CN106251929A - Copper slurry for crystal silicon solar battery front side conductive layer electrode and preparation method thereof - Google Patents
Copper slurry for crystal silicon solar battery front side conductive layer electrode and preparation method thereof Download PDFInfo
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- CN106251929A CN106251929A CN201610652250.2A CN201610652250A CN106251929A CN 106251929 A CN106251929 A CN 106251929A CN 201610652250 A CN201610652250 A CN 201610652250A CN 106251929 A CN106251929 A CN 106251929A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 94
- 239000010949 copper Substances 0.000 title claims abstract description 94
- 239000002002 slurry Substances 0.000 title claims abstract description 64
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 50
- 239000010703 silicon Substances 0.000 title claims abstract description 50
- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 239000011521 glass Substances 0.000 claims abstract description 22
- 239000010953 base metal Substances 0.000 claims abstract description 21
- 239000000428 dust Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 26
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000009792 diffusion process Methods 0.000 claims description 14
- 239000000787 lecithin Substances 0.000 claims description 14
- 235000010445 lecithin Nutrition 0.000 claims description 14
- 229940067606 lecithin Drugs 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001856 Ethyl cellulose Substances 0.000 claims description 13
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- 229920001249 ethyl cellulose Polymers 0.000 claims description 13
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229910003069 TeO2 Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000003064 anti-oxidating effect Effects 0.000 claims description 4
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 59
- 229910052709 silver Inorganic materials 0.000 description 57
- 239000004332 silver Substances 0.000 description 57
- 239000010410 layer Substances 0.000 description 33
- 210000004027 cell Anatomy 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000011160 research Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910004205 SiNX Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HMPVUDRACAQMSH-UHFFFAOYSA-N [Al].[Mo].[Mo].[Mo] Chemical compound [Al].[Mo].[Mo].[Mo] HMPVUDRACAQMSH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010982 kinetic investigation Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007723 transport mechanism Effects 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
-
- 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)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
A kind of copper for crystal silicon solar battery front side conductive layer electrode is starched, and the glass dust of copper nanoparticle, 1～5wt% by 85～95wt% and the organic carrier of 4～14wt% form.Organic carrier is placed in heated and stirred in thermostatic container, in container, adds copper nanoparticle and glass dust successively, then prepared mixture is placed in three-roll grinder grinding, afterwards by silk screen filter, obtain described copper slurry.Copper slurry is preset at crystal silicon solar battery front post-drying, prepares conductive layer copper electrode, as the conducting layer electrode of crystal silicon solar battery front nickel copper/aluminum stannum base metal combination electrode.
Description
Technical field
The present invention relates to a kind of copper slurry for crystal silicon solar battery electrode and preparation method thereof.
Background technology
Reducing cost is that solar cell future can be by one of essential condition of broader applications, the reduction master of battery cost
The raising of battery efficiency to be depended on and the reduction of battery manufacture material cost.On the one hand, the raising of photoelectric transformation efficiency increases
The generated output of unit are photovoltaic cell component, reduces the cost relevant to generating area accordingly.On the other hand, use
The reduction of material cost is prepared, it is also possible to effectively reduce the cost of solar cell in battery.After the eighties in 20th century, battery
The lifting of efficiency is mainly due to optimization (Green, the The path to 25% of the technology of preparing such as gate line electrode, silicon emitter
silicon solar cell efficiency:History of silicon cell evolution,
Prog.Photovolt:Res.Appl.,17(2009)183-189).The lifting master of conventional uniform emitter stage crystal silicon battery efficiency
The improvement of size performance to be depended on.Solar cell front surface gate line electrode the most all uses high temperature sintering after printing silver slurry
Method prepare, but the higher price of silver constrains the reduction of solar cell cost.Therefore, low cost, function admirable are sought
Novel conductive paste, substitute noble metal with base metal and prepare electrocondution slurry and become the inexorable trend of development.From British Electric
Research association has used aluminium dioxide as (Fedrizzi, Effect of powder since the conducting function phase of electrocondution slurry
painting procedures on the filiform corrosion of aluminium profiles,Progress
in organic coatings,59(2007)230-238；Maiti,Synthesis and characterization of
molybdenum aluminide nanoparticles reinforced aluminium matrix composites,
J.Alloy.Compd., 458 (2008) 450-456), various countries scientific research personnel has progressively carried out grinding about base metal electrocondution slurry
Study carefully application work.In terms of electrocondution slurry, starch (Wu, Preparation of micron-sized flake for copper
copper powder for base-metal-electrode multi-layer ceramic capacitor,journal
of materials processing technology,209(2009)1129-1133；Wu,Preparation of fine
copper powders and their application in bme-mlcc,Journal of University of
Science and Technology Beijing,Mineral,Metallurgy,Material,13(2006)250-255)、
Nickel slurry (Lee, Characteristics of surface-modified metal hydride electrode with
flake ni by the ball-milling process,J.Alloy.Compd.,330–332(2002)835-840；
Yoshinaga,Highly densed-mh electrode using flaky nickel powder and gas-
atomized hydrogen storage alloy powder,J.Alloy.Compd.,330–332(2002)846-850)、
Corronil slurry (Songping, Preparation of ultra fine copper nickel bimetallic
Powders for conductive thick film, Intermetallics, 15 (2007) 1316-1321), ormolu
Slurry (Kalendova, Comparison of the efficiency of inorganic nonmetal pigments
with zinc powder in anticorrosion paints,Progress in organic coatings,57
(2006)1-10；Renger,Rheology studies on highly filled nano-zirconia
Suspensions, Journal of the European Ceramic Society, 27 (2007) 2361-2367) all carry out
Study widely, and copper slurry be successfully applied to the electrode of hydrid integrated circuit and multi-chip module prepare (Wang,
Research of ltcc/cu,ag multilayer substrate in microelectronic packaging,
Materials Science and Engineering:B,94(2002)48-53)。
In recent years, the demand for the silver slurry succedaneum in solar cell field grows with each passing day, the main screening of alternative metals
Standard is exactly resistivity and price.The resistivity of silver is 1.59 × 10-8Ω m, and the resistivity of copper is the most slightly higher, is 1.75
×10-8Ω·m.Further, the price of copper is far below silver, and the data of Shanghai on the 1st July in 2016 futures exchange show, the valency of copper
Lattice are about 45 yuan/kg, and the price of silver is about 4309 yuan/kg (Http: //www.Shfe.Com.Cn/), the price of copper only phase
When one of nearly percentage in silver, therefore use copper as the conducting function phase of electrocondution slurry, preparation electricity can be reduced greatly
The material cost in pond.Copper, in resistivity and the advantage of two aspects of cost, becomes and substitutes the optimum selection of silver in electrocondution slurry, adopt
Substitute argentum powder with copper powder to starch as the copper of conducting function phase and become study hotspot in recent years.
The gate line electrode of conventional solar cell is sinter molding after silk screen printing silver is starched, and this process generally uses
Schubert Sintering Model (Schubert, Thick film metallisation of crystalline silicon
solar cells:Mechanisms,models and applications,PhD(2006)；Schubert,Current
transport mechanism in printed ag thick film contacts to an n-type-emiter of
a crystalline solar cell 19th European Solar Energy Conference and
Exhibition, (2004) 813 816) describe: in sintering process, organic carrier be heated after gradually volatiling reaction.Work as temperature
When reaching glass transition temperature, the glass dust in silver slurry starts to soften.Soften state glass-coated argentum powder, penetrate into silver slurry simultaneously
And infiltrate on the interface between silicon emitter and etch SiNx: H thin film.Soften state glass etching SiNx: after H thin film, glass dust
In lead oxide and silicon generation redox reaction, the interface zone at silicon emitter with printing slurry generates metallic lead, with slurry
Silver contact in material, reduces silver point, generates the pb-ag alloy of liquid phase, and silver has certain diffusion in silicon.Due to liquid phase
Pb-ag alloy is different to the etch rate in each crystal orientation of silicon emitter so that etched surface is inverted pyramid structure.When temperature reduces
Time, pb-ag alloy is according to phasor split-phase, and silver recrystallization is on (111) face of inverted pyramid.And when using copper slurry to substitute silver slurry, meeting
Two technical barriers occur, in sintering process, the oxidation of copper and the height of launch site caused due to the diffusion of copper are combined.One side
Face, copper is oxidizable relative to galactic pole, and the oxide layer of Surface Creation can not stop the continuation of internal oxidation occur (Hu,
Kinetic investigation of copper film oxidation by spectroscopic ellipsometry
and reflectometry,Journal of Vacuum Science&Technology A:Vacuum,Surfaces,and
Films, 18 (2000) 2527-2532), the copper oxide resistivity of generation is relatively big, significantly increases the line resistance of gate line electrode,
And then have impact on the raising of solar cell performance.And if entirely without the existence of oxygen, back surface and main schedule in sintering atmosphere
Resinous principle in starch adhesive material all can not become volatile oxide, it is difficult to removes from battery surface.On the other hand, due to copper
Having bigger diffusion coefficient in silicon materials, copper diffusion coefficient in silicon is about 7.3 × 10-8cm2/ s, much larger than the diffusion of silver
Coefficient 1.5 × 10-15cm2/s(Fisher,Diffusion in silicon,(1998)).Copper atom diffuses through deeply in silicon,
Can reduce the life-span of carrier, improve compound saturation current density J caused02And reduce open-circuit voltage, even and if at low temperature
It is also possible to penetrate emitter region under environment and causes electric leakage, especially hinder its popularization in shallow junction solar cell field.
In recent years, having carried out substantial amounts of work both at home and abroad in terms of the research of copper slurry, core is all intended to solve sintering process
In, the technical barrier of the oxidizable and easy diffusion of copper.In order to stop copper atom diffusion in silicon in sintering process, mainly use expansion
Dissipate barrier technology.The research that northeastern Japan university is correlated with, by preparing the oxidation of 5～10nm on battery emitter stage
Layer as diffusion impervious layer with stop copper diffusion.But, use preparation oxide layer as the method for diffusion impervious layer, add
Technology step, and the oxidation technology temperature of crystal silicon solar battery reaches more than 900 DEG C, relatively big to the hot injury of silicon chip, fall
Low solar cell electrical property.
And in order to suppress the oxidation of copper, mainly use silver-coated copper powder, low-temperature sintering, in organic carrier, increase reproducibility one-tenth
Divide, use the technology such as reductive sintered atmosphere.Silver-coated copper powder mainly has replacement method, chemical reduction method, displacement with chemistry again
The methods such as legal, atomized molten method.In terms of the research of silver-coated copper powder, Korean science technical college, Korea S's Materials Research Laboratories and
The joint research of KonKuk University of Korea S shows, the silver-coated copper powder that mean diameter 0.45 μm, silver content are 20wt% is placed in air
In one month, not oxidized (Jung, the Air-stable silver-coated copper of silver-coated copper powder of 95%
particles of sub-micrometer size,J.Colloid Interface Sci.,364(2011)574-581)。
The joint study silver copper-clad nano wire of Canada Calgary university and University of Alberta, when silver content is 66.52wt%,
Silver copper-clad nano wire has good non-oxidizability, increases weight and be reduced to silver from without 20.3% during silver cladding after nano wire oxidation
3.2% (Luo, Silver-coated copper nanowires with improved anti-oxidation during cladding
property as conductive fillers in low-density polyethylene,The Canadian
Journal of Chemical Engineering,91(2013)630-637).The research of Taiwan Feng Chia University shows, lamellar
The non-oxidizability of silver-coated copper powder is better than ball-type silver-coated copper powder (Lin, Effects of oxidation and particle
shape on critical volume fractions of silver-coated copper powders in
conductive adhesives for microelectronic applications,Polymer Engineering&
Science,44(2004)2075-2082).Guangdong University of Technology's research worker confirms experimentally, when the content of silver is
During 10wt%, it is possible to uniform parcel copper granule, silver-coated copper powder now have good non-oxidizability (Cao,
Fabrication and performance of silver coated copper powder,Electronic
Materials Letters,8(2012)467-470).Further investigations have shown that, increase RE-608 high-efficiency copper extractant with anti-
Between Ying Shi, reduce the concentration of silver nitrate, when the content of silver is 6.86wt% in silver-coated copper powder, it becomes possible to make silver-coated copper powder simultaneously
There is good non-oxidizability (Cao, Preparation of silver-coated copper powder and its
oxidation resistance research,Powder Technology,226(2012)53-56).Guangdong elegance and talent is high-new
Silver-coated copper powder prepared by Science and Technology Co., Ltd. when silver content is 5wt%～18wt%, problem of oxidation can improve 40～
140 DEG C, have good non-oxidizability (Tang founding father, the preparation of silver-coated copper powder and performance thereof, electronic component and material, 28
(2009)66-66).But, the technology of preparing of silver-coated copper powder is complex, and the clad ratio of silver copper-clad granule is with being evenly coated property still
For the problem existed, although and this technology can suppress the oxidation of copper, but material cost is still higher than using the slurry of copper powder,
It can only be a kind of cambic electrocondution slurry technology.Japan's AIST institute uses low-temperature sintering technology to process and with the addition of low melting point
The copper slurry of alloying pellet, relative to high temperature sintering environment, low-temperature sintering inhibits oxidation (Yoshiba, the Cost-of copper
effective front contact metalization by copper paste for screen-printed
crystalline silicon solar cells,27th European Photovoltaic Solar Energy
Conference and Exhibition,(2012)1730-1732).Kunming Institute of Precious Metals selects alkali glass as nothing
Machine binding agent, in organic carrier add reducing agent, copper slurry can in atmosphere direct sintering (Tan Fubin sinters in atmosphere
Copper electrocondution slurry, noble metal, 13 (1992) 40-44).But, the reducing agent dosage added in organic carrier is too small, can not
Effectively stoping the oxidation of copper, and when additive capacity is excessive, can reduce again the content of copper powder accordingly, the window of Technology is less.
Northeastern Japan university uses reducing atmosphere to be sintered technique, it is possible to the copper oxide on gate line electrode is reduced to metallic copper,
Thus reduce the line resistance of gate line electrode.But, reducibility gas mostly is flammable explosive gas, is prevented effectively from the most technically
Gas leakage is still that significant problem to be solved.
Summary of the invention
It is an object of the invention to the technical barrier overcoming prior art cost high, propose one for crystal silicon solar battery
Copper slurry of front side conductive layer electrode and preparation method thereof.The present invention uses copper slurry preparation nickel copper/aluminum stannum base metal combination electrode
Conducting layer electrode, can be greatly reduced cost of sizing agent.
For achieving the above object, the present invention use copper powder base metal granule as conducting function phase, in conjunction with Binder Phase with have
The performances such as airborne body regulation and control slurry bonding, thixotropy, rheological characteristic, are preset at crystal silicon solar battery front post-drying, prepare conduction
Layer copper electrode, as the conducting layer electrode of crystal silicon solar battery front nickel copper/aluminum stannum base metal combination electrode.
The present invention for crystal silicon solar battery front side conductive layer electrode copper slurry by 85～95wt% copper nanoparticle, 1～
The glass dust of 5wt% and the organic carrier composition of 4～14wt%.
The particle diameter of described copper nanoparticle is 500～800nm, and purity is more than 99%.
Described copper slurry is preset at crystal silicon solar battery front, prepares conductive layer copper electrode, as the crystal silicon sun after drying
The conducting layer electrode of battery front side nickel copper/aluminum stannum base metal combination electrode.Described crystal silicon solar battery front nickel copper/aluminum stannum
The bottom of base metal combination electrode is resistance diffusion layer nickel electrode, and middle level is conductive layer copper electrode, and top layer is anti oxidation layer aluminum stannum electricity
Pole.
The preparation method of described copper slurry is as follows:
(1) organic carrier is placed in container, described container is placed in the thermostatic water bath that temperature is 60～80 DEG C, with 90
～the organic carrier that the speed of 180 revs/min is stirred continuously in container, heated and stirred 1～after 10 hours, with 5～30g/min
Speed adds copper nanoparticle, prepares mixture a.
(2) thermostatic water bath temperature is brought up to 80～100 DEG C, be stirred continuously container with the speed of 120～200 revs/min
The mixture a that middle step (1) prepares, heated and stirred 1～after 5 hours, the speed with 1～5g/min adds glass dust, prepares mixed
Compound b.
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 6～8 hours, prepares
Mixture c.
(4) the mixture c prepared by the silk screen filter step (3) of 300～400 mesh, for crystal silicon solar battery just prepares
The copper slurry of face conducting layer electrode.
In described step (1) and step (2), the percentage by weight of the copper nanoparticle of addition, glass dust and organic carrier is
85～95wt%, 1～5wt% and 4～14wt%.
The particle diameter of described copper nanoparticle is 500～800nm, and purity is more than 99%.
Described glass dust is by the TeO of PbO, 20wt% of 50wt%2, the SiO of 15wt%2, the A1 of 5wt%2O3, 5wt%
B2O3Bi with 5wt%2O3Composition, by PbO, TeO2、SiO2、A12O3、B2O3And Bi2O3Mix in proportion and be placed on
Heating in 1400 DEG C of Muffle furnaces, after insulation 60min, quenching ball milling prepare.
Described organic carrier is by the butyl of 60wt%, the tributyl citrate of 15wt%, the ethyl of 3wt%
The Polyethylene Glycol composition of cellulose, the polyamide wax of 6wt%, the lecithin of 5wt%, the tributyl phosphate of 5wt% and 6wt%,
Butyl, tributyl citrate, ethyl cellulose, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol are pressed
Ratio mix homogeneously is placed in 80 DEG C of thermostatic containers, stirs 5 hours and prepares.
Beneficial effects of the present invention is embodied in:
(1) use copper slurry to replace silver slurry, the conducting layer electrode of preparation nickel copper/aluminum stannum base metal combination electrode, realize simultaneously
Low cost and satisfactory electrical conductivity.
(2) resistivity of silver is 1.59 × 10-8Ω m, and the resistivity of copper is the most slightly higher, is 1.75 × 10-8Ω·
M, therefore copper electrode resistivity is suitable with silver electrode.Further, the price of copper is about 45 yuan/kg, far below the valency of 4309 yuan/kg of silver
Lattice, it is ensured that the cheap advantage of copper electrode.
With regard to application prospect aspect, the data of IEA and CPIA show, end the accumulative installation amount in the whole world in 2015 more than 200GW,
Just install 53GW in only 2015 whole world, domestic installation 15GW.Global solar module yield in 2015 is about 60GW, domestic about
For 43GW.In the solar cell technology of preparing of various industrialization, crystal silicon solar battery technology accounts for more than 90% share, and silver-colored
Slurry is the prime cost expenditure of crystal silicon solar battery, and market potential is huge.Single according to the most conventional crystal silicon battery efficiency and silver slurry
Consumption budgetary estimate, within 2015, whole world silver slurry consumption is about 1626 tons, domestic about 1165 tons.Even if it is it is to say, sudden and violent at whole world silver valency
2015 fallen, whole world silver slurry also consumed nearly 9,800,000,000 yuan, domestic consumption nearly 7,000,000,000 yuan.And along with photovoltaic market is recovered, brilliant
Silion cell yield cumulative year after year, staple commodities price stabilizes, and the following silver that will consume hundreds of hundred million for 1 year is starched.And if adopted
Use base metal slurry, it will greatly reduce electrocondution slurry cost.Do a simple measuring and calculating, it is assumed that base metal combination electrode with
Silver electrode has same shape, and nickel, copper, the volume ratio of aluminum stannum single-layer electrodes are 2:40:1, simultaneously except gold in base metal slurry
Metal particles other component prices outer are identical with silver slurry, then after silver slurry is by base metal slurry replacing whole of the present invention, and whole world crystal silicon
Solar cell slurry one be only about consumption 100,000,000 yuan, domestic about consumption 0.7 hundred million yuan, one of percentage before just corresponding to, greatly
Reduce production cost.If silver slurry is all replaced by base metal slurry of the present invention, the whole world announced according to CPIA and state's inner assembly
Global and the domestic cost-effective volume of base metal slurry of yield estimation, in 2016 years, whole world cost of sizing agent can cut down 10,500,000,000
Unit, domestic cost of sizing agent cuts down 8,000,000,000 yuan.Although the present invention program adds secondary printing operation, add certain equipment and throw
Entering, but produce daily as a example by the product line of 30000 by wall scroll, the slurry consumption of 1 year just can save 7,800,000 yuan, completely covers and sets
Standby input, the printing equipment still more increased can use for many years.
Accompanying drawing explanation
Fig. 1 copper slurry component schematic diagram；
Fig. 2 crystal silicon solar battery front nickel copper/aluminum stannum base metal combined electrode structure schematic diagram.
Detailed description of the invention
As it is shown in figure 1, the present invention for the copper slurry of crystal silicon solar battery front side conductive layer electrode by 85～95wt% receive
Rice copper powder, 1～the glass dust of 5wt% and the organic carrier composition of 4～14wt%.
The present invention uses copper powder base metal granule as conducting function phase, regulates and controls slurry in conjunction with Binder Phase and organic carrier and glues
The performances such as knot, thixotropy, rheological characteristic, are preset at crystal silicon solar battery front post-drying, prepare conductive layer copper electrode, as crystal silicon
The conducting layer electrode of solar cell front nickel copper/aluminum stannum base metal combination electrode.Described crystal silicon solar battery front nickel copper/
The bottom of aluminum stannum base metal combination electrode is resistance diffusion layer nickel electrode, and middle level is conductive layer copper electrode, and top layer is anti oxidation layer aluminum
Tin electrode, as shown in Figure 2.
Embodiment 1
(1) organic carrier of 14wt% is placed in container, described container is placed in the thermostatic water bath that temperature is 60 DEG C,
The organic carrier being stirred continuously in container with the speed of 180 revs/min, heated and stirred, after 10 hours, adds with the speed of 5g/min
Enter the copper nanoparticle of 85wt%, prepare mixture a.Wherein, the particle diameter of copper nanoparticle is 500～800nm, and purity is more than 99%；
Organic carrier is by the butyl of 60wt%, the tributyl citrate of 15wt%, the ethyl cellulose of 3wt%, 6wt%
Polyamide wax, the lecithin of 5wt%, the tributyl phosphate of 5wt% and 6wt% Polyethylene Glycol composition, by butyl,
After tributyl citrate, ethyl cellulose, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol mix in proportion
It is placed in 80 DEG C of thermostatic containers, stirs 5 hours and prepare.
(2) thermostatic water bath temperature is brought up to 80 DEG C, the step (1) being stirred continuously in container with the speed of 200 revs/min
The mixture a prepared, heated and stirred, after 5 hours, adds the glass dust of 1wt%, prepares mixture b with the speed of 1g/min.Glass
Glass powder is by the TeO of PbO, 20wt% of 50wt%2, the SiO of 15wt%2, the A1 of 5wt%2O3, the B of 5wt%2O3With 5wt%'s
Bi2O3Composition, by PbO, TeO2、SiO2、A12O3、B2O3And Bi2O3Mix in proportion to be placed in 1400 DEG C of Muffle furnaces and add
Heat, after insulation 60min, quenching ball milling prepare.
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 8 hours, prepares mixed
Compound c.
(4) the mixture c prepared by the silk screen filter step (3) of 300 mesh, prepares for crystal silicon solar battery front side conductive
The copper slurry of layer electrode.
Embodiment 2
(1) organic carrier of 10wt% is placed in container, described container is placed in the thermostatic water bath that temperature is 70 DEG C,
The organic carrier being stirred continuously in container with the speed of 140 revs/min, heated and stirred, after 5 hours, adds with the speed of 20g/min
Enter the copper nanoparticle of 85wt%, prepare mixture a.Wherein, the particle diameter of copper nanoparticle is 500～800nm, and purity is more than 99%；
Organic carrier is by the butyl of 60wt%, the tributyl citrate of 15wt%, the ethyl cellulose of 3wt%, 6wt%
Polyamide wax, the lecithin of 5wt%, the tributyl phosphate of 5wt% and 6wt% Polyethylene Glycol composition, by butyl,
After tributyl citrate, ethyl cellulose, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol mix in proportion
It is placed in 80 DEG C of thermostatic containers, stirs 5 hours and prepare.
(2) thermostatic water bath temperature is brought up to 90 DEG C, the step (1) being stirred continuously in container with the speed of 160 revs/min
The mixture a prepared, heated and stirred, after 3 hours, adds the glass dust of 5wt%, prepares mixture b with the speed of 3g/min.Glass
Glass powder is by the TeO of PbO, 20wt% of 50wt%2, the SiO of 15wt%2, the A1 of 5wt%2O3, the B of 5wt%2O3With 5wt%'s
Bi2O3Composition, by PbO, TeO2、SiO2、A12O3、B2O3And Bi2O3Mix in proportion to be placed in 1400 DEG C of Muffle furnaces and add
Heat, after insulation 60min, quenching ball milling prepare.
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 7 hours, prepares mixed
Compound c.
(4) the mixture c prepared by the silk screen filter step (3) of 400 mesh, prepares for crystal silicon solar battery front side conductive
The copper slurry of layer electrode.
Embodiment 3
(1) organic carrier of 10wt% is placed in container, described container is placed in the thermostatic water bath that temperature is 80 DEG C,
The organic carrier being stirred continuously in container with the speed of 90 revs/min, heated and stirred, after 1 hour, adds with the speed of 30g/min
The copper nanoparticle of 89wt%, prepares mixture a.Wherein, the particle diameter of copper nanoparticle is 500～800nm, and purity is more than 99%；Have
Airborne body by the butyl of 60wt%, the tributyl citrate of 15wt%, the ethyl cellulose of 3wt%, 6wt% poly-
The Polyethylene Glycol composition of amide waxe, the lecithin of 5wt%, the tributyl phosphate of 5wt% and 6wt%, by butyl, lemon
Lemon acid tributyl, ethyl cellulose, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol mix in proportion rearmounted
In 80 DEG C of thermostatic containers, stir 5 hours and prepare.
(2) thermostatic water bath temperature is brought up to 100 DEG C, the step being stirred continuously in container with the speed of 120 revs/min
(1) the mixture a prepared, heated and stirred, after 1 hour, adds the glass dust of 1wt%, prepares mixture b with the speed of 5g/min.
Glass dust is by the TeO of PbO, 20wt% of 50wt%2, the SiO of 15wt%2, the A1 of 5wt%2O3, the B of 5wt%2O3With 5wt%'s
Bi2O3Composition, by PbO, TeO2、SiO2、A12O3、B2O3And Bi2O3Mix in proportion to be placed in 1400 DEG C of Muffle furnaces and add
Heat, after insulation 60min, quenching ball milling prepare.
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 6 hours, prepares mixed
Compound c.
(4) the mixture c prepared by the silk screen filter step (3) of 350 mesh, prepares for crystal silicon solar battery front side conductive
The copper slurry of layer electrode.
Embodiment 4
(1) organic carrier of 4wt% is placed in container, described container is placed in the thermostatic water bath that temperature is 65 DEG C,
The organic carrier being stirred continuously in container with the speed of 120 revs/min, heated and stirred, after 8 hours, adds with the speed of 15g/min
Enter the copper nanoparticle of 95wt%, prepare mixture a.Wherein, the particle diameter of copper nanoparticle is 500～800nm, and purity is more than 99%；
Organic carrier is by the butyl of 60wt%, the tributyl citrate of 15wt%, the ethyl cellulose of 3wt%, 6wt%
Polyamide wax, the lecithin of 5wt%, the tributyl phosphate of 5wt% and 6wt% Polyethylene Glycol composition, by butyl,
After tributyl citrate, ethyl cellulose, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol mix in proportion
It is placed in 80 DEG C of thermostatic containers, stirs 5 hours and prepare.
(2) thermostatic water bath temperature is brought up to 85 DEG C, the step (1) being stirred continuously in container with the speed of 180 revs/min
The mixture a prepared, heated and stirred, after 3 hours, adds the glass dust of 1wt%, prepares mixture b with the speed of 4g/min.Glass
Glass powder is by the TeO of PbO, 20wt% of 50wt%2, the SiO of 15wt%2, the A1 of 5wt%2O3, the B of 5wt%2O3With 5wt%'s
Bi2O3Composition, by PbO, TeO2、SiO2、A12O3、B2O3And Bi2O3Mix in proportion to be placed in 1400 DEG C of Muffle furnaces and add
Heat, after insulation 60min, quenching ball milling prepare.
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 6.5 hours, prepares
Mixture c.
(4) the mixture c prepared by the silk screen filter step (3) of 300 mesh, prepares for crystal silicon solar battery front side conductive
The copper slurry of layer electrode.
Embodiment 5
(1) organic carrier of 8wt% is placed in container, described container is placed in the thermostatic water bath that temperature is 75 DEG C,
The organic carrier being stirred continuously in container with the speed of 160 revs/min, heated and stirred, after 3 hours, adds with the speed of 25g/min
Enter the copper nanoparticle of 90wt%, prepare mixture a.Wherein, the particle diameter of copper nanoparticle is 500～800nm, and purity is more than 99%；
Organic carrier is by the butyl of 60wt%, the tributyl citrate of 15wt%, the ethyl cellulose of 3wt%, 6wt%
Polyamide wax, the lecithin of 5wt%, the tributyl phosphate of 5wt% and 6wt% Polyethylene Glycol composition, by butyl,
After tributyl citrate, ethyl cellulose, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol mix in proportion
It is placed in 80 DEG C of thermostatic containers, stirs 5 hours and prepare.
(2) thermostatic water bath temperature is brought up to 95 DEG C, the step (1) being stirred continuously in container with the speed of 160 revs/min
The mixture a prepared, heated and stirred, after 2 hours, adds the glass dust of 2wt%, prepares mixture b with the speed of 2g/min.Glass
Glass powder is by the TeO of PbO, 20wt% of 50wt%2, the SiO of 15wt%2, the A1 of 5wt%2O3, the B of 5wt%2O3With 5wt%'s
Bi2O3Composition, by PbO, TeO2、SiO2、A12O3、B2O3And Bi2O3Mix in proportion to be placed in 1400 DEG C of Muffle furnaces and add
Heat, after insulation 60min, quenching ball milling prepare.
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 7.5 hours, prepares
Mixture c.
(4) the mixture c prepared by the silk screen filter step (3) of 400 mesh, prepares for crystal silicon solar battery front side conductive
The copper slurry of layer electrode.
Performance test example
Use 156 × 156mm2Polysilicon chip, embodiment 1～5 preparation conductive layer copper electrode corresponding to cell performance
Can, at AM 1.5G, 100mW/cm2, under conditions of 25 DEG C, use the test of I-V tester, result is as shown in table l.
Table 1, embodiment battery performance.
| The present invention | Open-circuit voltage (V) | Short circuit current (A) | Fill factor, curve factor (%) | Electricity conversion (%) |
| Embodiment 1 | 0.622 | 8.88 | 78.01 | 17.72 |
| Embodiment 2 | 0.623 | 8.84 | 78.09 | 17.68 |
| Embodiment 3 | 0.625 | 8.86 | 78.01 | 17.77 |
| Embodiment 4 | 0.627 | 8.86 | 77.84 | 17.79 |
| Embodiment 5 | 0.628 | 8.84 | 78.16 | 17.83 |
Claims (6)
1. the copper slurry for crystal silicon solar battery front side conductive layer electrode, it is characterised in that: described copper slurry by 85～
The glass dust of the copper nanoparticle of 95wt%, 1～5wt% and the organic carrier composition of 4～14wt%；The grain of described copper nanoparticle
Footpath is 500～800nm, and purity is more than 99%；Described copper slurry is preset at crystal silicon solar battery front, prepares conductive layer after drying
Copper electrode, as the conducting layer electrode of crystal silicon solar battery front nickel copper/aluminum stannum base metal combination electrode；Described crystal silicon is too
The bottom of sun battery front side nickel copper/aluminum stannum base metal combination electrode is resistance diffusion layer nickel electrode, and middle level is conductive layer copper electrode,
Top layer is anti oxidation layer aluminum tin electrode.
2. the preparation method that the copper for crystal silicon solar battery front side conductive layer electrode described in claim 1 is starched, its feature exists
In: described preparation method step is as follows:
(1) organic carrier is placed in container, described container is placed in the thermostatic water bath that temperature is 60～80 DEG C, with 90～
The speed of 180 revs/min is stirred continuously the organic carrier in container, heated and stirred 1～after 10 hours, with the speed of 5～30g/min
Rate adds copper nanoparticle, prepares mixture a；
(2) thermostatic water bath temperature is brought up to 80～100 DEG C, be stirred continuously in container step with the speed of 120～200 revs/min
Suddenly the mixture a that (1) prepares, heated and stirred 1～after 5 hours, the speed with 1～5g/min adds glass dust, prepares mixture
b；
(3) the mixture b that step (2) prepares being placed in three-roll grinder grinding, milling time is 6～8 hours, prepares mixing
Thing c；
(4) the mixture c prepared by the silk screen filter step (3) of 300～400 mesh, prepares and leads for crystal silicon solar battery front
The copper slurry of electric layer electrode.
The preparation method that copper for crystal silicon solar battery front side conductive layer electrode the most according to claim 2 is starched, it is special
Levy and be: in described step (1) and step (2), the percentage by weight of the copper nanoparticle, glass dust and the organic carrier that are added
It is respectively 85～95wt%, 1～5wt% and 4～14wt%.
Preparation method the most according to claim 2, it is characterised in that: the particle diameter of described copper nanoparticle be 500～
800nm, purity is more than 99%.
Preparation method the most according to claim 2, it is characterised in that: described glass dust is by PbO, 20wt% of 50wt%
TeO2, the SiO of 15wt%2, the A1 of 5wt%2O3, the B of 5wt%2O3Bi with 5wt%2O3Composition, by PbO, TeO2、SiO2、
A12O3、B2O3And Bi2O3Mix in proportion and be placed in 1400 DEG C of Muffle furnaces heating, quenching ball milling system after insulation 60min
?.
Preparation method the most according to claim 2, it is characterised in that: described organic carrier is by the diethylene glycol of 60wt%
Butyl ether, the tributyl citrate of 15wt%, the ethyl cellulose of 3wt%, the polyamide wax of 6wt%, the lecithin of 5wt%,
The tributyl phosphate of 5wt% and the Polyethylene Glycol composition of 6wt%, by butyl, tributyl citrate, ethyl cellulose
Element, polyamide wax, lecithin, tributyl phosphate and Polyethylene Glycol mix in proportion and are placed in 80 DEG C of thermostatic containers, stir
Mix 5 hours and prepare.
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| CN107622809A (en) * | 2017-09-25 | 2018-01-23 | 江苏时瑞电子科技有限公司 | A kind of copper electrode paste and preparation method thereof |
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Application publication date: 20161221 |