CN114464338B - Front-side conductive silver paste of solar cell and preparation method thereof - Google Patents
Front-side conductive silver paste of solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN114464338B CN114464338B CN202111435811.0A CN202111435811A CN114464338B CN 114464338 B CN114464338 B CN 114464338B CN 202111435811 A CN202111435811 A CN 202111435811A CN 114464338 B CN114464338 B CN 114464338B
- Authority
- CN
- China
- Prior art keywords
- parts
- nano
- silver paste
- solar cell
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 50
- 239000003549 soybean oil Substances 0.000 claims abstract description 50
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 42
- 150000007524 organic acids Chemical class 0.000 claims abstract description 24
- 229920000620 organic polymer Polymers 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 20
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 13
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 10
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 30
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229920000414 polyfuran Polymers 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 11
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 11
- 229920001197 polyacetylene Polymers 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052680 mordenite Inorganic materials 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- -1 polyparaphenylene Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 238000003079 width control Methods 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 208000029154 Narrow face Diseases 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Development (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Life Sciences & Earth Sciences (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a front-side conductive silver paste of a solar cell and a preparation method thereof, wherein the preparation material of the conductive silver paste comprises the following components in parts by weight: 40-50 parts of bisphenol A epoxy resin; 20-40 parts of nano silver particles; 30-50 parts of nano glass powder; 50-60 parts of organic carrier mixed solution; 8-10 parts of tetraethyl titanate; 6-9 parts of alkaline amine; 5-10 parts of anhydride; 8-15 parts of boron trifluoride monoethylamine complex; the organic carrier mixed solution comprises 15-20% of organic acid doped conductive organic polymer/epoxidized soybean oil and 80-85% of high boiling point solvent. The invention can effectively wet the contact between the inorganic powder and the mesh cloth material, provides more excellent fine line ink permeability, is suitable for the high-speed printing of the superfine grid of the current large-area silicon wafer, and has excellent line width control capability for the fine grid, thereby forming better electrode aspect ratio.
Description
Technical Field
The invention belongs to the technical field of conductive silver paste, and particularly relates to conductive silver paste for the front surface of a solar cell and a preparation method thereof.
Background
The front-side conductive silver paste of the solar cell is one of the most critical factors for determining the conversion efficiency of the solar cell, and the screen printing process combining ultra-fine line and dense grid design is the most effective and direct method for improving the efficiency of the cell besides pushing up the sheet resistance of the silicon wafer. In recent years, the front-side conductive silver paste consumption of the photovoltaic industry in China always occupies more than 75% of the world, but first-line battery piece manufacturers at home and abroad still rely on imported products for high-efficiency front-side conductive silver paste selection. In recent two years, home-made silver manufacturers have a situation of quick direct tracking, but the market share of the silver manufacturers is still lower than 50 percent.
The front-side conductive silver paste of the solar cell is subjected to screen printing, drying and high-temperature sintering to form a front-side silver electrode on the silicon wafer, so that the photoelectric effect of conducting the cell is achieved, and sunlight is converted into current. The printed auxiliary grid wires matched with the ultra-fine line screen design can form relatively less light shielding, and can receive more sunlight, so that higher current can be generated, namely, higher battery conversion efficiency is achieved.
Therefore, the trend of the screen printing of the non-net-junction screen printing process has become the most direct way to improve the conversion efficiency of the battery in recent years. The development of the net gauze and the wire diameter of the net edition without knots in the last 10 years is changed from the opening of 400/18 to be more than or equal to 50um to the current opening of 480/11 and 520/11 to be less than or equal to 18um, the consumption of single silver paste is also reduced from 200mg to 80mg, and the net edition with the wire diameter of 9um is also in the research and development stage. The light shielding is reduced through the design of the fine line grid line, higher current is generated, namely, the battery is higher in conversion efficiency, meanwhile, the requirement of reducing cost and unit consumption is effectively met, and the evolution of the extremely fine line trend is also faced with the problem of low mass production yield under high-speed printing.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides an organic carrier mixed solution comprising an organic acid doped conductive organic polymer/epoxy soybean oil with the mass fraction concentration of 15-20% and a high-boiling point solvent with the mass fraction concentration of 80-85%, wherein the epoxy soybean oil and the high-boiling point solvent in the organic carrier solution are subjected to grafting copolymerization with bisphenol A epoxy resin through basic amine serving as a curing agent, anhydride serving as a crosslinking agent and boron trifluoride monoethylamine complex serving as an accelerating agent to form a conductive silver paste solution which wraps nano glass powder and nano silver particles, the conductive silver paste solution can effectively wet the contact between inorganic powder and mesh materials, provides more excellent fine line ink penetrating capability, is suitable for high-speed printing of an ultrafine grid of a current large-area silicon wafer, and has excellent line width control capability for the fine grid, so that a better electrode aspect ratio can be formed.
The technical scheme of the invention is as follows: the front-side conductive silver paste for the solar cell comprises the following components in parts by weight:
the organic carrier mixed solution comprises an organic acid doped conductive organic polymer/epoxidized soybean oil with the mass fraction concentration of 15-20% and a high boiling point solvent with the mass fraction concentration of 80-85%.
Further, the preparation method of the organic acid doped conductive organic polymer/epoxidized soybean oil comprises the following steps:
M1: mixing 4-7 parts of aniline and 10-15 parts of organic acid in 200-300 parts of distilled water, and stirring at 200-250rpm for 45-60min at 0-4 ℃ to form a mixed solution;
m2: slowly adding 10-15 parts of ammonium persulfate and 10-15 parts of conductive organic polymer into the mixed solution obtained in the step M1, so that the molar ratio of the ammonium persulfate to the organic acid to the conductive organic polymer is 0.5-1:0.5-1:1-1.5, and stirring for 1h-1.2h at a rotating speed of 150-170 rpm;
M3: adding 25-30 parts of acetone into the mixture obtained in the step M2 to finish polymerization, so as to obtain an organic acid doped conductive organic polymer precursor;
m4: washing the precursor of the organic acid doped conductive organic polymer obtained in the step M3 by using distilled water and acetone alternately for 3-5 times, and drying overnight in a baking oven at 60-70 ℃ to obtain the organic acid doped conductive organic polymer;
M5: dissolving the organic acid doped conductive organic polymer obtained in the step M4 and solid-phase epoxy soybean oil in 300-500 parts of acetone, and dissolving for 1-1.5 hours by adopting ultrasonic waves;
M6: stirring the mixture in the step M5 at 50-60 ℃ for 4-5 hours to completely volatilize acetone, and drying the obtained mixture in a vacuum oven to obtain the organic acid doped conductive organic polymer/epoxidized soybean oil;
the organic acid is one or more of camphorsulfonic acid, dodecylbenzene sulfonic acid or p-toluene sulfonic acid.
Further, the preparation method of the epoxidized soybean oil comprises the following steps:
a1: uniformly mixing 70-80 parts of soybean oil with 20-30 parts of acetic acid, then placing the mixture and 40-50 parts of mordenite catalyst at the bottom of a bottle together, and standing and soaking for 20-30 min;
A2: dropwise adding 100-120 parts of H 2O2 into the mixture obtained in the step A1, continuously stirring at a rotating speed of 100-150rpm in the dropwise adding process, and maintaining the temperature at 65-75 ℃;
a3: passing the mixture obtained in the step A2 through a polyvinylidene fluoride filter membrane with the thickness of 3-5 mu m to remove mordenite catalyst, washing a liquid phase layer obtained by separation by adopting Na 2CO3 solution with the mass fraction concentration of 2-3%, and then removing water by adopting MgSO 4;
a4: and (3) drying the substance obtained in the step A3 in a vacuum oven at 55-65 ℃ overnight to obtain the solid-phase epoxidized soybean oil.
Further, the particle size of the nano silver particles is 2nm-5nm.
Further, the nano glass powder is one or more of nano Bi 2O3, nano BN, nano B 2O3, nano P 2O5, nano TiO 2 and nano A1 2O3.
Further, the anhydride is one or more of maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride and methyl hexahydrophthalic anhydride.
Further, the conductive organic polymer is one or more of polyacetylene, polyfuran or polyparaphenylene.
Further, the basic amine used as the curing agent is one or more of tributylamine, hexamethylenetetramine, diethylenetriamine and ethylenediamine.
Further, the high boiling point solvent is butyl anhydride acetate, diethylene glycol butyl ether acetate and diethylene glycol diethyl ether acetate.
The invention also provides a preparation method of the front-side conductive silver paste of the solar cell, which comprises the following steps:
S1: dissolving the nano silver particles in 50-100mL of NH 4 OH, stirring for 2-5min, and then adding into 4-8mL of formic acid to activate the nano silver particles;
s2: mixing the mixed solution with activated nano silver particles obtained in the step S1 with the nano glass powder in parts by weight, adding the organic carrier mixed solution in parts by weight, stirring at a speed of 120-150rpm for 20-30 min at a temperature of 30-40 ℃, and dropwise adding the tetraethyl titanate in parts by weight in the stirring process for promoting the adhesive force of the nano glass powder taking the organic carrier as a matrix and the nano silver particles during loading;
s3: and (2) adding the bisphenol A epoxy resin, the alkaline amine serving as a curing agent, the anhydride serving as a crosslinking agent and the boron trifluoride monoethylamine complex serving as an accelerator into the mixed solution obtained in the step (S2), stirring at 120-150 ℃ and a rotating speed of 100-150rpm, and standing at room temperature for 15-30 min to obtain the conductive silver paste on the front surface of the solar cell.
The beneficial technical effects of the invention are as follows:
1. The conductive silver paste solution which is formed by graft copolymerization of alkaline amine serving as a curing agent, anhydride serving as a cross-linking agent and boron trifluoride monoethylamine complex serving as an accelerator and bisphenol A epoxy resin and wraps nano glass powder and nano silver particles can effectively wet the contact between inorganic powder and mesh materials, provides excellent fine line ink penetrating capability, is suitable for high-speed printing of superfine grids of current large-area silicon wafers, and has excellent line width control capability for fine grids, so that a better electrode height-width ratio can be formed.
2. The conductive silver paste provided by the invention adopts a novel organic carrier mixed solution comprising an organic acid doped conductive organic polymer/epoxy soybean oil with the mass fraction concentration of 15-20% and a high-boiling point solvent with the mass fraction concentration of 80-85%, and has a unique dispersing effect on the current high-solid-content positive silver paste design, so that the optimal compatibility and lubricating function between inorganic powder and mesh materials can be achieved. Secondly, preparing an organic carrier in a common activation mode, so that silver microparticles and nano glass powder can be uniformly dispersed in an organic carrier mixed solution to produce the novel ultrafine linear front conductive silver paste suitable for advanced screen printing
3. According to the conductive silver paste provided by the invention, inorganic powder such as nano silver particles and nano glass powder with different particle sizes is wrapped by the organic carrier mixed solution, so that a lubricating medium between the inorganic powder and a mesh-free mesh cloth material (such as polyimide or epoxy resin) for preparing a front electrode of a solar cell is effectively formed, the high-solid-content paste has better ink permeability under a narrow-opening screen printing technology, is widely applicable to different production line printing conditions, and effectively controls the aspect ratio of grid lines, and is directly reflected in better photoelectric conversion efficiency.
4. The glass powder of the conductive silver paste provided by the invention adopts nano-scale, can be more fully loaded in the organic carrier mixed solution, improves the loading rate, further improves the welding rate of the nano silver particles welded on a silicon wafer substrate prepared by a battery piece, does not adopt oxide glass powder containing lead as a welding material, and reduces the harm to human bodies.
5. The conductive silver paste provided by the invention adopts a self-prepared organic carrier mixed solution comprising an organic acid doped conductive organic polymer/epoxy soybean oil with the mass fraction concentration of 15% -20% and a high-boiling point solvent with the mass fraction concentration of 80% -85%, and does not adopt an organic carrier formed by terpineol matched with polyester such as glycol ethyl ether acetate and the like which are commonly adopted in the prior art, so that the problem of poor curing capability caused by stronger volatility of the organic carrier provided by the prior art is avoided, and the conductive silver paste has more excellent fine grid line ink penetration capability.
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 a front-side conductive silver paste of a solar cell, which is prepared from the following components in parts by weight:
The organic carrier mixed solution comprises dodecylbenzene sulfonic acid doped polyfuran/epoxy soybean oil with the mass fraction concentration of 15% and butyl anhydride acetate with the mass fraction concentration of 85%.
The preparation method of the dodecylbenzene sulfonic acid doped polyfuran/epoxy soybean oil comprises the following steps:
M1: mixing 4 parts of aniline and 15 parts of dodecylbenzene sulfonic acid in300 parts of distilled water, and stirring at 200rpm for 60min at 0 ℃ to form a mixed solution;
M2: slowly adding 12 parts of ammonium persulfate and 12 parts of polyfuran into the mixed solution obtained in the step M1, enabling the molar ratio of the ammonium persulfate to the dodecylbenzene sulfonic acid to the polyfuran to be 0.5:0.5:1, and stirring at a rotating speed of 150rpm for 1.2 hours;
M3: adding 25 parts of acetone into the mixture obtained in the step M2 to finish polymerization, so as to obtain a dodecylbenzenesulfonic acid doped polyfuran precursor;
m4: washing the dodecylbenzenesulfonic acid doped polyfuran precursor obtained in the step M3 by using distilled water and acetone alternately for 3 times, and then drying overnight in a 60 ℃ oven to obtain the dodecylbenzenesulfonic acid doped polyfuran;
m5: dissolving the dodecylbenzenesulfonic acid doped polyfuran obtained in the step M4 and solid-phase epoxy soybean oil in 300 parts of acetone, and dissolving for 1h by adopting ultrasonic waves;
M6: and (3) stirring the mixture obtained in the step M5 at 50 ℃ for 4 hours to completely volatilize the acetone, and drying the obtained mixture in a vacuum oven to obtain the dodecylbenzenesulfonic acid doped polyfuran/epoxidized soybean oil.
The preparation method of the epoxidized soybean oil adopted in the embodiment comprises the following steps:
a1: uniformly mixing 80 parts of soybean oil and 20 parts of acetic acid, then placing the mixture and 40 parts of mordenite catalyst at the bottom of a bottle together, and standing and soaking for 20min;
a2: dropwise adding 100 parts of H 2O2 into the mixture obtained in the step A1, continuously stirring at a speed of 100rpm in the dropwise adding process, and maintaining the temperature at 70 ℃;
A3: passing the mixture obtained in the step A2 through a polyvinylidene fluoride filter membrane with the thickness of 3 mu m to remove a mordenite catalyst, washing a liquid phase layer obtained by separation by adopting Na 2CO3 solution with the mass fraction concentration of 2%, and then removing water by adopting MgSO 4;
a4: and (3) drying the substance obtained in the step A3 in a vacuum oven at 55 ℃ overnight to obtain the solid-phase epoxidized soybean oil.
The embodiment also provides a preparation method of the front-side conductive silver paste of the solar cell, which comprises the following steps:
S1: 30 parts of nano silver particles with the particle size of 5nm are dissolved in 50mL of NH 4 OH, stirred for 2min, added into 6mL of formic acid, and activated;
S2: mixing the mixed solution with activated nano silver particles obtained in the step S1 with 40 parts of nano B 2O3 with the particle size of 20nm, adding 50 parts of organic carrier mixed solution, stirring at the speed of 120rpm for 30min at the temperature of 30 ℃, and dropwise adding 8 parts of tetraethyl titanate in the stirring process to promote the adhesive force of the nano B 2O3 taking the organic carrier as a matrix and the nano silver particles during loading;
s3: and (2) adding 40 parts of bisphenol A epoxy resin, 9 parts of hexamethylenetetramine serving as a curing agent, 7 parts of hexahydrophthalic anhydride serving as a cross-linking agent and 11 parts of boron trifluoride monoethylamine complex serving as an accelerator into the mixed solution obtained in the step (S2), stirring at 120 ℃ and 150rpm, and standing at room temperature for 15min to obtain the conductive silver paste on the front surface of the solar cell.
Example 2
The embodiment provides a front-side conductive silver paste of a solar cell, which is prepared from the following components in parts by weight:
The organic carrier mixed solution comprises 20% of camphorsulfonic acid doped polyacetylene/epoxidized soybean oil and 80% of diethylene glycol diethyl ether acetate.
The preparation method of the camphorsulfonic acid doped polyacetylene/epoxidized soybean oil comprises the following steps:
m1: mixing 5 parts of aniline and 12 parts of camphorsulfonic acid in 250 parts of distilled water, and stirring at 220rpm for 50min at 2 ℃ to form a mixed solution;
M2: slowly adding 10 parts of ammonium persulfate and 15 parts of polyacetylene into the mixed solution obtained in the step M1, enabling the molar ratio of the ammonium persulfate to the camphorsulfonic acid to the polyacetylene to be 0.75:1:1.5, and stirring at 160rpm for 1h;
M3: adding 30 parts of acetone into the mixture obtained in the step M2 to finish polymerization, so as to obtain a camphorsulfonic acid doped polyacetylene precursor;
M4: washing the camphorsulfonic acid doped polyacetylene precursor obtained in the step M3 by using distilled water and acetone alternately for 5 times, and then drying the precursor in a drying oven at 65 ℃ overnight to obtain camphorsulfonic acid doped polyacetylene;
M5: dissolving camphorsulfonic acid doped polyacetylene obtained in the step M4 and solid-phase epoxy soybean oil in 500 parts of acetone, and dissolving for 1.5 hours by adopting ultrasonic waves;
m6: stirring the mixture obtained in the step M5 at 55 ℃ for 4.5 hours to volatilize acetone completely, and drying the obtained mixture in a vacuum oven to obtain camphorsulfonic acid doped polyacetylene/epoxidized soybean oil;
the preparation method of the epoxidized soybean oil adopted in the embodiment comprises the following steps:
a1: uniformly mixing 70 parts of soybean oil with 25 parts of acetic acid, then placing the mixture and 45 parts of mordenite catalyst at the bottom of a bottle together, standing and soaking for 30min;
A2: dropwise adding 110 parts of H 2O2 into the mixture obtained in the step A1, continuously stirring at 150rpm in the dropwise adding process, and maintaining the temperature at 65 ℃;
A3: passing the mixture obtained in the step A2 through a polyvinylidene fluoride filter membrane with the thickness of 4 mu m to remove mordenite catalyst, washing a liquid phase layer obtained by separation by adopting Na 2CO3 solution with the mass fraction concentration of 2.5%, and then removing water by adopting MgSO 4;
a4: and (3) drying the substance obtained in the step A3 in a vacuum oven at 60 ℃ overnight to obtain the solid-phase epoxidized soybean oil.
The invention also provides a preparation method of the front-side conductive silver paste of the solar cell, which comprises the following steps:
S1: dissolving 20 parts of nano silver particles with the particle size of 3nm in 80mL of NH 4 OH, stirring for 4min, and adding into 8mL of formic acid to activate the nano silver particles;
S2: mixing the mixed solution with activated nano silver particles obtained in the step S1 with 5 parts of nano BN with the particle size of 45nm, 15 parts of nano Bi 2O3 with the particle size of 30nm and 10 parts of nano P 2O5 with the particle size of 50nm, adding 55 parts of organic carrier mixed solution, stirring at the speed of 150rpm for 20min at the temperature of 35 ℃, and dropwise adding 10 parts of tetraethyl titanate in the stirring process for promoting the adhesive force when the nano BN, the nano Bi 2O3, the nano P 2O5 and the nano silver particles taking the organic carrier as a matrix are loaded;
S3: and (2) adding the bisphenol A epoxy resin, the diethylenetriamine serving as a curing agent, 5 parts of glutaric anhydride serving as a cross-linking agent and 15 parts of boron trifluoride monoethylamine complex serving as an accelerator into the mixed solution obtained in the step (S2), stirring at 130 ℃ and 100rpm, and standing at room temperature for 30min to obtain the conductive silver paste on the front surface of the solar cell.
Example 3
The conductive silver paste for the front surface of the solar cell comprises the following components in parts by weight:
The organic carrier mixed solution comprises p-toluenesulfonic acid doped poly-p-phenylene/epoxidized soybean oil with the mass fraction concentration of 18%, and diethylene glycol butyl ether acetate with the mass fraction concentration of 82%.
The preparation method of the p-toluenesulfonic acid doped poly-p-phenylene/epoxidized soybean oil comprises the following steps:
m1: mixing 7 parts of aniline and 10 parts of p-toluenesulfonic acid in 200 parts of distilled water, and stirring at 250rpm for 45min at 4 ℃ to form a mixed solution;
M2: slowly adding 15 parts of ammonium persulfate and 10 parts of polyparaphenylene into the mixed solution obtained in the step M1, so that the molar ratio of the ammonium persulfate to the polyparatoluene sulfonic acid to the polyparaphenylene is 1:0.8:0.7, and stirring at 170rpm for 1.1h;
M3: adding 27 parts of acetone into the mixture obtained in the step M2 to finish polymerization, so as to obtain a p-toluenesulfonic acid doped poly-p-phenylene/epoxidized soybean oil precursor;
m4: washing the p-toluenesulfonic acid doped poly-p-phenylene/epoxidized soybean oil precursor obtained in the step M3 by adopting distilled water and acetone alternately for 3 times, and then drying the p-toluenesulfonic acid doped poly-p-phenylene/epoxidized soybean oil precursor in a 70 ℃ oven overnight to obtain p-toluenesulfonic acid doped poly-p-phenylene;
M5: dissolving the p-toluenesulfonic acid doped poly-p-phenylene and solid-phase epoxidized soybean oil obtained in the step M4 in 400 parts of acetone, and adopting ultrasonic dissolution for 1.2 hours;
M6: and (3) stirring the mixture obtained in the step M5 at 60 ℃ for 5 hours to completely volatilize the acetone, and drying the obtained mixture in a vacuum oven to obtain the p-toluenesulfonic acid doped poly-p-phenylene/epoxidized soybean oil.
The preparation method of the epoxidized soybean oil adopted in the embodiment comprises the following steps:
A1: uniformly mixing 75 parts of soybean oil and 30 parts of acetic acid, then placing the mixture and 50 parts of mordenite catalyst at the bottom of a bottle together, standing and soaking for 25min;
A2: dropwise adding 120 parts of H 2O2 into the mixture obtained in the step A1, continuously stirring at 120rpm in the dropwise adding process, and maintaining the temperature at 75 ℃;
A3: passing the mixture obtained in the step A2 through a polyvinylidene fluoride filter membrane with the thickness of 5 mu m to remove a mordenite catalyst, washing a liquid phase layer obtained by separation by adopting a Na 2CO3 solution with the mass fraction concentration of 3%, and then removing water by adopting MgSO 4;
A4: and (3) drying the substance obtained in the step A3 in a vacuum oven at 65 ℃ overnight to obtain the solid-phase epoxidized soybean oil.
The invention also provides a preparation method of the front-side conductive silver paste of the solar cell, which comprises the following steps:
S1: dissolving 40 parts of nano silver particles with the particle size of 3nm in 100mL of NH 4 OH, stirring for 5min, and adding into 4mL of formic acid to activate the nano silver particles;
S2: mixing the mixed solution with activated nano silver particles obtained in the step S1 with 50 parts of nano A1 2O3 with the particle size of 35nm, adding 60 parts of organic carrier mixed solution, stirring at the speed of 125rpm for 25min at the temperature of 40 ℃, and dropwise adding 9 parts of tetraethyl titanate in the stirring process to promote the adhesion of the nano A1 2O3 with the particle size of 35nm and the load with the particle size of 3nm by taking an organic carrier as a matrix;
S3: and (2) adding 43 parts of bisphenol A epoxy resin, 6 parts of tributylamine serving as a curing agent, 10 parts of maleic anhydride serving as a cross-linking agent and 8 parts of boron trifluoride monoethylamine complex serving as an accelerator into the mixed solution obtained in the step (S2), stirring at 150 ℃ and 130rpm, and standing at room temperature for 20min to obtain the conductive silver paste on the front surface of the solar cell.
Comparative example 1
The present comparative example differs from example 1 only in that dodecylbenzenesulfonic acid-doped polyfuran/soybean oil was used in the organic carrier mixed solution in the raw material for preparing the conductive silver paste, dodecylbenzenesulfonic acid-doped polyfuran/epoxidized soybean oil was not used, and the preparation method and procedure of dodecylbenzenesulfonic acid-doped polyfuran/soybean oil used in the present comparative example were as described in example 1, using soybean oil instead of epoxidized soybean oil prepared in example 1.
Comparative example 2
The comparative example differs from example 1 only in that epoxidized soybean oil was used in the organic vehicle mixed solution in the raw material for preparing the conductive silver paste, and the preparation method and procedure of the epoxidized soybean oil were as described in example 1.
Comparative example 3
The comparative example differs from example 1 only in that the solvent used in the organic vehicle mixed solution in the raw material for preparing the conductive silver paste is not a high boiling point solvent, butyl anhydride acetate, and octanol in the prior art is used instead of butyl anhydride acetate in example 1.
Comparative example 4
The present comparative example differs from example 1 only in that in the raw material for preparing the conductive silver paste, curing agent EH-3293S was used instead of hexamethyltetramine, hydrogen-containing polysiloxane crosslinking agent of Si-H bond was used instead of hexahydrophthalic anhydride, and imidazole-based accelerator was used instead of boron trifluoride monoethylamine complex.
Test example 1
The solid content of the conductive silver pastes prepared in examples 1 to 3 and comparative examples 1 to 3 was measured as follows:
a. Opening an analytical balance and setting zero;
b. recording the weight of the crucible (data 1) on a clean crucible electronic balance, and setting the electronic balance to zero;
c. 1.0-2.0g silver paste is weighed on a crucible, and after the reading of an electronic balance is stable, the reading is recorded
(Data 2);
d. And (3) placing the crucible weighing the silver paste into a muffle furnace, and sintering for 10min at 750 ℃. Taking out the crucible after cooling to room temperature, placing the crucible on an electronic balance for weighing, and recording and reading (data 3);
e. The solid content calculation formula is as follows:
The results are shown in Table 1. The solid content measurement can be used for calculating the content of metallic silver, and is the silver powder content and performance, which are main factors for determining the quality and electrical performance of the coating, so that the larger the solid content is, the more excellent the performance of the prepared conductive silver paste is.
Test example 2
The viscosities of the conductive silver pastes prepared in examples 1 to 3 and comparative examples 1 to 3 were measured as follows:
a. the Brookfield DV1 viscosity tester is turned on, and the test can be performed when the water bath is heated and kept at 25 ℃. The slurry to be measured is placed for more than 1h at room temperature.
B. Filling a proper amount of slurry, and inserting into a rotor SC-14; standing for 10 minutes at the constant temperature of 25 ℃ in water bath;
c. The rotational speed was adjusted to 10/50/100rpm, measurement was started, and the value after 1min of each rotational speed was read and recorded (at this time, the viscosity count value should be relatively stable). The results are shown in Table 1. The viscosity represents the adhesive force of the conductive silver paste from the side, so that the higher the viscosity represents the higher adhesive force, the higher the adhesive force represents the stronger the sintering or bonding strength of the nano silver particles and the substrate bonded with the nano silver particles, and the higher the photoelectric conversion capability of the solar cell.
Test example 3
The conductive silver pastes prepared in examples 1 to 3 and comparative examples 1 to 3 were printed on SiN layers (166×166 mm) of silicon wafer substrates by screen printing technique, and their printing properties were examined. The electrical and printing screen sizes used were, respectively, mesh-free screen 480 and 520 mesh/11 μm line diameter/total thickness 22-25 μm/opening 14-16 μm (narrow face opening) and mesh-free screen 520 mesh/11 μm line diameter/total thickness 22-25 μm/opening 18 μm,15 μm,13 μm,11 μm (narrow face opening). The battery piece is dried in an infrared drying furnace, then sintered in a belt sintering furnace for 40 seconds at 920-930 ℃. And cooling the sintered conductive paste to form the electrode. The sheet resistance of the printed electrode is directly measured by adopting a resistance tester, the smaller the sheet resistance value is, the lower the surface impurity concentration of the prepared solar cell is, the lower the surface impurity recombination center is, and the higher the surface minority carrier survival rate is, so that the lower the power loss in the photoelectric conversion process is, the total power loss caused by printing the printing template of the solar cell with a high-thin grid line is, the filling factor is improved, and the preparation of the high-efficiency solar cell is ensured. The results are shown in Table 1.
Test example 4
The photoelectric conversion efficiency of the solar cell prepared from the conductive silver paste prepared in examples 1 to 3 and comparative examples 1 to 3 was measured, and the specific steps were as follows:
The resulting solar cell was placed in a Berger solar cell tester under one light source condition for efficiency measurement. Xenon arc lamps in solar cell testers simulate sunlight of known intensity and radiate onto the light-receiving front surface of the cell. The voltage (V) and current (I) at a load resistance setting of about 400 are measured using a four-point contact method to determine a voltage-current curve of the battery, and then the battery conversion Efficiency (EFF) is calculated from the curve. The results are shown in Table 1.
TABLE 1
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 (9)
1. The front-side conductive silver paste for the solar cell is characterized by comprising the following components in parts by weight:
40-50 parts of bisphenol A epoxy resin;
20-40 parts of nano silver particles;
30-50 parts of nano glass powder with the particle size of 20-50 nm;
50-60 parts of organic carrier mixed solution;
8-10 parts of tetraethyl titanate;
6-9 parts of alkaline amine as a curing agent;
5-10 parts of anhydride serving as a cross-linking agent;
8-15 parts of boron trifluoride monoethylamine complex as a promoter;
The organic carrier mixed solution comprises an organic acid doped conductive organic polymer/epoxidized soybean oil with the mass fraction concentration of 15-20% and a high boiling point solvent with the mass fraction concentration of 80-85%;
The high boiling point solvent is butyl anhydride acetate, diethylene glycol butyl ether acetate and diethylene glycol diethyl ether acetate.
2. The solar cell front side conductive silver paste according to claim 1, wherein the preparation method of the organic acid doped conductive organic polymer/epoxy soybean oil comprises the following steps:
M1: mixing 4-7 parts of aniline and 10-15 parts of organic acid in 200-300 parts of distilled water, and stirring at 200-250rpm for 45-60min at 0-4 ℃ to form a mixed solution;
m2: slowly adding 10-15 parts of ammonium persulfate and 10-15 parts of conductive organic polymer into the mixed solution obtained in the step M1, so that the molar ratio of the ammonium persulfate to the organic acid to the conductive organic polymer is 0.5-1:0.5-1:1-1.5, and stirring for 1h-1.2h at a rotating speed of 150-170 rpm;
M3: adding 25-30 parts of acetone into the mixture obtained in the step M2 to finish polymerization, so as to obtain an organic acid doped conductive organic polymer precursor;
m4: washing the precursor of the organic acid doped conductive organic polymer obtained in the step M3 by using distilled water and acetone alternately for 3-5 times, and drying overnight in a baking oven at 60-70 ℃ to obtain the organic acid doped conductive organic polymer;
M5: dissolving the organic acid doped conductive organic polymer obtained in the step M4 and solid-phase epoxy soybean oil in 300-500 parts of acetone, and dissolving for 1-1.5 hours by adopting ultrasonic waves;
M6: stirring the mixture in the step M5 at 50-60 ℃ for 4-5 hours to completely volatilize acetone, and drying the obtained mixture in a vacuum oven to obtain the organic acid doped conductive organic polymer/epoxidized soybean oil;
the organic acid is one or more of camphorsulfonic acid, dodecylbenzene sulfonic acid or p-toluene sulfonic acid.
3. The solar cell front side conductive silver paste of claim 2, wherein the preparation method of the epoxidized soybean oil comprises the following steps:
A1: uniformly mixing 70-80 parts of soybean oil with 20-30 parts of acetic acid, then placing the mixture and 40-50 parts of mordenite catalyst at the bottom of a bottle together, and standing and soaking for 20-30 min;
A2: dropwise adding 100-120 parts of H 2O2 into the mixture obtained in the step A1, continuously stirring at a rotating speed of 100-150rpm in the dropwise adding process, and maintaining the temperature at 65-75 ℃;
A3: passing the mixture obtained in the step A2 through a polyvinylidene fluoride filter membrane with the thickness of 3-5 mu m to remove mordenite catalyst, washing a liquid phase layer obtained by separation by adopting Na 2CO3 solution with the mass fraction concentration of 2-3%, and then removing water by adopting MgSO 4;
a4: and (3) drying the substance obtained in the step A3 in a vacuum oven at 55-65 ℃ overnight to obtain the solid-phase epoxidized soybean oil.
4. The front side conductive silver paste of claim 1, wherein the nano silver particles have a particle size of 2nm to 5nm.
5. The solar cell front side conductive silver paste of claim 1, wherein the nano glass powder is one or more of nano Bi 2O3, nano BN, nano B 2O3, nano P 2O5, nano TiO 2, and nano Al 2O3.
6. The front side conductive silver paste of claim 1, wherein the acid anhydride is one or more of maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
7. The solar cell front side conductive silver paste of claim 1, wherein the conductive organic polymer is one or more of polyacetylene, polyfuran, or polyparaphenylene.
8. The front-side conductive silver paste for a solar cell according to claim 1, wherein the basic amine as the curing agent is one or more of tributylamine, hexamethylenetetramine, diethylenetriamine and ethylenediamine.
9. The method for preparing the conductive silver paste for the front surface of the solar cell according to any one of claims 1 to 8, comprising the following steps:
S1: dissolving the nano silver particles in 50-100 mL parts by weight of NH 4 OH, stirring for 2-5min, and then adding into 4-8mL of formic acid to activate the nano silver particles;
s2: mixing the mixed solution with activated nano silver particles obtained in the step S1 with the nano glass powder in parts by weight, adding the organic carrier mixed solution in parts by weight, stirring at a speed of 120-150rpm for 20-30 min at a temperature of 30-40 ℃, and dropwise adding the tetraethyl titanate in parts by weight in the stirring process for promoting the adhesive force of the nano glass powder taking the organic carrier as a matrix and the nano silver particles during loading;
s3: and (2) adding the bisphenol A epoxy resin, the alkaline amine serving as a curing agent, the anhydride serving as a crosslinking agent and the boron trifluoride monoethylamine complex serving as an accelerator into the mixed solution obtained in the step (S2), stirring at 120-150 ℃ and a rotating speed of 100-150rpm, and standing at room temperature for 15-30 min to obtain the conductive silver paste on the front surface of the solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111435811.0A CN114464338B (en) | 2021-11-29 | 2021-11-29 | Front-side conductive silver paste of solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111435811.0A CN114464338B (en) | 2021-11-29 | 2021-11-29 | Front-side conductive silver paste of solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114464338A CN114464338A (en) | 2022-05-10 |
| CN114464338B true CN114464338B (en) | 2024-06-28 |
Family
ID=81405194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111435811.0A Active CN114464338B (en) | 2021-11-29 | 2021-11-29 | Front-side conductive silver paste of solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114464338B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116031012B (en) * | 2023-01-10 | 2023-09-22 | 惠州市帕克威乐新材料有限公司 | Nano conductive silver paste and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821898A (en) * | 2007-09-26 | 2010-09-01 | 第一工业制药株式会社 | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
| CN102629496A (en) * | 2012-04-27 | 2012-08-08 | 西安银泰新能源材料科技有限公司 | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5819712B2 (en) * | 2011-11-28 | 2015-11-24 | 京都エレックス株式会社 | Heat curable conductive paste composition |
| CN102831955B (en) * | 2012-08-24 | 2014-08-20 | 合肥中南光电有限公司 | Silver paste with nanoscale mixed silver powder on front surface of solar cell and preparation method of silver paste |
| JP6266241B2 (en) * | 2013-07-12 | 2018-01-24 | 富山薬品工業株式会社 | Conductive polymer composition and method for producing the same |
| CN104464887B (en) * | 2014-11-17 | 2016-09-14 | 苏州斯迪克新材料科技股份有限公司 | A kind of nano-silver thread conductive silver paste and preparation method thereof |
| CN107331434A (en) * | 2017-06-30 | 2017-11-07 | 北京市合众创能光电技术有限公司 | A kind of crystal silicon solar energy battery major-minor grid line separation printing positive silver paste combination and preparation method thereof |
| CN108806823A (en) * | 2018-06-14 | 2018-11-13 | 扬州鑫晶光伏科技有限公司 | Environment-friendlyconductive conductive silver paste material and preparation method thereof and crystal silicon solar batteries prepared therefrom |
| CN110176325A (en) * | 2019-06-10 | 2019-08-27 | 苏州柏特瑞新材料有限公司 | A kind of low-temperature bake heterojunction solar battery conductive silver paste and preparation method thereof |
| CN110504070A (en) * | 2019-09-30 | 2019-11-26 | 无锡帝科电子材料股份有限公司 | Electrocondution slurry, preparation method and application, electrode of solar battery and solar battery comprising it |
| CN113035408B (en) * | 2020-03-17 | 2024-02-02 | 深圳市百柔新材料技术有限公司 | Solar cell grid line slurry and preparation method thereof, and solar cell |
-
2021
- 2021-11-29 CN CN202111435811.0A patent/CN114464338B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821898A (en) * | 2007-09-26 | 2010-09-01 | 第一工业制药株式会社 | Process for producing electroconductive polymer electrode and dye-sensitized solar cell comprising the electroconductive polymer electrode |
| CN102629496A (en) * | 2012-04-27 | 2012-08-08 | 西安银泰新能源材料科技有限公司 | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114464338A (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102136308B (en) | Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste | |
| CN101952903B (en) | Aluminum pastes and use thereof in the production of silicon solar cells | |
| CN114464338B (en) | Front-side conductive silver paste of solar cell and preparation method thereof | |
| CN101990688A (en) | Aluminum pastes and use thereof in the production of silicon solar cells | |
| CN103582916B (en) | For silver paste composition forming electrode and preparation method thereof | |
| CN102324266B (en) | Glass-powder-free crystalline silicon solar battery aluminum paste and preparation method thereof | |
| CN102347094A (en) | Aluminium paste for preparing crystal silicon solar cell aluminium back surface field and manufacture method thereof | |
| CN102460602A (en) | Paste and solar cell using the same | |
| US10497819B2 (en) | Efficient back surface field paste for crystalline silicon solar cells and preparation method thereof | |
| CN109215837A (en) | A kind of conductive silver slurry used for solar batteries and preparation method thereof | |
| CN114267474A (en) | High-performance metallization paste for solar cell and preparation method thereof | |
| CN109659068B (en) | Low-temperature curing type back silver paste for all-aluminum back surface field crystalline silicon solar cell | |
| CN102103895B (en) | Silver paste used for positive electrodes of solar batteries and grid lines, preparation method thereof and solar battery containing same | |
| CN108511107A (en) | A kind of back of the body passivation aluminium paste and preparation method thereof containing porous structure powder | |
| CN105244074B (en) | A kind of crystal silicon solar energy battery aluminium paste | |
| CN116779212A (en) | Front silver-aluminum paste for TOPCON solar cell and preparation method and application thereof | |
| CN103824653A (en) | Method for preparing back-field slurry of high-performance crystal silicon solar cell | |
| CN114429830B (en) | Metal slurry with good fluidity and uniformity and preparation method thereof | |
| CN102568647B (en) | For paste composition and the solar cell comprising said composition of the rear electrode of solar cell | |
| CN104575667A (en) | Conductive silver paste for frontage of crystalline silicon solar cell | |
| CN106280167A (en) | A kind of solaode aluminium paste organic binder bond | |
| CN115798786B (en) | High-adhesion back surface field aluminum conductive paste for crystalline silicon solar cell and preparation method thereof | |
| CN116072327B (en) | Ferrite magnetic core, composite silver paste thereof, preparation method and application | |
| CN117457258B (en) | Preparation method and application of conductive silver paste | |
| CN110120276B (en) | Conductive paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |