CN109346241A - A kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force - Google Patents
A kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force Download PDFInfo
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- CN109346241A CN109346241A CN201811144440.9A CN201811144440A CN109346241A CN 109346241 A CN109346241 A CN 109346241A CN 201811144440 A CN201811144440 A CN 201811144440A CN 109346241 A CN109346241 A CN 109346241A
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- silver
- solar cell
- silicon solar
- silver paste
- high adhesion
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000004332 silver Substances 0.000 title claims abstract description 58
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 26
- 239000010703 silicon Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 25
- 150000007974 melamines Chemical class 0.000 claims abstract description 29
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003851 corona treatment Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 abstract description 20
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000005611 electricity Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- 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
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force, the following steps are included: step 1, weighs following raw material: silver-carrying modified melamine 15-25 parts, silver nanowires 50-60 parts of pretreatment, modified diadust 5-9 parts, 1-3 parts of curing agent, 0.2-0.8 parts of curing accelerator, 10-18 parts of solvent.Silver paste of the invention not only conducts electricity very well, adhesive force is strong simultaneously, and compared with the existing technology under the conditions of guaranteeing to conduct electricity very well, acid-proof alkaline, wash-resistant property are superior to comparative example, it applies in silicon solar cell front as electrode material, there is good application value.
Description
Technical field
The present invention relates to front electrode of solar battery technical fields, and in particular to a kind of silicon solar cell front electrode
The silver paste preparation method for material of high adhesion force.
Background technique
Solar battery is the device for directly luminous energy being converted to by photoelectric effect or photochemical effect electric energy, as long as
Arrived by illumination, moment can output voltage and electric current, solar battery can be divided into: silicon solar according to the difference of material therefor
Battery, multicomponent compound film solar battery, polymer multi-layer modified electrode type solar battery, nanocrystalline solar electricity
Pond, organic solar batteries, plastic solar cell, wherein silicon solar cell is that current development is most mature, in the application
Leading position is occupied, and silver paste is to be printed on battery front and back sides, is handled by high temperature sintering, and silver powder is made to be attached to battery surface shape
At positive and negative electrode.
Existing Chinese patent literature (publication number: CN106128554B) discloses a kind of anti-aging crystal silicon solar batteries back
Electrode silver plasm includes following component by weight percentage: silver-colored aluminium mixed powder 45~49%, unorganic glass powder 4~6%, inorganic anti-
Aging auxiliary agent 0~3% and organic bond 42~51%；Silver-colored aluminium mixed powder is the mixture of spherical silver powder and spherical aluminium powder,
Silver paste adhesive property depends primarily on organic bond in the document, and organic bond is conventional raw material, as the time increases, glues
Relay decline, then influences silver paste performance.
Existing Chinese patent literature (publication number: CN105895191B) discloses a kind of low temperature that solar battery uses and leads
A kind of electric silver paste and preparation method thereof, and in particular to low temperature silver paste and preparation method thereof based on silver nanoparticle fiber.Base of the present invention
It in the low temperature silver paste of silver nanoparticle fiber, is made of following weight percent composition: silver nanoparticle fiber 50~70%, silver cladding glass
Powder 10~20%, organic carrier 15~25%, inorganic additive are 0~5%, replace silver using silver nanoparticle fiber in the document
Powder, though effect is good, silver nanoparticle fiber and organic carrier interface compatibility are poor, then influence overall performance.
Summary of the invention
In view of the drawbacks of the prior art, the object of the present invention is to provide a kind of silicon solar cell front electrode high adhesion forces
Silver paste preparation method for material, to solve the problems mentioned in the above background technology.
The present invention solves technical problem and adopts the following technical scheme that
The present invention provides a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force, including it is following
Step:
Step 1 weighs following raw material: silver-carrying modified melamine 15-25 parts, pretreatment silver nanowires 50-60
Part, modified diadust 5-9 parts, 1-3 parts of curing agent, 0.2-0.8 parts of curing accelerator, 10-18 parts of solvent；
Melamine silver-carrying modified in step 1, solvent are added in magnetic stirring apparatus by step 2, start magnetic agitation
Device, speed of agitator rise to 550-650r/min, and whipping temp is 75-85 DEG C, stirs 5-15min, then add silver nanowires,
Modified diadust, speed of agitator are down to 350-450r/min, stir 15-25min, then add curing agent, solidification promotees
Into agent, speed of agitator is down to 120-160r/min, continues to stir 1-3h to get silver paste of the invention.
Preferably, the silver-carrying modified melamine the preparation method comprises the following steps:
Step 1 prepares modified cyanurotriamide: melamine, paraformaldehyde being mixed according to 1:2.5, are subsequently sent to
In three-necked flask, distilled water and alkali are added, is warming up to 70-80 DEG C under agitation, 30-40min is reacted, then adds
Modifying agent terephthalaldehyde adjusts pH to 7.5, spare；
Step 2 pre-processes Nano silver grain: Nano silver grain being added in dehydrated alcohol and is mixed, then ultrasound
Disperse 10-20min, silane coupling agent KH-560 hydro-thermal process 15-25min is added, hydrothermal temperature is 65-75 DEG C, then water again
It washes, is centrifuged, dries；
Step 3, by pretreatment Nano silver grain, anhydrous second made from the modified cyanurotriamide of step 1 preparation, step 2
Alcohol is sequentially sent to be reacted in autoclave, reaction pressure 3-4MPa, and the reaction time is that 35-45min changes to get silver is carried
Property melamine.
Preferably, Nano silver grain partial size is 4-10nm in the step 2.
Preferably, the pretreatment silver nanowires method is that silver nanowires corona combines low-temperature plasma alternate treatment
4min。
Preferably, the corona joint low-temperature plasma processing method is the glass container that silver nanoparticle is first placed in aqueous solution
In, it is placed between upper/lower electrode, voltage 6KV, handles 15s, subsequent sided corona treatment 45s, processing power 5Kw.
Preferably, the silver nanowires length is 40-80um, diameter 30-50nm.
Preferably, the preparation method of the modified diadust is that diadust, oleic acid are added in ball mill
Carry out ball milling, rotational speed of ball-mill 300-400r/min, ball milling 1-2h be subsequently sent in reaction kettle, add in deionized water into
Then the concentrated sulfuric acid, concentrated nitric acid is added according to weight ratio 2:1 in row ultrasonic disperse 15-25min, continues to stir 25-35min, subsequent water
It washes, filter, dry.
Preferably, the curing agent is one of methyl ethyl ketone peroxide, benzoyl peroxide or a variety of compositions.
Preferably, the curing accelerator is organic tin curing accelerator.
Preferably, the solvent is propylene glycol methyl ether acetate.
Silver-carrying modified melamine is mixed with by modified cyanurotriamide and Nano silver grain, and modified cyanurotriamide passes through three
Poly cyanamid, formaldehyde are made through polycondensation reaction, and there are a large amount of imino group and hydroxyls in space, are formed in the case where acting on curing agent empty
Between reticular structure, improve the adhesive force of material, assembled in space net structure by Nano silver grain, silver nanowires passes through hydrogen bond side
Formula is interspersed in space net structure in conjunction with silver-carrying modified melamine, and Nano silver grain synergistic combination in reticular structure,
Enhance electric conductivity, silver nanowires enhances its surface-active, while improving silver nanoparticle by corona joint low-temperature plasma processing
Line and silver-carrying modified melamine bond strength, diadust increase by modified specific surface area, and it is indirectly to improve raw material
The compactness of touching, while surface is modified by the nitration mixture of strong oxidizing property, in conjunction with silver-carrying modified melamine, forms crossover network knot
Structure, system is more stable, and then adhesive force and electric conductivity are significantly improved, and the present invention is relative to inorganic assistant in existing literature
SiC、Al2O3、La2O3Equal additives, it will be apparent that advantage is that diadust hardness itself is big, good mechanical property, after being modified
Specific surface area improves, while surface is modified, and enhances in conjunction with silver-carrying modified melamine, forms stable system, adhesive force
And other effects can significantly increase.
Compared with prior art, the present invention have it is following the utility model has the advantages that
Silver paste of the invention not only conducts electricity very well, while adhesive force is strong, is guaranteeing electric conductivity compared with the existing technology
Under the conditions of energy is good, acid-proof alkaline, wash-resistant property are superior to comparative example, apply in silicon solar cell front as electrode material
Material has good application value.
Specific embodiment
Combined with specific embodiments below, technical scheme in the embodiment of the invention is clearly and completely described, shows
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1.
A kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force of the present embodiment, including following step
It is rapid:
Step 1 weighs following raw material: 15 parts of silver-carrying modified melamine, changes 50 parts of silver nanowires of pretreatment
Property 5 parts of diadust, 1 part of curing agent, 0.2 part of curing accelerator, 10 parts of solvent；
Melamine silver-carrying modified in step 1, solvent are added in magnetic stirring apparatus by step 2, start magnetic agitation
Device, speed of agitator rise to 550r/min, and whipping temp is 75 DEG C, stirs 5min, then add silver nanowires, modified diamond
Micro mist, speed of agitator are down to 350r/min, stir 15min, then add curing agent, curing accelerator, speed of agitator is down to
120r/min continues to stir 1h to get silver paste of the invention.
The silver-carrying modified melamine of the present embodiment the preparation method comprises the following steps:
Step 1 prepares modified cyanurotriamide: melamine, paraformaldehyde being mixed according to 1:2.5, are subsequently sent to
In three-necked flask, distilled water and alkali are added, is warming up to 70 DEG C under agitation, 30min is reacted, then adds modifying agent
Terephthalaldehyde adjusts pH to 7.5, spare；
Step 2 pre-processes Nano silver grain: Nano silver grain (partial size 4nm) being added in dehydrated alcohol and is mixed
It closes, subsequent ultrasonic disperse 10min, silane coupling agent KH-560 hydro-thermal process 15min is added, hydrothermal temperature is 65 DEG C, then again
Washing, centrifugation, drying；
Step 3, by pretreatment Nano silver grain, anhydrous second made from the modified cyanurotriamide of step 1 preparation, step 2
Alcohol is sequentially sent to be reacted in autoclave, reaction pressure 3MPa, and the reaction time is 35min to get silver-carrying modified three
Poly cyanamid.
The pretreatment silver nanowires method of the present embodiment is that silver nanowires corona combines low-temperature plasma alternate treatment 4min.
The corona joint low-temperature plasma processing method of the present embodiment is the glass container that silver nanoparticle is first placed in aqueous solution
In, it is placed between upper/lower electrode, voltage 6KV, handles 15s, subsequent sided corona treatment 45s, processing power 5Kw.
The silver nanowires length of the present embodiment is 40um, diameter 30nm.
The preparation method of the modification diadust of the present embodiment be by diadust, oleic acid be added in ball mill into
Row ball milling, rotational speed of ball-mill 300r/min, ball milling 1h are subsequently sent in reaction kettle, are added and are carried out ultrasound point in deionized water
15min is dissipated, the concentrated sulfuric acid, concentrated nitric acid then is added according to weight ratio 2:1, continues to stir 25min, then washes, filters, is dry,
?.
The curing agent of the present embodiment is methyl ethyl ketone peroxide.
The curing accelerator of the present embodiment is organic tin curing accelerator.
The solvent of the present embodiment is propylene glycol methyl ether acetate.
Embodiment 2.
A kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force of the present embodiment, including following step
It is rapid:
Step 1 weighs following raw material: 25 parts of silver-carrying modified melamine, changes 60 parts of silver nanowires of pretreatment
Property 9 parts of diadust, 3 parts of curing agent, 0.8 part of curing accelerator, 18 parts of solvent；
Melamine silver-carrying modified in step 1, solvent are added in magnetic stirring apparatus by step 2, start magnetic agitation
Device, speed of agitator rise to 650r/min, and whipping temp is 85 DEG C, stirs 15min, then add silver nanowires, modified Buddha's warrior attendant
Stone micro mist, speed of agitator are down to 450r/min, stir 25min, then add curing agent, curing accelerator, speed of agitator drop
To 160r/min, continue to stir 3h to get silver paste of the invention.
The silver-carrying modified melamine of the present embodiment the preparation method comprises the following steps:
Step 1 prepares modified cyanurotriamide: melamine, paraformaldehyde being mixed according to 1:2.5, are subsequently sent to
In three-necked flask, distilled water and alkali are added, is warming up to 80 DEG C under agitation, 40min is reacted, then adds modifying agent
Terephthalaldehyde adjusts pH to 7.5, spare；
Step 2, pre-process Nano silver grain: by Nano silver grain (partial size 4-10nm) be added in dehydrated alcohol into
Silane coupling agent KH-560 hydro-thermal process 25min is added in row mixing, subsequent ultrasonic disperse 20min, and hydrothermal temperature is 75 DEG C, with
It washes again afterwards, is centrifuged, dries；
Step 3, by pretreatment Nano silver grain, anhydrous second made from the modified cyanurotriamide of step 1 preparation, step 2
Alcohol is sequentially sent to be reacted in autoclave, reaction pressure 4MPa, and the reaction time is 45min to get silver-carrying modified three
Poly cyanamid.
The pretreatment silver nanowires method of the present embodiment is that silver nanowires corona combines low-temperature plasma alternate treatment 4min.
The corona joint low-temperature plasma processing method of the present embodiment is the glass container that silver nanoparticle is first placed in aqueous solution
In, it is placed between upper/lower electrode, voltage 6KV, handles 15s, subsequent sided corona treatment 45s, processing power 5Kw.
The silver nanowires length of the present embodiment is 80um, diameter 50nm.
The preparation method of the modification diadust of the present embodiment be by diadust, oleic acid be added in ball mill into
Row ball milling, rotational speed of ball-mill 400r/min, ball milling 2h are subsequently sent in reaction kettle, are added and are carried out ultrasound point in deionized water
25min is dissipated, the concentrated sulfuric acid, concentrated nitric acid then is added according to weight ratio 2:1, continues to stir 35min, then washes, filters, is dry,
?.
The curing agent of the present embodiment is benzoyl peroxide.
The curing accelerator of the present embodiment is organic tin curing accelerator.
The solvent of the present embodiment is propylene glycol methyl ether acetate.
Embodiment 3.
A kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force of the present embodiment, including following step
It is rapid:
Step 1 weighs following raw material: 20 parts of silver-carrying modified melamine, changes 55 parts of silver nanowires of pretreatment
Property 7 parts of diadust, 2 parts of curing agent, 0.5 part of curing accelerator, 14 parts of solvent；
Melamine silver-carrying modified in step 1, solvent are added in magnetic stirring apparatus by step 2, start magnetic agitation
Device, speed of agitator rise to 600r/min, and whipping temp is 80 DEG C, stirs 10min, then add silver nanowires, modified Buddha's warrior attendant
Stone micro mist, speed of agitator are down to 400r/min, stir 20min, then add curing agent, curing accelerator, speed of agitator drop
To 140r/min, continue to stir 2h to get silver paste of the invention.
The silver-carrying modified melamine of the present embodiment the preparation method comprises the following steps:
Step 1 prepares modified cyanurotriamide: melamine, paraformaldehyde being mixed according to 1:2.5, are subsequently sent to
In three-necked flask, distilled water and alkali are added, is warming up to 75 DEG C under agitation, 35min is reacted, then adds modifying agent
Terephthalaldehyde adjusts pH to 7.5, spare；
Step 2 pre-processes Nano silver grain: Nano silver grain (partial size 7nm) being added in dehydrated alcohol and is mixed
It closes, subsequent ultrasonic disperse 15min, silane coupling agent KH-560 hydro-thermal process 20min is added, hydrothermal temperature is 70 DEG C, then again
Washing, centrifugation, drying；
Step 3, by pretreatment Nano silver grain, anhydrous second made from the modified cyanurotriamide of step 1 preparation, step 2
Alcohol is sequentially sent to be reacted in autoclave, reaction pressure 3.5MPa, and the reaction time is 40min to get silver-carrying modified
Melamine.
The pretreatment silver nanowires method of the present embodiment is that silver nanowires corona combines low-temperature plasma alternate treatment 4min.
The corona joint low-temperature plasma processing method of the present embodiment is the glass container that silver nanoparticle is first placed in aqueous solution
In, it is placed between upper/lower electrode, voltage 6KV, handles 15s, subsequent sided corona treatment 45s, processing power 5Kw.
The silver nanowires length of the present embodiment is 60um, diameter 40nm.
The preparation method of the modification diadust of the present embodiment be by diadust, oleic acid be added in ball mill into
Row ball milling, rotational speed of ball-mill 350r/min, ball milling 1.5h are subsequently sent in reaction kettle, are added and are carried out ultrasound in deionized water
Disperse 20min, the concentrated sulfuric acid, concentrated nitric acid then is added according to weight ratio 2:1, continues to stir 30min, then wash, filter, is dry
It is dry.
The curing agent of the present embodiment is benzoyl peroxide.
The curing accelerator of the present embodiment is organic tin curing accelerator.
The solvent of the present embodiment is propylene glycol methyl ether acetate.
Comparative example 1.
It is essentially identical with the material and preparation process of embodiment 3, it has only the difference is that modified using modified cyanurotriamide.
Comparative example 2.
It is essentially identical with the material and preparation process of embodiment 3, it has only the difference is that being not added with modified diadust.
Comparative example 3.
It is essentially identical with the material and preparation process of embodiment 3, it has only the difference is that modified diadust is changed to Al2O3。
Comparative example 4
A kind of low temperature that solar battery uses is disclosed using Chinese patent literature (publication number: CN105895191B) to lead
3 raw material of embodiment and preparation method in electric silver paste and preparation method thereof.
The embodiment 1-3 and comparative example 1-4 silver paste prepared is printed on solar battery front side, is then in temperature
1h is calcined at 320 DEG C, forms silver layer, is protected 12h at being again then 35 DEG C in temperature, is carried out washability test；Washability test
Method is solar cell front side silver is placed on straight line swaging machine to carry out brushing, until silver layer is ruptured to obtain and be scrubbed time.
Silver paste in embodiment 1-3 and comparative example 1-4 is prepared into silver layer using the method in wash-resistant property test, with
Acid-proof alkaline test is carried out afterwards；10% sodium hydroxide solution, the immersion of 10% acetum is respectively adopted, when measurement immersion passes through
Between.
Test result is as follows for embodiment 1-3 and comparative example 1-4 adhesion performance
Obtained from embodiment 1-3 and comparative example 1-4,1-3 of the embodiment of the present invention relative to comparative example 1-4, resistance to acid and alkali,
Washability, peel strength are superior to comparative example, while the embodiment of the present invention 3, relative to comparative example 4, washability number improves 75
Secondary, increase rate 52.45%, in addition, resistance to acid and alkali embodiment of the present invention 1-3 passes through in 96h, and comparative example 4, alkali resistance exist
48h does not pass through, and acid resistance does not pass through in 96h, it is known that adhesive force of the invention, which has, to be significantly improved.
The present invention further measures silver paste electric conductivity, probes into adhesive force and electric conductivity after measuring silver paste adhesive force
Relationship between energy, and corresponding adjustment is made, coordinate electric conductivity mutually with adhesive force, makes the silver paste performance prepared more
It is perfect.
Electrical property is measured using silicon solar cell efficiency test device
| Series resistance (Ω) | Transfer efficiency (%) | |
| Embodiment 1 | 0.00185 | 18.06 |
| Embodiment 2 | 0.00186 | 18.05 |
| Embodiment 3 | 0.00183 | 18.08 |
| Comparative example 1 | 0.00198 | 17.84 |
| Comparative example 2 | 0.00194 | 17.92 |
| Comparative example 3 | 0.00191 | 17.95 |
| Comparative example 4 | 0.00182 | 18.10 |
It is obtained from silicon solar cell efficiency, the embodiment of the present invention 1-3, relative to comparative example 4, transfer efficiency is slightly lower
In comparative example 4, but differ smaller, it is known that, the present invention is improving silver paste adhesive force simultaneously, and transfer efficiency is ensured.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force, which is characterized in that including following step
It is rapid:
Step 1 weighs following raw material: silver-carrying modified melamine 15-25 parts, pretreatment silver nanowires 50-60 parts,
Modified diadust 5-9 parts, 1-3 parts of curing agent, 0.2-0.8 parts of curing accelerator, 10-18 parts of solvent；
Melamine silver-carrying modified in step 1, solvent are added in magnetic stirring apparatus by step 2, start magnetic stirring apparatus,
Speed of agitator rises to 550-650r/min, and whipping temp is 75-85 DEG C, stirs 5-15min, then adds silver nanowires, changes
Property diadust, speed of agitator is down to 350-450r/min, stirs 15-25min, then adds curing agent, solidification promotes
Agent, speed of agitator are down to 120-160r/min, continue to stir 1-3h to get silver paste of the invention.
2. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 1,
Be characterized in that, the silver-carrying modified melamine the preparation method comprises the following steps:
Step 1 prepares modified cyanurotriamide: melamine, paraformaldehyde being mixed according to 1:2.5, are subsequently sent to three mouthfuls
In flask, distilled water and alkali are added, is warming up to 70-80 DEG C under agitation, 30-40min is reacted, then adds modification
Agent terephthalaldehyde adjusts pH to 7.5, spare；
Step 2 pre-processes Nano silver grain: Nano silver grain being added in dehydrated alcohol and is mixed, subsequent ultrasonic disperse
Silane coupling agent KH-560 hydro-thermal process 15-25min is added in 10-20min, and hydrothermal temperature is 65-75 DEG C, then washes again, from
The heart, drying；
Step 3, will the modified cyanurotriamide of step 1 preparation, pretreatment Nano silver grain made from step 2, dehydrated alcohol according to
It is reacted in secondary feeding autoclave, reaction pressure 3-4MPa, the reaction time is 35-45min to get silver-carrying modified three
Poly cyanamid.
3. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 2,
It is characterized in that, Nano silver grain partial size is 4-10nm in the step 2.
4. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 1,
It is characterized in that, the pretreatment silver nanowires method is that silver nanowires corona combines low-temperature plasma alternate treatment 4min.
5. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 4,
It being characterized in that, the corona combines low-temperature plasma processing method to be first placed in silver nanoparticle in the glass container of aqueous solution, and
It is placed between upper/lower electrode, voltage 6KV, handles 15s, subsequent sided corona treatment 45s, processing power 5Kw.
6. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 4,
It is characterized in that, the silver nanowires length is 40-80um, diameter 30-50nm.
7. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 1,
It is characterized in that, the preparation method of the modified diadust is that diadust, oleic acid are added in ball mill to carry out ball
Mill, rotational speed of ball-mill 300-400r/min, ball milling 1-2h are subsequently sent in reaction kettle, are added and are carried out ultrasound in deionized water
Disperse 15-25min, the concentrated sulfuric acid, concentrated nitric acid then is added according to weight ratio 2:1, continues to stir 25-35min, then wash, take out
Filter, drying.
8. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 1,
It is characterized in that, the curing agent is one of methyl ethyl ketone peroxide, benzoyl peroxide or a variety of compositions.
9. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 1,
It is characterized in that, the curing accelerator is organic tin curing accelerator.
10. a kind of silver paste preparation method for material of silicon solar cell front electrode high adhesion force according to claim 1,
It is characterized in that, the solvent is propylene glycol methyl ether acetate.
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| DE1258088B (en) * | 1961-11-04 | 1968-01-04 | Duerrwaechter E Dr Doduco | Process for the production of resin silver solutions |
| US5057245A (en) * | 1990-04-17 | 1991-10-15 | Advanced Products, Inc. | Fast curing and storage stable thermoset polymer thick film compositions |
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