 20 parts of organic solvent, 0.2 part of surfactant, 0.3 part of coupling agent, 0.2 part of maleic anhydride grafting compatilizer, 2 parts of silver coated glass powder, 12 parts of glass powder, 70 parts of silver powder and 1 part of nano alloy powder.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is methanol, and the lipophilic organic solvent is dimethyl adipate.
The organic resin is thermoplastic resin, and the thermoplastic resin is polyethylene.
The maleic anhydride grafted compatilizer is maleic anhydride grafted ethylene-vinyl acetate copolymer.
The silver powder is spherical silver powder, and the D50 of the silver powder is 400nm.
The nano alloy powder is tin-based alloy powder, and the grain diameter of the nano alloy powder is 100nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding ammonia water with the concentration of 0.01mol/L (the mass ratio is 1:1) into silver nitrate solution with the concentration of 0.01mol/L, and stirring for 1h to obtain silver ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the anhydrous ethanol accounts for 5% of the mass of the silver ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver ammonia solution.
C. adding glass powder into the mixed solution, performing ultrasonic dispersion for 10min by using a cell ultrasonic pulverizer, and then heating in a water bath at 80 ℃ for 2h to obtain a mixed solution containing activated glass powder;
d. Slowly dripping glucose solution with the concentration of 0.01mlo/L into the mixed solution obtained in the step c, and reacting for 20min under the conditions of water bath heating and magnetic stirring after 3min of dripping; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; and finally, placing the glass powder in an oven at 90 ℃ for drying treatment for 6 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell,
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolution temperature is 120 ℃, the time is 2 hours, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotating speed of 3000RPM, and reacting for 2 hours at an activation temperature of 60 ℃ to obtain an organic carrier with the viscosity of 45 Pa.S;
(3) Adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 4 hours at 60 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 350 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
Example 2
The embodiment provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 10 parts of organic resin, 10 parts of organic solvent, 0.5 part of surfactant, 0.3 part of coupling agent, 0.4 part of maleic anhydride grafting compatilizer, 5 parts of silver coated glass powder, 5 parts of glass powder, 80 parts of silver powder and 3 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is polypropylene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is ethanol, and the lipophilic organic solvent is diethylene glycol dimethyl ether.
The maleic anhydride grafted compatilizer is maleic anhydride grafted polypropylene.
The silver powder is flake silver powder, and the D50 of the silver powder is 400nm.
The nano alloy powder is lead-base alloy powder, and the grain diameter of the nano alloy powder is 300nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding ammonia water with the concentration of 0.05mol/L (the mass ratio is 1:10) into silver nitrate solution with the concentration of 0.05mol/L, and stirring for 2 hours to obtain silver ammonia solution;
b. Adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 15% of the mass of the silver ammonia solution, and the polyvinylpyrrolidone accounts for 3% of the mass of the silver ammonia solution.
C. Adding glass powder into the mixed solution, performing ultrasonic dispersion for 30min by using a cell ultrasonic pulverizer, and then heating in a water bath at 60 ℃ for 4h to obtain a mixed solution containing activated glass powder;
d. Slowly dripping glucose solution with the concentration of 0.1mlo/L into the mixed solution obtained in the step c, and reacting for 60min under the conditions of water bath heating and magnetic stirring after 3min of dripping; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; finally, placing the glass powder in an oven at 80 ℃ for drying treatment for 6-8 hours to obtain the silver coated glass powder.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell,
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolution temperature is 140 ℃ for 1h, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotating speed of 2000RPM, and reacting for 1h at an activation temperature of 80 ℃ to obtain an organic carrier with the viscosity of 30 Pa.S;
(3) Adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 6 hours at 40 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 150 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
Example 3
The embodiment provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 8 parts of organic resin, 15 parts of organic solvent, 0.3 part of surfactant, 0.2 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 4 parts of silver coated glass powder, 10 parts of glass powder, 75 parts of silver powder and 2 parts of nano alloy powder.
The organic resin is a thermoplastic resin, and the thermoplastic resin is polystyrene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is acetone, and the lipophilic organic solvent is diethylene glycol butyl ether acetate.
The maleic anhydride grafted compatilizer is maleic anhydride grafted polyethylene.
The silver powder is linear silver powder, and the D50 of the silver powder is 600nm.
The nano alloy powder is aluminum-based alloy powder, and the particle size of the nano alloy powder is 200nm.
The silver-coated glass powder is prepared by the following method:
a. Slowly dropwise adding ammonia water with the concentration of 0.02mol/L (mass ratio of 1:5) into silver nitrate solution with the concentration of 0.03mol/L, and stirring for 2 hours to obtain silver ammonia solution;
adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 10% of the mass of the silver ammonia solution, and the polyvinylpyrrolidone accounts for 2% of the mass of the silver ammonia solution.
B. Adding glass powder into the mixed solution, performing ultrasonic dispersion for 20min by using a cell ultrasonic pulverizer, and then heating in a water bath at 70 ℃ for 3h to obtain a mixed solution containing activated glass powder;
d. Slowly dripping glucose solution with the concentration of 0.05mlo/L into the mixed solution obtained in the step c, and reacting for 40min under the conditions of water bath heating and magnetic stirring after 3min of dripping; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; and finally, placing the glass powder in an oven at the temperature of 85 ℃ and drying for 7 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell,
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolution temperature is 130 ℃, the time is 1h, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotation speed of 2500RPM, and reacting for 1h at an activation temperature of 70 ℃ to obtain an organic carrier with the viscosity of 40 Pa.S;
(3) Adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5 hours at 50 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 200 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
Example 4
The embodiment provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 8 parts of organic resin, 12 parts of organic solvent, 0.4 part of surfactant, 0.1 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 3 parts of silver coated glass powder, 8 parts of glass powder, 72 parts of silver powder and 2.5 parts of nano alloy powder.
The organic resin is a thermoplastic resin, and the thermoplastic resin is polyvinyl butyral.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is formic acid, and the lipophilic organic solvent is diethylene glycol dibutyl ether.
The maleic anhydride grafted compatilizer is a mixture of maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polypropylene.
The silver powder is irregular silver powder, and the D50 of the silver powder is 500nm.
The nano alloy powder is copper-based alloy powder, and the particle size of the nano alloy powder is 100nm.
The silver-coated glass powder is prepared by the following method:
a. Slowly dropwise adding ammonia water with the concentration of 0.03mol/L (the mass ratio is 1:6) into silver nitrate solution with the concentration of 0.02mol/L, and stirring for 2 hours to obtain silver ammonia solution;
b. Adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the anhydrous ethanol accounts for 8% of the mass of the silver ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver ammonia solution.
C. adding glass powder into the mixed solution, performing ultrasonic dispersion for 10min by using a cell ultrasonic pulverizer, and then heating in a water bath at 60 ℃ for 4h to obtain a mixed solution containing activated glass powder;
d. slowly dripping glucose solution with the concentration of 0.02mlo/L into the mixed solution obtained in the step c, and reacting for 50min under the conditions of water bath heating and magnetic stirring after 3min of dripping; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; and finally, placing the glass powder in an oven at 88 ℃ for drying treatment for 7 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell,
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolution temperature is 120 ℃, the time is 2 hours, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotation speed of 2500RPM, and reacting for 1 hour at an activation temperature of 70 ℃ to obtain an organic carrier with the viscosity of 40 Pa.S;
(3) Adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5 hours at 50 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 180 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
Example 5
The embodiment provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 8 parts of organic resin, 12 parts of organic solvent, 0.4 part of surfactant, 0.1 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 3 parts of silver coated glass powder, 8 parts of glass powder, 72 parts of silver powder and 2.5 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is a mixture of polyethylene and polystyrene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is formic acid, and the lipophilic organic solvent is diethylene glycol dibutyl ether.
The maleic anhydride grafted compatilizer is a mixture of maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polypropylene.
The silver powder is irregular silver powder, and the D50 of the silver powder is 500nm.
The nano alloy powder is copper-based alloy powder, and the particle size of the nano alloy powder is 100nm.
The silver-coated glass powder is prepared by the following method:
a. Slowly dropwise adding ammonia water with the concentration of 0.03mol/L (the mass ratio is 1:6) into silver nitrate solution with the concentration of 0.02mol/L, and stirring for 2 hours to obtain silver ammonia solution;
Adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the anhydrous ethanol accounts for 8% of the mass of the silver ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver ammonia solution.
B. adding glass powder into the mixed solution, performing ultrasonic dispersion for 10min by using a cell ultrasonic pulverizer, and then heating in a water bath at 60 ℃ for 4h to obtain a mixed solution containing activated glass powder;
d. slowly dripping glucose solution with the concentration of 0.02mlo/L into the mixed solution obtained in the step c, and reacting for 50min under the conditions of water bath heating and magnetic stirring after 3min of dripping; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; and finally, placing the glass powder in an oven at 88 ℃ for drying treatment for 7 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell,
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolution temperature is 120 ℃, the time is 2 hours, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotation speed of 2500RPM, and reacting for 1 hour at an activation temperature of 70 ℃ to obtain an organic carrier with the viscosity of 40 Pa.S;
(3) Adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5 hours at 50 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 180 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
Example 6
The embodiment provides high-performance metalized slurry for a solar cell, which comprises the following raw materials in parts by weight: 6 parts of organic resin, 16 parts of organic solvent, 0.3 part of surfactant, 0.2 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 4 parts of silver coated glass powder, 9 parts of glass powder, 75 parts of silver powder and 2 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is a mixture of polyethylene and polypropylene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is acetic acid, and the lipophilic organic solvent is dioctyl phthalate.
The maleic anhydride grafted compatilizer is a mixture of maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene.
The silver powder is spherical silver powder and flake silver powder, and the D50 of the silver powder is 400nm.
The nano alloy powder is tin-copper alloy powder, and the particle size of the nano alloy powder is 200nm.
The silver-coated glass powder is prepared by the following method:
a. Slowly dropwise adding ammonia water with the concentration of 0.04mol/L (mass ratio of 1:8) into silver nitrate solution with the concentration of 0.03mol/L, and stirring for 1.5h to obtain silver ammonia solution;
b. Adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the anhydrous ethanol accounts for 8% of the mass of the silver ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver ammonia solution.
C. Adding glass powder into the mixed solution, performing ultrasonic dispersion for 15min by using a cell ultrasonic pulverizer, and then heating in a water bath at 70 ℃ for 3h to obtain a mixed solution containing activated glass powder;
d. Slowly dripping glucose solution with the concentration of 0.08mlo/L into the mixed solution obtained in the step c, after 2.5min of dripping, and reacting for 30min under the conditions of water bath heating and magnetic stirring; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; and finally, placing the glass powder in an oven at 82 ℃ for drying treatment for 6.5 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metalized slurry for the solar cell,
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolution temperature is 110 ℃, the time is 1.5h, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at 2800RPM (revolutions per minute), and reacting for 1.5h at 65 ℃ to obtain an organic carrier with the viscosity of 40 Pa.S;
(3) Adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5.5 hours at 45 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 300 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
Comparative example 1
This comparative example is essentially the same as example 1, with the only difference that a conventional organic solvent is selected.
Comparative example 2
This comparative example is essentially the same as example 1, except that the organic vehicle is prepared by conventional stress stirring and rolling mill grinding activation.
Comparative example 3
The high performance metallization paste for solar cells of this comparative example was prepared by the method of example in patent 201911377189.5.
Test case
The high-performance metallized slurry for solar cells prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to performance test by the following methods: the contact resistivity was tested according to TLM rule; the composite current was tested using SunsVoc tester.
The test results are shown in the following table:
The performance comparison of the examples 1-6 and the comparative examples 1-3 shows that the conversion efficiency of the high-performance metallized slurry for the solar cell prepared by the invention is 25.8%, and is improved by 13% compared with the comparative example 3, meanwhile, the contact resistivity is less than 1mΩ.cm 2, and the composite current is less than 50fA/cm 2, so that the high-performance metallized slurry for the solar cell prepared by the invention has the advantages of high conversion efficiency, low composite current and low contact resistivity.
Although the embodiments of the present invention have been disclosed in the foregoing description and drawings, it is not limited to the details of the embodiments and examples, but is to be applied to all the fields of application of the present invention, it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (8)
1. The high-performance metalized slurry for the solar cell is characterized by comprising the following raw materials in parts by weight: 5 to 10 parts of organic resin, 10 to 20 parts of organic solvent, 0.2 to 0.5 part of surfactant, 0.1 to 0.3 part of coupling agent, 0.2 to 0.4 part of maleic anhydride grafting compatilizer, 2 to 5 parts of silver coated glass powder, 5 to 12 parts of glass powder, 70 to 80 parts of silver powder and 1 to 3 parts of nano alloy powder;
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is at least one of methanol, ethanol, acetone, formic acid and acetic acid; the lipophilic organic solvent is at least one of dimethyl adipate, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, terpineol and dioctyl phthalate;
the preparation method of the high-performance metalized slurry for the solar cell comprises the following steps of:
(1) Putting the silver-coated glass powder, the silver powder and the nano alloy powder into a ball mill, and grinding the mixture while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) Putting an organic solvent and an organic resin into a reaction kettle according to a proportion, heating and stirring to dissolve the resin, wherein the resin dissolving temperature is 120-140 ℃ for 1-2 h, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at a rotating speed of 2000-3000 RPM, and reacting for 1-2 h at an activating temperature of 60-80 ℃ to obtain an organic carrier with the viscosity of 30-45 Pa.S;
(3) Adding the mixed powder obtained in the step (1) into the organic carrier obtained in the step (2), and stirring for 4-6 hours at the temperature of 40-60 ℃ to obtain uniformly mixed slurry;
(4) Grinding the slurry obtained in the step (3) in a three-roller mill, and finely adjusting an organic solvent to ensure that the fineness of the silver slurry is below 25 mu m and the viscosity is 150-350 Pa.S, thereby preparing the high-performance metalized slurry for the solar cell.
2. The high-performance metallized paste for solar cells according to claim 1, wherein the organic resin is a thermoplastic resin, and the thermoplastic resin is at least one of polyethylene, polypropylene, polystyrene and polyvinyl butyral.
3. The high performance metallization paste for solar cells according to claim 1, wherein the maleic anhydride grafted compatibilizer is at least one of a maleic anhydride grafted ethylene-vinyl acetate copolymer, a maleic anhydride grafted polypropylene, and a maleic anhydride grafted polyethylene.
4. The high-performance metallization paste for solar cells according to claim 1, wherein the silver powder is one or more of spherical silver powder, plate-like silver powder, irregular silver powder, and linear silver powder; the D50 of the silver powder is 400-600 nm.
5. The high-performance metallized paste for solar cells according to claim 1, wherein the nano alloy powder is at least one of tin-based, lead-based, aluminum-based, copper-based alloy powder; the grain diameter of the nano alloy powder is 100-300 nm.
6. The high performance metallization paste for solar cells of claim 1, wherein the silver-coated glass frit is prepared by the following method:
a. Slowly dripping ammonia water with the concentration of 0.01-0.05 mol/L into silver nitrate solution with the concentration of 0.01-0.05 mol/L, and stirring for 1-2 h to obtain silver ammonia solution;
b. Adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver ammonia solution, and magnetically stirring until the absolute ethyl alcohol and polyvinylpyrrolidone are fully dissolved to obtain a mixed solution;
c. Adding glass powder into the mixed solution obtained in the step b, performing ultrasonic dispersion for 10-30 min by using a cell ultrasonic pulverizer, and then heating in a water bath at 60-80 ℃ for 2-4 h to obtain a mixed solution containing activated glass powder;
d. Slowly dripping glucose solution with the concentration of 0.01-0.1 mol/L into the mixed solution obtained in the step c, after 2-3 min of dripping, and reacting for 20-60 min under the conditions of water bath heating and magnetic stirring; after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and centrifuging for 3 times respectively; finally, placing the glass powder in an oven with the temperature of 80-90 ℃ and drying for 6-8 hours to obtain the silver coated glass powder.
7. The high-performance metallization paste for solar cells according to claim 6, wherein the mass ratio of the silver nitrate solution to the ammonia water in the step a is 1:1-10.
8. The high-performance metallization paste for solar cells according to claim 6, wherein the absolute ethyl alcohol in the step b accounts for 5-15% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1-3% of the mass of the silver-ammonia solution.
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