CN109671784B - Preparation process of binder for solar cell back electrode slurry - Google Patents
Preparation process of binder for solar cell back electrode slurry Download PDFInfo
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- CN109671784B CN109671784B CN201811356807.3A CN201811356807A CN109671784B CN 109671784 B CN109671784 B CN 109671784B CN 201811356807 A CN201811356807 A CN 201811356807A CN 109671784 B CN109671784 B CN 109671784B
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- 239000011230 binding agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011267 electrode slurry Substances 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920002752 Konjac Polymers 0.000 claims abstract description 37
- 235000010485 konjac Nutrition 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 241001312219 Amorphophallus konjac Species 0.000 claims abstract description 33
- 235000001206 Amorphophallus rivieri Nutrition 0.000 claims abstract description 33
- 239000000252 konjac Substances 0.000 claims abstract description 33
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000013312 flour Nutrition 0.000 claims abstract description 28
- 229920005610 lignin Polymers 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229920002472 Starch Polymers 0.000 claims abstract description 10
- 239000008107 starch Substances 0.000 claims abstract description 10
- 235000019698 starch Nutrition 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- 239000002003 electrode paste Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000005251 gamma ray Effects 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007767 bonding agent Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 238000005286 illumination Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 4
- 229940031826 phenolate Drugs 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
Classifications
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- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a preparation process of a binder for solar cell back electrode slurry, which comprises the following steps: step one, mixing 40-50 parts of modified konjac flour and 20-30 parts of defatted starch, then adding 25-35 parts of deionized water while stirring, then adding 5-15 parts of modified montmorillonite, increasing the stirring speed to 300-400r/min, and stirring for 20-30 min. The konjac flour aqueous solution has high viscosity, the bonding strength is higher than that of other biological adhesives, the konjac flour aqueous solution is suitable for being used as a main material of a bonding agent, the activity of the konjac flour is enhanced by modifying the konjac flour aqueous solution with lignin phenolization liquid, hydroxyl groups contained on the surface of the konjac flour are increased, and the defatted starch also contains a large number of hydroxyl groups.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation process of a binder for solar cell back electrode slurry.
Background
Solar energy is a new energy source, which is more and more concerned by people, and the solar energy is converted into electric energy to be used for a photovoltaic panel, a photovoltaic panel component is a power generation device which can generate direct current when exposed to the sun, the solar energy is composed of solid photovoltaic cells which are almost completely made of semiconductor materials (such as silicon), and the solid photovoltaic cells can be operated for a long time without causing any loss because of no movable parts, simple photovoltaic cells can provide energy sources for watches and computers, more complex photovoltaic systems can provide illumination for houses, traffic signal lamps and monitoring systems, and are incorporated into a power grid for power supply, the photovoltaic panel component can be made into different shapes, and the components can be connected to generate more electric energy; and the electrode slurry has weak bonding force with the silicon plate, so that a binder is required to be used as an auxiliary material to improve the performance of the electrode slurry.
Although the existing binder is environment-friendly, the performance of the existing binder is deteriorated after long-term illumination, so that the adhesive force between electrode slurry and a photovoltaic panel is reduced, meanwhile, the raw materials are mixed, so that the electrode slurry is easy to agglomerate, and the photoelectric conversion efficiency is influenced, and the existing Chinese patent document (publication number: CN105469854B) discloses a plant source composite binder for the electrode slurry of the optical back of a polycrystalline silicon solar cell, wherein the content of each component is as follows by weight: 6-10 parts of Arabic gum, 2-6 parts of algin, 0.2-2 parts of sesbania gum, 0.05-0.2 part of talcum powder and 100 parts of water, and although the adhesive is environment-friendly, the crosslinking degree is large, the agglomeration is easy, the electrode slurry cannot be well dispersed, and the photoelectric conversion efficiency is influenced.
Chinese patent document (publication number: CN106675449B) discloses a high-safety cathode slurry binder for lithium ion batteries, which is prepared from raw materials such as sodium carboxymethylcellulose, styrene butadiene rubber, sodium alginate, a binder additive and the like, wherein the binder has good binding performance, but the styrene butadiene rubber raw material influences the photoelectric conversion efficiency of the electrode slurry.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a preparation process of a binder for a solar cell back electrode paste, so as to solve the problems in the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation process of a binder for solar cell back electrode slurry, which comprises the following steps:
step one, mixing 40-50 parts of modified konjac flour and 20-30 parts of defatted starch, then adding 25-35 parts of deionized water while stirring, then adding 5-15 parts of modified montmorillonite, increasing the stirring speed to 300-400r/min, stirring for 20-30min, then reducing the rotating speed to 80-140r/min, stirring for 50-60min, then adding 4-8 parts of modified nano titanium dioxide, then transferring to a high-pressure reaction kettle, reacting for 30-40min, and finishing the reaction to obtain a premix;
the preparation method of the modified konjac flour comprises the following steps: mixing the konjac flour and the lignin phenolization liquid according to a weight ratio of 5:1, then sending the mixture into a four-neck flask to react for 30-40min at a reaction temperature of 65-75 ℃, then adding glacial acetic acid to adjust the pH value to 5.0, then carrying out ultrasonic dispersion for 10-20min, then standing and aging for 20-30min, then adding nano calcium titanate accounting for 4-8% of the total amount of the konjac flour, then stirring at a stirring speed of 100-200r/min, stirring for 20-30min, and then washing, centrifuging and drying to obtain the konjac powder;
and step two, adding 2-7 parts of ammonium persulfate into the premix prepared in the step one, then carrying out water bath treatment, wherein the water bath temperature is 75-85 ℃, carrying out water bath for 40-50min, then transferring the product into an irradiation bag, filling nitrogen, sealing, and then carrying out irradiation treatment to obtain the binder.
Preferably, in the step one, the lignin phenolization liquid is obtained by mixing lignin and phenol according to a weight ratio of 5:2, then adding phosphoric acid accounting for 4-6% of the total weight of the lignin and the phenol, and then liquefying at 100-120 ℃ for 1-2 h.
Preferably, the preparation method of the modified montmorillonite comprises the steps of adding natural montmorillonite into deionized water for ultrasonic dispersion, then adding glacial acetic acid to adjust the pH value to 5.0-6.0, then sending into a magnetic stirrer, heating to 65-75 ℃, then adding hexadecyl trimethyl ammonium bromide accounting for 6-10% of the total weight of the montmorillonite, reacting for 30-40min, then centrifuging, then sending into a drying box at 80 ℃ for drying for 2-3h, then heating to 200 ℃ at 5 ℃/min, preserving the temperature for 30-40min, and then cooling to room temperature at 2 ℃/min.
Preferably, the specific surface area of the natural montmorillonite is 600-1000m2(ii)/g, the interlayer spacing is 1-3 nm.
Preferably, the preparation method of the modified nano titanium dioxide comprises the steps of adding the nano titanium dioxide into a sodium hydroxide solution with the mass fraction of 30-40%, performing ultrasonic dispersion for 20-30min, then adding a hydrogen peroxide solution with the mass fraction of 90%, reacting for 15-25min, standing for 10-20min, then adding a silane coupling agent, transferring to a reaction kettle, reacting for 1-2h at the reaction temperature of 85-95 ℃, and then washing, ionizing and drying.
Preferably, the silane coupling agent is gamma-aminopropyltriethoxysilane.
Preferably, the reaction temperature in the high-pressure reaction kettle in the step one is 90-110 ℃ and the reaction pressure is 2-6 MPa.
Preferably, the reaction temperature in the high-pressure reaction kettle in the step one is 100 ℃ and the reaction pressure is 4 MPa.
Preferably, the irradiation treatment in the second step adopts gamma ray irradiation for 2-6min, and the irradiation dose is 2-12 KGy.
Preferably, the irradiation treatment in the second step adopts gamma ray irradiation for 3min, and the irradiation dose is 7 KGy.
Compared with the prior art, the invention has the following beneficial effects:
the konjak powder aqueous solution has high viscosity, the bonding strength is higher than that of other biological adhesives, the konjak powder aqueous solution is suitable for being used as a main material of an adhesive, the lignin phenolization liquid is adopted for modifying the konjak powder, the activity of the konjak powder is enhanced, the hydroxyl group contained on the surface is increased, the degreased starch also contains a large amount of hydroxyl group, the hydroxyl group and the degreased starch are combined by an initiator, the bonding force between the raw materials is improved, the bonding strength is improved, the uncombined hydroxyl group is combined with the active group in the raw materials, the water resistance of the material is further improved, the montmorillonite is modified, the montmorillonite becomes bulked and has increased volume in the montmorillonite sheet layer, the montmorillonite sheet layer has negative charge, the montmorillonite is uniformly dispersed in the raw materials of the adhesive and forms a stable system with the adhesive, the conductive raw material in the electrode slurry has positive charge and is close to the montmorillonite, and the distribution of the ionized particles in the electrode, the photoelectric conversion efficiency is improved, the compatibility among the added modified nano titanium dioxide, the konjac flour and the degreased starch is improved, and meanwhile, the modified nano titanium dioxide can be uniformly dispersed among the raw materials, so that the binding force among the raw materials is improved, the bonding strength is further enhanced, and the weather resistance of the material is improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1.
The preparation process of the binder for the solar cell back electrode paste comprises the following steps:
step one, mixing 40 parts of modified konjac flour and 20 parts of defatted starch, then adding 25 parts of deionized water while stirring, then adding 5 parts of modified montmorillonite, increasing the stirring speed to 300r/min, stirring for 20min, then reducing the speed to 80r/min, stirring for 50min, then adding 4 parts of modified nano titanium dioxide, then transferring to a high-pressure reaction kettle, reacting for 30min, and obtaining a premix after the reaction is finished;
the preparation method of the modified konjac flour comprises the following steps: mixing konjac flour and lignin phenolate liquid according to a weight ratio of 5:1, then sending the mixture into a four-neck flask to react for 30min at a reaction temperature of 65 ℃, then adding glacial acetic acid to adjust the pH value to 5.0, then carrying out ultrasonic dispersion for 10min, then standing and aging for 20min, then adding nano calcium titanate with the total content of the konjac flour being 4%, then stirring at a stirring speed of 100r/min for 20min, and then washing, centrifuging and drying the mixture to obtain the konjac powder/lignin phenolate liquid;
and step two, adding 2 parts of ammonium persulfate into the premix prepared in the step one, then carrying out water bath treatment at the water bath temperature of 75 ℃ for 40min, then transferring the product into an irradiation bag, filling nitrogen, sealing, and then carrying out irradiation treatment to obtain the binder.
In the first step of this example, the lignin phenolized solution is obtained by mixing lignin and phenol at a weight ratio of 5:2, then adding phosphoric acid in an amount of 4% of the total weight of lignin and phenol, and then liquefying at 100 ℃ for 1 hour.
The preparation method of the modified montmorillonite comprises the steps of adding natural montmorillonite into deionized water for ultrasonic dispersion, then adding glacial acetic acid to adjust the pH value to 5.0, then sending the mixture into a magnetic stirrer, heating the mixture to 65 ℃, then adding hexadecyl trimethyl ammonium bromide accounting for 6% of the total weight of the montmorillonite, reacting for 30min, then centrifuging, sending the mixture into a drying oven at 80 ℃ for drying for 2h, then heating the mixture to 200 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min, and then cooling the mixture to the room temperature at the speed of 2 ℃/min.
The specific surface area of the natural montmorillonite of this example was 600m2G, interlayer spacing of 1 nm.
The preparation method of the modified nanometer titanium dioxide comprises the steps of adding the nanometer titanium dioxide into a sodium hydroxide solution with the mass fraction of 30%, performing ultrasonic dispersion for 20min, then adding a hydrogen peroxide solution with the mass fraction of 90%, reacting for 15min, standing for 10min, then adding a silane coupling agent, transferring to a reaction kettle, reacting for 1h at the reaction temperature of 85 ℃, and then washing, ionizing and drying.
The silane coupling agent of this example was gamma-aminopropyltriethoxysilane.
In the first step of this example, the reaction temperature in the autoclave was 90 ℃ and the reaction pressure was 2 MPa.
In the second step of this embodiment, gamma-ray irradiation is performed for 2min, and the irradiation dose is 2 KGy.
Example 2.
The preparation process of the binder for the solar cell back electrode paste comprises the following steps:
step one, mixing 50 parts of modified konjac flour and 30 parts of defatted starch, then adding 35 parts of deionized water, stirring while adding, then adding 15 parts of modified montmorillonite, stirring at a rotating speed increased to 400r/min for 30min, then reducing the rotating speed to 140r/min, stirring for 60min, then adding 8 parts of modified nano titanium dioxide, then transferring to a high-pressure reaction kettle, reacting for 40min, and obtaining a premix after the reaction is finished;
the preparation method of the modified konjac flour comprises the following steps: mixing konjac flour and lignin phenolate liquid according to a weight ratio of 5:1, then sending the mixture into a four-neck flask to react for 40min at a reaction temperature of 75 ℃, then adding glacial acetic acid to adjust the pH value to 5.0, then carrying out ultrasonic dispersion for 20min, then standing and aging for 30min, then adding nano calcium titanate accounting for 8% of the total weight of the konjac flour, then stirring at a stirring speed of 200r/min for 30min, and then washing, centrifuging and drying the mixture to obtain the konjac powder;
and step two, adding 7 parts of ammonium persulfate into the premix prepared in the step one, then carrying out water bath treatment, wherein the water bath temperature is 85 ℃, carrying out water bath for 50min, then transferring the product into an irradiation bag, filling nitrogen, sealing, and then carrying out irradiation treatment to obtain the binder.
In the first step of this example, the lignin phenolized solution is obtained by mixing lignin and phenol at a weight ratio of 5:2, then adding phosphoric acid in an amount of 6% of the total weight of lignin and phenol, and then liquefying at 120 ℃ for 2 hours.
The preparation method of the modified montmorillonite comprises the steps of adding natural montmorillonite into deionized water for ultrasonic dispersion, then adding glacial acetic acid to adjust the pH value to 6.0, then sending the mixture into a magnetic stirrer, heating the mixture to 75 ℃, then adding hexadecyl trimethyl ammonium bromide accounting for 10% of the total weight of the montmorillonite, reacting for 40min, then centrifuging, sending the mixture into a drying oven at 80 ℃ for drying for 3h, then heating the mixture to 200 ℃ at the speed of 5 ℃/min, preserving the temperature for 40min, and then cooling the mixture to the room temperature at the speed of 2 ℃/min.
The specific surface area of the natural montmorillonite of this example was 1000m2(g), the interlayer spacing was 3 nm.
The preparation method of the modified nanometer titanium dioxide comprises the steps of adding the nanometer titanium dioxide into a sodium hydroxide solution with the mass fraction of 40%, conducting ultrasonic dispersion for 30min, then adding a hydrogen peroxide solution with the mass fraction of 90%, conducting reaction for 25min, then standing for 20min, then adding a silane coupling agent, transferring the mixture into a reaction kettle, conducting reaction at the temperature of 95 ℃ for 2h, and then conducting water washing, ion drying, and thus obtaining the modified nanometer titanium dioxide.
The silane coupling agent of this example was gamma-aminopropyltriethoxysilane.
In the step one of this example, the reaction temperature in the autoclave was 110 ℃ and the reaction pressure was 6 MPa.
In the second step of this embodiment, gamma-ray irradiation is performed for 6min, and the irradiation dose is 12 KGy.
Example 3.
The preparation process of the binder for the solar cell back electrode paste comprises the following steps:
step one, mixing 45 parts of modified konjac flour and 25 parts of defatted starch, then adding 30 parts of deionized water while stirring, then adding 10 parts of modified montmorillonite, increasing the stirring speed to 350r/min, stirring for 25min, then reducing the speed to 110r/min, stirring for 55min, then adding 6 parts of modified nano titanium dioxide, then transferring to a high-pressure reaction kettle, reacting for 35min, and obtaining a premix after the reaction is finished;
the preparation method of the modified konjac flour comprises the following steps: mixing konjac flour and lignin phenolate liquid according to a weight ratio of 5:1, then sending the mixture into a four-neck flask to react for 35min at a reaction temperature of 70 ℃, then adding glacial acetic acid to adjust the pH value to 5.0, then carrying out ultrasonic dispersion for 15min, then standing and aging for 25min, then adding nano calcium titanate accounting for 4-8% of the total weight of the konjac flour, then stirring at a stirring speed of 150r/min for 25min, and then washing, centrifuging and drying the mixture to obtain the konjac powder;
and step two, adding 4.5 parts of ammonium persulfate into the premix prepared in the step one, then carrying out water bath treatment, wherein the water bath temperature is 80 ℃, carrying out water bath for 45min, then transferring the product into an irradiation bag, filling nitrogen, sealing, and then carrying out irradiation treatment to obtain the binder.
In the first step of this example, the lignin phenolized solution is obtained by mixing lignin and phenol at a weight ratio of 5:2, then adding phosphoric acid in an amount of 5% of the total weight of lignin and phenol, and then liquefying at 110 ℃ for 1.5 h.
The preparation method of the modified montmorillonite comprises the steps of adding natural montmorillonite into deionized water for ultrasonic dispersion, then adding glacial acetic acid to adjust the pH value to 5.5, then sending the mixture into a magnetic stirrer, heating to 70 ℃, then adding hexadecyl trimethyl ammonium bromide accounting for 8% of the total weight of the montmorillonite, reacting for 35min, then centrifuging, sending the mixture into a drying oven at 80 ℃ for drying for 2.5h, then heating to 200 ℃ at 5 ℃/min, preserving the heat for 35min, and then cooling to the room temperature at 2 ℃/min.
The specific surface area of the natural montmorillonite of this example was 800m2In terms of a/g, the interlayer spacing was 2 nm.
The preparation method of the modified nanometer titanium dioxide comprises the steps of adding the nanometer titanium dioxide into a sodium hydroxide solution with the mass fraction of 35%, conducting ultrasonic dispersion for 25min, then adding a hydrogen peroxide solution with the mass fraction of 90%, conducting reaction for 20min, standing for 15min, then adding a silane coupling agent, transferring the mixture into a reaction kettle, conducting reaction at the reaction temperature of 90 ℃ for 1.5h, and then conducting water washing, ion drying, and thus obtaining the modified nanometer titanium dioxide.
The silane coupling agent of this example was gamma-aminopropyltriethoxysilane.
In the first step of this example, the reaction temperature in the autoclave was 100 ℃ and the reaction pressure was 4 MPa.
In the second step of this embodiment, gamma-ray irradiation is performed for 3min, and the irradiation dose is 7 KGy.
Comparative example 1.
The difference from example 3 is that the konjac flour was not modified with lignin phenolization solution.
Comparative example 2.
The difference from example 3 is that no irradiation treatment was performed in step two.
Comparative example 3.
Chinese patent literature (publication number: CN105469854B) discloses a raw material and a method in example 1 in a plant-based composite binder for a polycrystalline silicon solar cell photo-back electrode paste.
The binders prepared in examples 1 to 3 and comparative examples 1 to 3 were mixed with the electrode paste, and the solar cell electrodes were manufactured by a screen printing process, and were respectively immersed in water at 26 ℃ for 1 hour and irradiated at an illumination intensity of 400LX for 1 hour under normal conditions, to perform a performance test.
The results of the performance measurements of examples 1 to 3 and comparative examples 1 to 3 are as follows
As shown in examples 1-3 and comparative examples 1-3, in example 3 of the present invention, the adhesive strength was improved by 2.17MPa under normal conditions compared to comparative example 3, and the adhesive strength was 0.98MPa in comparative example 3 and 5.98MPa in example 3 after soaking in water at 26 ℃ for 1 hour; the stability rate of soaking in water at 26 ℃ for 1 hour under the water soaking/normal condition is determined, the stability rate of soaking in water at 26 ℃ for 1 hour under the illumination intensity is determined to be 400LX under the illumination intensity for 1 hour, the stability rate of soaking in water at 26 ℃ for 1 hour is 86.8% in example 3, the stability rate of soaking in water at 26 ℃ for 1 hour is 20.6% in comparative example 3, the stability rate is increased by 66.2%, the stability rate of soaking in water at 400LX for 1 hour is 88.8% in example 3, the stability rate of soaking in water at comparative example 3 is 28.1% and the stability rate is increased by 60.7%.
The invention also researches the influence of the modified nano titanium dioxide on the bonding strength and the photoelectric conversion efficiency of the binder.
According to the invention, nano titanium dioxide is not added, the bonding strength and the photoelectric conversion efficiency are remarkably reduced when the nano titanium dioxide is measured under the conditions that the illumination intensity is 400LX, the water is illuminated for 1h and is soaked in water at 26 ℃ for 1h, meanwhile, the performance is also deteriorated when no hydrogen peroxide solution is added in the modification, and the hydrogen peroxide solution can oxidize the nano titanium dioxide, so that the activity of the acidified nano titanium dioxide is maintained, the organic reaction degree of the nano titanium dioxide is improved, and the compatibility of the nano titanium dioxide and other raw materials is further enhanced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation process of a binder for solar cell back electrode paste is characterized by comprising the following steps:
step one, mixing 40-50 parts of modified konjac flour and 20-30 parts of defatted starch, then adding 25-35 parts of deionized water while stirring, then adding 5-15 parts of modified montmorillonite, increasing the stirring speed to 300-400r/min, stirring for 20-30min, then reducing the rotating speed to 80-140r/min, stirring for 50-60min, then adding 4-8 parts of modified nano titanium dioxide, then transferring to a high-pressure reaction kettle, reacting for 30-40min, and finishing the reaction to obtain a premix;
the preparation method of the modified konjac flour comprises the following steps: mixing the konjac flour and the lignin phenolization liquid according to a weight ratio of 5:1, then sending the mixture into a four-neck flask to react for 30-40min at a reaction temperature of 65-75 ℃, then adding glacial acetic acid to adjust the pH value to 5.0, then carrying out ultrasonic dispersion for 10-20min, then standing and aging for 20-30min, then adding nano calcium titanate accounting for 4-8% of the total amount of the konjac flour, then stirring at a stirring speed of 100-200r/min, stirring for 20-30min, and then washing, centrifuging and drying to obtain the konjac powder;
step two, adding 2-7 parts of ammonium persulfate into the premix prepared in the step one, then carrying out water bath treatment, wherein the water bath temperature is 75-85 ℃, carrying out water bath for 40-50min, then transferring the product into an irradiation bag, filling nitrogen, sealing, and then carrying out irradiation treatment to obtain the binder of the invention;
adding natural montmorillonite into deionized water for ultrasonic dispersion, then adding glacial acetic acid to adjust the pH value to 5.0-6.0, then sending into a magnetic stirrer, heating to 65-75 ℃, then adding hexadecyl trimethyl ammonium bromide accounting for 6-10% of the total weight of the montmorillonite, reacting for 30-40min, then centrifuging, then sending into a drying oven at 80 ℃ for drying for 2-3h, then heating to 200 ℃ at 5 ℃/min, preserving the heat for 30-40min, and then cooling to room temperature at 2 ℃/min;
the preparation method of the modified nano titanium dioxide comprises the steps of adding nano titanium dioxide into a sodium hydroxide solution with the mass fraction of 30-40%, performing ultrasonic dispersion for 20-30min, then adding a hydrogen peroxide solution with the mass fraction of 90%, reacting for 15-25min, standing for 10-20min, then adding a silane coupling agent, transferring to a reaction kettle, reacting for 1-2h at the reaction temperature of 85-95 ℃, and then washing, ionizing and drying.
2. The process for preparing the adhesive for the back electrode paste of the solar cell as claimed in claim 1, wherein the lignin phenolization solution in the first step is obtained by mixing lignin and phenol according to a weight ratio of 5:2, then adding phosphoric acid accounting for 4-6% of the total weight of the lignin and phenol, and then liquefying at 100-120 ℃ for 1-2 h.
3. The process for preparing the adhesive for the back electrode paste of the solar cell as claimed in claim 1, wherein the specific surface area of the natural montmorillonite is 600-1000m2(ii)/g, the interlayer spacing is 1-3 nm.
4. The process for preparing the adhesive for the back electrode paste of the solar cell according to claim 1, wherein the silane coupling agent is γ -aminopropyltriethoxysilane.
5. The process for preparing the binder for the solar cell back electrode paste according to claim 1, wherein the reaction temperature in the first-step high-pressure reaction kettle is 90-110 ℃ and the reaction pressure is 2-6 MPa.
6. The process of claim 5, wherein the reaction temperature in the first autoclave is 100 ℃ and the reaction pressure is 4 MPa.
7. The process for preparing the adhesive for the back electrode paste of the solar cell according to claim 1, wherein the irradiation treatment in the second step is performed by gamma ray irradiation for 2-6min at an irradiation dose of 2-12 KGy.
8. The process for preparing the adhesive for the back electrode paste of the solar cell according to claim 7, wherein the irradiation treatment in the second step is performed with gamma rays for 3min, and the irradiation dose is 7 KGy.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103830736A (en) * | 2014-03-05 | 2014-06-04 | 中国科学院青岛生物能源与过程研究所 | Production method of starch empty capsule |
| CN103834066A (en) * | 2014-03-05 | 2014-06-04 | 中国科学院青岛生物能源与过程研究所 | Low-viscosity starch glue for preparing starch capsules as well as preparation method and application of low-viscosity starch glue |
| CN105349062A (en) * | 2015-11-19 | 2016-02-24 | 太仓市金锚化工有限公司 | Environment-friendly type high-performance water-proof starch adhesive |
| CN105469854A (en) * | 2015-11-24 | 2016-04-06 | 青岛能迅新能源科技有限公司 | Plant-source composite binder used for polycrystalline silicon solar cell light back side electrode slurry and preparation method thereof |
| CN106103630A (en) * | 2013-12-20 | 2016-11-09 | 新西兰森林研究机构有限公司 | Adhesive agent |
| CN106675424A (en) * | 2016-12-29 | 2017-05-17 | 郑州佰沃生物质材料有限公司 | Biomass synthetic resin and method for producing coconut palm mattress by use of biomass synthetic resin as adhesive |
| CN108136037A (en) * | 2015-10-28 | 2018-06-08 | 科技创新动量基金(以色列)参股有限公司 | Complex biological adhesive seal agent |
| CN108285556A (en) * | 2017-01-17 | 2018-07-17 | 武汉力诚生物科技有限公司 | A kind of plant polyose aeroge absorbing sound and lowering noise material and preparation method |
| CN108531059A (en) * | 2018-04-21 | 2018-09-14 | 郭平 | A kind of montmorillonite intercalation modified polyurethane paint of UV radiation |
| CN108795375A (en) * | 2017-04-27 | 2018-11-13 | 四川美登家具有限公司 | A kind of multi-functional wood furniture adhesive special and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100210745A1 (en) * | 2002-09-09 | 2010-08-19 | Reactive Surfaces, Ltd. | Molecular Healing of Polymeric Materials, Coatings, Plastics, Elastomers, Composites, Laminates, Adhesives, and Sealants by Active Enzymes |
-
2018
- 2018-11-15 CN CN201811356807.3A patent/CN109671784B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103630A (en) * | 2013-12-20 | 2016-11-09 | 新西兰森林研究机构有限公司 | Adhesive agent |
| CN103830736A (en) * | 2014-03-05 | 2014-06-04 | 中国科学院青岛生物能源与过程研究所 | Production method of starch empty capsule |
| CN103834066A (en) * | 2014-03-05 | 2014-06-04 | 中国科学院青岛生物能源与过程研究所 | Low-viscosity starch glue for preparing starch capsules as well as preparation method and application of low-viscosity starch glue |
| CN108136037A (en) * | 2015-10-28 | 2018-06-08 | 科技创新动量基金(以色列)参股有限公司 | Complex biological adhesive seal agent |
| CN105349062A (en) * | 2015-11-19 | 2016-02-24 | 太仓市金锚化工有限公司 | Environment-friendly type high-performance water-proof starch adhesive |
| CN105469854A (en) * | 2015-11-24 | 2016-04-06 | 青岛能迅新能源科技有限公司 | Plant-source composite binder used for polycrystalline silicon solar cell light back side electrode slurry and preparation method thereof |
| CN106675424A (en) * | 2016-12-29 | 2017-05-17 | 郑州佰沃生物质材料有限公司 | Biomass synthetic resin and method for producing coconut palm mattress by use of biomass synthetic resin as adhesive |
| CN108285556A (en) * | 2017-01-17 | 2018-07-17 | 武汉力诚生物科技有限公司 | A kind of plant polyose aeroge absorbing sound and lowering noise material and preparation method |
| CN108795375A (en) * | 2017-04-27 | 2018-11-13 | 四川美登家具有限公司 | A kind of multi-functional wood furniture adhesive special and preparation method thereof |
| CN108531059A (en) * | 2018-04-21 | 2018-09-14 | 郭平 | A kind of montmorillonite intercalation modified polyurethane paint of UV radiation |
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