CN105810759B - A kind of silver-colored aluminum slurry used for solar batteries - Google Patents
A kind of silver-colored aluminum slurry used for solar batteries Download PDFInfo
- Publication number
- CN105810759B CN105810759B CN201610264780.XA CN201610264780A CN105810759B CN 105810759 B CN105810759 B CN 105810759B CN 201610264780 A CN201610264780 A CN 201610264780A CN 105810759 B CN105810759 B CN 105810759B
- Authority
- CN
- China
- Prior art keywords
- silver
- powder
- aluminum slurry
- glass dust
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 65
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002002 slurry Substances 0.000 title claims abstract description 60
- 239000011521 glass Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000428 dust Substances 0.000 claims abstract description 34
- 239000004411 aluminium Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 9
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- -1 silver aluminum Chemical compound 0.000 claims description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 235000010445 lecithin Nutrition 0.000 claims description 11
- 239000000787 lecithin Substances 0.000 claims description 11
- 229940067606 lecithin Drugs 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 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 4
- 229920000180 alkyd Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 25
- 239000004332 silver Substances 0.000 abstract description 9
- 229910052709 silver Inorganic materials 0.000 abstract description 9
- 239000004615 ingredient Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 13
- 238000007639 printing Methods 0.000 description 7
- 229910052810 boron oxide Inorganic materials 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 description 1
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 1
- 229940067626 phosphatidylinositols Drugs 0.000 description 1
- 150000003905 phosphatidylinositols Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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
-
- 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)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of silver-colored aluminum slurry, include the following component of percentage by weight：Conducting metal powder 60 85%, graphene 2 10%, glass dust 6 18%, organic binder bond 9 20%, auxiliary agent 1 3% amounts to 100%；The conducting metal powder is silver powder and aluminium powder, and the part by weight of silver powder and aluminium powder is 6：2‑3：5；The glass dust is constituted comprising following component：SiO23 17%, TiO21 2%, Bi2O335 52%, Al2O34 8%, SrCl21 7%, B2O315 38%, SnO22~5%, CaO 0.1~2%, amounts to 100%.Being contained in the silver-colored aluminum slurry of the present invention based on silver powder and aluminium powder causes metal ingredient, wherein the aluminium applied and silver are collectively as conducting metal powder, because aluminium powder instead of the silver powder of part, so the cost of electrocondution slurry is reduced well.Simultaneously the electric conductivity after silver-colored aluminum slurry sintering is added present invention adds black alkene.
Description
Technical field
The present invention relates to semi-conducting material, more particularly to a kind of silver-colored aluminum slurry used for solar batteries, is that a kind of electrode is special
Conductive material, belongs to electronic applications, conductive material field.
Background technology
Solar cell is the semiconductor devices converted solar energy into electrical energy.Solar cell is a kind of emerging green
The energy, effectively can replace traditional energy using solar energy, reduce the discharge of carbon dioxide, conservation of nature environment, and realization can
Sustainable development.
In the processing preparation process of existing solar cell, it is necessary to introduce electrode in the front and back of cell panel, often
Electrode material is silver paste, silver-colored aluminum slurry and aluminum slurry.Silver paste is conductive can good, the stronger spy of adaptability
Point, but with the development of electronic applications, the consumption of silver paste is increasing.Silver itself is as precious metal material, and price is even more
As market conditions significantly increase, directly result in the silver paste price that electronic applications use increases year by year.
Although also there is the producer that part is replaced using silver-colored aluminium paste and aluminium paste in the prior art, the resistance of aluminium paste is relative
Higher, and it is big then to there is mixture homogeneity control difficulty as the silver-colored aluminium paste of middle transition, electric conductivity is difficult to reach expected
Problem.
The content of the invention
It is an object of the invention to overcome the silver paste price in the presence of prior art high, and there is electric conductivity in substitute
Can, there is provided a kind of silver-colored aluminum slurry for the deficiency of problems such as adhesion.The silver-colored aluminum slurry used for solar batteries of the present invention has
Mixing uniformity is good, and electric conductivity is protruded, the characteristics of being firmly combined with substrate.
In order to realize foregoing invention purpose, the invention provides following technical scheme：
A kind of silver-colored aluminum slurry, includes the following component of percentage by weight：Conducting metal powder 60-85%, graphene 2-
10%, glass dust 6-18%, organic binder bond 9-20%, auxiliary agent 1-3%, amount to 100%.
The conducting metal powder is silver powder and aluminium powder, and the part by weight of silver powder and aluminium powder is 6：2-3：5.
The glass dust is constituted comprising following component：SiO23-17%, TiO21-2%, Bi2O335-52%, Al2O34-
8%, SrCl21-7%, B2O315-38%, SnO22~5%, CaO 0.1~2%, amounts to 100%.
First, being contained in silver-colored aluminum slurry of the invention causes metal ingredient based on silver powder and aluminium powder, wherein applying
Aluminium and silver collectively as conducting metal powder, because aluminium powder instead of the silver powder of part, so the cost of electrocondution slurry is obtained
Reduction well.Then, appropriate graphene is added in silver-colored aluminum slurry of the invention, can be with when graphene is used alone
Used as conductive material, and show the conductive capability of graphene even than ordinary metallic material more according to reliable research
By force, thus mixing graphene in the slurry can promote slurry sinter after electric conductivity.Meanwhile, what is more important graphite
Alkene is made up of carbon, can be played reduction protection effect to the aluminium powder in slurry during sintering, be reduced sintering
During aluminium powder oxidation generation alundum (Al2O3) ratio, meanwhile, the aluminum oxide on reduction aluminium powder surface reduces the electricity after sintering
Boundary layer in extremely, improves the electric conductivity of electrode.
Secondly, glass frit component of the invention has selected lead-free glass powder, and it is applied by special into component selections and ratio
Adjustment meticulously, using bismuth oxide and boron oxide as the partial substitute of silica, is made with silica, bismuth oxide and boron oxide
For the main body of the basic phase of glass.Because both bismuth oxide and boron oxide have good concertedness, substitute after part of silica
The agent structure of the basic phase of the glass dust of formation, with more preferable stability and fusing feature, can be played more in sintering process
Good cementation, the electrode of sintering curing and the new of solar base plate and degree are more preferable, and what can more be stablized is bonded in thereon, protects
Demonstrate,prove the stability and durability of electrode.Particularly the usage ratio control of bismuth oxide and boron oxide is close to 2：When 1 or so, collaboration
Property it is optimal, the easy sinterability and caking property of silver-colored aluminum slurry are optimal.After strontium chloride is added, collaboration can be cooperatively formed with boron oxide and is made
With reduction sintering temperature.The application of strontium chloride has harmful effect for the structural stability and wearability of glass dust, unsuitable excessive
Use.The present invention is by the selection to each component in glass dust and its consumption proportion, and each components matching ratio is suitable so that use
Conductive silver paste made from the glass dust has that environment-friendly, sintering character is excellent, electric conductivity is excellent.
Further, the weight percentage of the glass dust is 7-18%, optimizes electricity after the consumption of glass dust, adjustment sintering
The accounting of extremely middle glass phase, it is ensured that the bonding stability of conductive electrode is preferable, while because glass phase in conductive electrode
Caused resistance rise control is in relatively low scope, it is ensured that the electric conductivity of electrode in solar cells.It is preferred that glass
The content of powder is 10-17%, and the caking property and electric conductivity after glass powder sintering are preferable within this range, is particularly and solar energy
The combination great efforts of cell basis layer.For more specifically, the weight percentage of the glass dust can for 11%, 13%,
14%th, the specific number such as 16%.
Further, the weight percentage of the organic binder bond is 10-19%, can from suitable organic binder bond
It is more preferable with the pattern that coordination electrode is printed during silk-screen printing, close to preferable electrode shape after sintering, for lifting
The electricity conversion of solar cell has certain help.Preferably 12-18%, within this range organic binder bond
The basic role of performance is optimal, and printing effect is best, and residue is less after organic binder bond carbonization after sintering, for electrode
The influence of electric conductivity is small.For more specifically, the weight percentage of the organic binder bond can for 12%, 14%,
The 16% specific number of grade.
Further, the organic binder bond is constituted comprising following component：Rosin resin 10-20%, ethyl cellulose 10-
25%, butyl carbitol 5-10%, isophthalic alkyd resin 5-10%, dimethyl succinate 10-20%, terpinol 20-
40%, amount to 100%.The composition that the organic binder bond of the present invention is selected employs rosin resin, ethyl cellulose simultaneously, easily
It is uniformly dispersed, does not reunite with silver powder, can be good at ensureing the printing uniformity and thickness control of electrode, and protects sintering shape
Looks.The butyl carbitol and terpinol of selection have the effect of the mobility and stability that ensure silver-colored aluminum slurry, it can be ensured that silver
Aluminum slurry property more stable and consistent during storage, it is to avoid the window of silver-colored aluminum slurry printing is narrow to cause processing difficulties.Its
The isophthalic alkyd resin and Petropols of middle selection are the compositions of electrode preboarding after auxiliary printing, and it coordinates butyl card
Must alcohol and when terpinol, be mutually dissolved good dispersion, and after mutually phased soln is scattered can to silver powder, glass dust formation compared with
Good package structure, the i.e. distributing homogeneity of silver powder wherein, free-running property are all more protruded, more conducively the printing shaping of electrode.
Meanwhile, finely dispersed terpinol and Petropols can react to form specific consolidated structures when sintering so that electricity
The relatively reliable stabilization of form extremely in use.
Further, 10-20% lecithin is also included in organic binder bond.Lecithin is applied to belong to first in silver-colored aluminum slurry
Secondary to attempt, lecithin is to be present in one group of filemot oil material among animal vegetable tissue and yolk, and it is constituted into
Dividing includes phosphoric acid, choline, aliphatic acid, glycerine, glycolipid, triglyceride and phosphatide (such as phosphatidyl choline, phosphatidyl-ethanolamine
And phosphatidylinositols).Inventor has found, after lecithin and silver-colored aluminum slurry mixing, can combine, realize with silver powder particulate component
For the peptizaiton of silver powder particle, it is often more important that lecithin can also interact with graphene, exist in lecithin
In the case of, graphene dispersion is more uniform, and the electric conductivity increase for electrode has great importance.In lecithin and stone
The unique design feature of black alkene, when sintering curing, can be combined with each other reaction, realize unique attachment structure, enhancing
The Performance Strength of electrode.
Further, the auxiliary agent is polyamide wax.Polyamide wax is a kind of thixotropy additive, is formed in silver-colored aluminum slurry
Powerful network structure, its excellent thixotropic property, with excellent resist sagging ability, anti-settling ability, can keep slurry
Storage stability, prevent slurry be layered wash rice liquid the problems such as occur.Electrode during screen printing electrode can preferably be controlled
Pattern, improve electrode sintering before structural stability.Preferred promoter consumption is 1-1.4%.
A kind of method for preparing above-mentioned silver-colored aluminum slurry, comprises the following steps：
Step (1) prepares glass dust
Take glass dust raw material to be well mixed in proportion, be put into crucible, smelting temperature is 1100-1250 DEG C, and melting 1-2 is small
When；After the completion of melting, water smoke quenching, ball milling obtains the glass dust that particle diameter is not more than 5 microns after drying.
Step (2) prepares premixed solution
Raw material is weighed in proportion, other compositions beyond rosin resin are mixed, 80-110 DEG C is heated to, and stirs 0.5-2
Hour, it is well mixed, obtains premixed solution.
Step (3) prepares silver-colored aluminum slurry
Premixed solution prepared by step 2, insulation adds silver powder, aluminium powder, glass dust and graphene, is uniformly mixed,
Rosin resin and polyamide wax are eventually adding, is ground 10-60 minutes with three-high mill, prepares conductive silver aluminum slurry.
Compared with prior art, beneficial effects of the present invention：
1. cause metal ingredient based on silver powder and aluminium powder are contained in the silver-colored aluminum slurry of the present invention, wherein the aluminium applied
With silver collectively as conducting metal powder, because aluminium powder instead of the silver powder of part, so the cost of electrocondution slurry is obtained very well
Reduction.
, can be as leading when graphene is used alone 2. add appropriate graphene in the silver-colored aluminum slurry of the present invention
Electric material is used, and shows that the conductive capability of graphene is even more stronger than ordinary metallic material according to reliable research, therefore
The graphene of mixing in the slurry can promote the electric conductivity after slurry sintering.
3. the graphene of the present invention is made up of carbon, the aluminium powder in slurry can be played during sintering
Reduction protection is acted on, the aluminum oxide on reduction aluminium powder surface, is reduced the boundary layer in the electrode after sintering, is improved the electric conductivity of electrode
Energy.
4. the glass frit component mixing ratio of the present invention is suitable, glass dust is used as using silica, bismuth oxide and boron oxide
The bulk composition of basic phase, reduces sintering temperature, with excellent sintering character, meanwhile, the compatibility with organic adhesive
Good, the electrode of sintering curing and the new of solar base plate and degree are more preferable, and what can more be stablized be bonded in thereon, it is ensured that electrode it is steady
Qualitative and durability.
Embodiment
The present invention additionally provides a kind of method for preparing above-mentioned silver-colored aluminum slurry simultaneously, comprises the following steps：
Step (1) prepares glass dust
Following raw material is taken in proportion：SiO23-17%, TiO21-2%, Bi2O335-52%, Al2O34-8%,
SrCl21-7%, B2O315-38%, SnO22~5%, CaO 0.1~2%, amounts to 100%.It is well mixed, it is put into crucible
In, smelting temperature is 1100-1250 DEG C, melting 1-2 hours.After the completion of melting, water smoke quenching, ball milling obtains particle diameter after drying
No more than 5 microns of glass dust.
Step (2) prepares premixed solution
Raw material is weighed in proportion, other compositions beyond rosin resin are mixed, 80-110 DEG C is heated to, and stirs 0.5-2
Hour, preferably 1-1.5 hours, it is well mixed, obtains premixed solution.
Step (3) prepares silver-colored aluminum slurry
Premixed solution prepared by step 2, insulation adds silver powder, aluminium powder, glass dust and graphene, is uniformly mixed,
Rosin resin and polyamide wax are eventually adding, is ground 10-60 minutes with three-high mill, prepares conductive silver aluminum slurry.
Further, ball milling processing is carried out using planetary ball mill when ball milling in step 1.It is preferred that ball milling process
In, ethanol solution protection.It is fast with ball milling speed using Alcohol Protection ball milling, the high advantage of ball milling quality.Further,
Ball milling is carried out using a diameter of 3-15mm zirconium oxide bead.Hardness is suitable, and grinding efficiency is high, and ball mill grinding granularity is tiny.
Further, when step 2 preferably prepares premixed solution, during heating stirring is mixed, when temperature is increased to 70
When more than DEG C, it is protected by using nitrogen atmosphere.
Further, in step 3, when adding silver powder, aluminium powder, glass dust and graphene, sequentially add in the following order：
Glass dust, silver powder, aluminium powder, graphene.Often add after a component, stirring adds next component in 5-20 minutes.
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of above-mentioned theme of the invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.Not specified percentage is weight percentage in the present invention.
Embodiment 1-5
Prepare glass dust
Following raw material is taken in proportion：SiO23-17%, TiO21-2%, Bi2O335-52%, Al2O34-8%,
SrCl21-7%, B2O315-38%, SnO22~5%, CaO 0.1~2%, amounts to 100%.It is well mixed, it is put into crucible
In, smelting temperature is 1100-1250 DEG C, melting 1-2 hours.After the completion of melting, water smoke quenching, ball milling obtains particle diameter after drying
No more than 5 microns of glass dust.Specific embodiment 1-5 material rate see the table below.
The glass dust raw material component ratio of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| SiO2 | 4.3 | 11.9 | 10.4 | 12.7 | 16.9 |
| TiO2 | 1.3 | 1.3 | 1.1 | 1.4 | 1.9 |
| Bi2O3 | 38.9 | 51.8 | 47.4 | 36.1 | 43.6 |
| Al2O3 | 4.1 | 4.8 | 6.2 | 5.2 | 7.1 |
| SrCl2 | 7.0 | 1.2 | 4.3 | 2.2 | 4.6 |
| B2O3 | 39.4 | 24.6 | 27.2 | 37.9 | 22.3 |
| SnO2 | 4.1 | 4.2 | 2.9 | 3.2 | 3.3 |
| CaO | 1.0 | 0.1 | 0.4 | 1.3 | 0.4 |
Embodiment 6-13
Prepare conductive silver aluminum slurry
Raw material is taken in the ratio of table 2.Other compositions beyond rosin resin will be mixed, be heated to 80-110 DEG C, stirring
0.5-2 hours, preferably 1-1.5 hours, it is well mixed, obtains premixed solution.Premixed solution is incubated, silver powder, aluminium powder, glass is added
Glass powder and graphene, are uniformly mixed, and are eventually adding rosin resin and polyamide wax, are ground 10-60 minutes with three-high mill,
Prepare conductive silver aluminum slurry.Specific embodiment 6-13 material rate see the table below.It is prepared by embodiment 6-7 Application Examples 1
Glass dust, embodiment 8-9 Application Examples 2 prepare glass dust, embodiment 10-13 Application Examples 5 prepare glass dust.
The conductive silver aluminum slurry component ratio of table 2
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| Silver powder | 35.7 | 43.0 | 41.4 | 43.9 | 41.3 | 47.6 | 38.2 | 28.5 |
| Aluminium powder | 32.3 | 17.0 | 35.6 | 20.1 | 26.7 | 23.4 | 34.8 | 41.5 |
| Graphene | 7.0 | 5.0 | 8.0 | 7.0 | 5.0 | 4.0 | 5.0 | |
| Glass dust | 12.0 | 14.0 | 6.0 | 14.0 | 10.0 | 12.0 | 9.0 | 10.0 |
| Rosin resin | 2.9 | 3.4 | 1.3 | 1.3 | 2.4 | 1.7 | 2.1 | 2.2 |
| Ethyl cellulose | 3.8 | 3.8 | 1.9 | 2.9 | 3.2 | 2.4 | 1.3 | 2.6 |
| Butyl carbitol | 1.4 | 1.6 | 0.7 | 1.1 | 0.7 | 0.7 | 0.8 | 0.9 |
| Isophthalic alkyd resin | 1.4 | 1.4 | 0.6 | 0.8 | 1.1 | 0.9 | 1.0 | 0.8 |
| Dimethyl succinate | 3.1 | 2.7 | 1.7 | 1.3 | 1.7 | 1.9 | 1.8 | 1.4 |
| Terpinol | 5.4 | 5.0 | 3.8 | 4.6 | 4.9 | 2.4 | 3.1 | 5.1 |
| Auxiliary agent | 2.0 | 1.0 | 2.0 | 2.0 | 1.0 | 1.0 | 2.0 | 1.0 |
| Lecithin | 1.0 | 2.0 | 1.0 |
Test case
The electrode of the sunny energy battery of technique printing printed to the silver-colored aluminum slurry of above-described embodiment 6-13 preparations using printed network,
The resistance of electrode is tested, pulling force, softening temperature is as a result as shown in the table.
The test result of table 3
| Resistance (string resistance) | Pulling force | Softening temperature (DEG C) | |
| Embodiment 6 | 0.045 | 1.7 | 494 |
| Embodiment 7 | 0.032 | 2.5 | 505 |
| Embodiment 8 | 0.029 | 3.4 | 510 |
| Embodiment 9 | 0.031 | 2.9 | 476 |
| Embodiment 10 | 0.033 | 2.4 | 481 |
| Embodiment 11 | 0.024 | 2.8 | 479 |
| Embodiment 12 | 0.027 | 2.9 | 484 |
| Embodiment 13 | 0.024 | 3.2 | 482 |
From passing through test result, conductive silver aluminum slurry of the invention has conductive characteristic good, and stretching resistance is stronger, burns
The characteristics of junction temperature is low, is used as the resistance control that can be good at ensureing inside solar energy battery after the electrode print of solar cell
System is conducive to improving the electricity conversion of solar cell, improves the utilization rate of solar energy in extremely low level.
The above results show that graphene in the slurry can promote the electric conductivity after slurry sintering, embodiment 11-13
Result show that after application graphene and lecithin is added in slurry simultaneously, the mixing ratios of various components is suitable, Neng Gougeng
Plus the resistance effectively reduced after the resistance characteristic of electrode, electrode sintering curing shows extremely low level, for improving the sun
The optical energy utilization efficiency of energy battery has great importance.Moreover, embodiment 11-13 silver-colored aluminium paste formula can also provide compared with
Good stretching resistance performance, it is ensured that silver-colored aluminum slurry printing is made after electrode, can during long-term use good holding electrode
With the adhesion of solar cell substrate, the damage for preventing external force from causing improves the service life of solar cell.
Finally, additionally by the contrast to softening temperature, it can be found that the overall softening temperature of the silver-colored aluminum slurry of the present invention
It is relatively low, when using silver-colored aluminum slurry, it can preferably reduce damage of the electrode sintering process high temperature for solar cell
Wound, improves the electricity conversion of solar cell.Graphene and lecithin are played in embodiment after particularly coordinating and optimizing
Chemiluminescence, the properties of silver-colored aluminum slurry have greatly improved or lifted, with important actual application value.
Claims (7)
1. a kind of silver-colored aluminum slurry, includes the following component of percentage by weight：Conducting metal powder 60-85%, graphene 2-10%,
Glass dust 10-17%, organic binder bond 9-20%, auxiliary agent 1-3%, amount to 100%；
The conducting metal powder is silver powder and aluminium powder, and the part by weight of silver powder and aluminium powder is 6：2-3：5；
The glass dust is constituted comprising following component：SiO23-17%, TiO21-2%, Bi2O335-52%, Al2O3 4-
8%, SrCl21-7%, B2O315-38%, SnO22~5%, CaO 0.1~2%, amounts to 100%；
The auxiliary agent is polyamide wax.
2. silver aluminum slurry as claimed in claim 1, it is characterised in that the weight percentage of organic binder bond is 10-19%.
3. silver aluminum slurry as claimed in claim 2, it is characterised in that the weight percentage of organic binder bond is 12-18%.
4. silver aluminum slurry as claimed in claim 1, it is characterised in that the organic binder bond includes following component and constituted：Rosin
Resin 10-20%, ethyl cellulose 10-25%, butyl carbitol 5-10%, isophthalic alkyd resin 5-10%, fourth two
Dimethyl phthalate 10-20%, terpinol 20-40%, amount to 100%.
5. silver aluminum slurry as claimed in claim 4, it is characterised in that 10-20% lecithin is also included in organic binder bond.
6. silver aluminum slurry as claimed in claim 5, it is characterised in that auxiliary dosage is 1-1.4%.
7. a kind of method for preparing the silver-colored aluminum slurries of claim 4-6, comprises the following steps：
Step (1) prepares glass dust
Following raw material is taken in proportion：SiO23-17%, TiO21-2%, Bi2O335-52%, Al2O34-8%, SrCl2 1-
7%, B2O3 15-38%, SnO2 2~5%, CaO 0.1~2%, amount to 100%；It is well mixed, it is put into crucible, melting
Temperature is 1100-1250 DEG C, melting 1-2 hours；After the completion of melting, water smoke quenching, ball milling obtains particle diameter after drying and is not more than 5
The glass dust of micron；
Step (2) prepares premixed solution
Raw material is weighed in proportion, other compositions beyond rosin resin are mixed, 80-110 DEG C is heated to, and is stirred 0.5-2 hours,
It is well mixed, obtain premixed solution；
Step (3) prepares silver-colored aluminum slurry
Premixed solution prepared by step 2, insulation adds silver powder, aluminium powder, glass dust and graphene, is uniformly mixed, finally
Rosin resin and polyamide wax are added, is ground 10-60 minutes with three-high mill, prepares conductive silver aluminum slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610264780.XA CN105810759B (en) | 2016-04-26 | 2016-04-26 | A kind of silver-colored aluminum slurry used for solar batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610264780.XA CN105810759B (en) | 2016-04-26 | 2016-04-26 | A kind of silver-colored aluminum slurry used for solar batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105810759A CN105810759A (en) | 2016-07-27 |
| CN105810759B true CN105810759B (en) | 2017-07-25 |
Family
ID=56457642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610264780.XA Active CN105810759B (en) | 2016-04-26 | 2016-04-26 | A kind of silver-colored aluminum slurry used for solar batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105810759B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110391040A (en) * | 2018-04-19 | 2019-10-29 | 无锡优顺能源开发科技有限公司 | A kind of photovoltaic cell electrocondution slurry |
| CN112992402B (en) * | 2021-04-16 | 2021-10-08 | 西安宏星电子浆料科技股份有限公司 | Silver and two-dimensional MXene mixed system conductor slurry for chip resistor and preparation method thereof |
| CN113793716B (en) * | 2021-11-17 | 2022-02-25 | 西安宏星电子浆料科技股份有限公司 | Low-voltage coefficient resistance paste |
| CN115069103A (en) * | 2022-08-09 | 2022-09-20 | 南通市盛远石墨烯新材料有限公司 | High dispersion stable form graphite alkene composite conductive paste preparation equipment |
| CN115838303B (en) * | 2023-02-22 | 2023-04-28 | 西安石油大学 | Silver paste for aluminum nitride ceramics |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522140A (en) * | 2011-12-27 | 2012-06-27 | 彩虹集团公司 | Aluminum paste for silicon-based solar cell and preparation method for aluminum paste |
| CN102629496A (en) * | 2012-04-27 | 2012-08-08 | 西安银泰新能源材料科技有限公司 | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry |
| CN102701595A (en) * | 2012-07-02 | 2012-10-03 | 昆明理工大学 | Lead-free glass powder and preparation method thereof |
| CN103117109A (en) * | 2012-12-07 | 2013-05-22 | 蚌埠市智峰科技有限公司 | Lead-free solar cell silver aluminum copper powder mixed paste containing graphite powder |
| CN105255422A (en) * | 2015-11-17 | 2016-01-20 | 张建刚 | Electrically conductive and thermally conductive graphene slurry and preparation method thereof |
-
2016
- 2016-04-26 CN CN201610264780.XA patent/CN105810759B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522140A (en) * | 2011-12-27 | 2012-06-27 | 彩虹集团公司 | Aluminum paste for silicon-based solar cell and preparation method for aluminum paste |
| CN102629496A (en) * | 2012-04-27 | 2012-08-08 | 西安银泰新能源材料科技有限公司 | Crystalline silicon solar battery front side electrode lead-free conductive lead slurry and preparation method of crystalline silicon solar battery front side electrode lead-free conductive lead slurry |
| CN102701595A (en) * | 2012-07-02 | 2012-10-03 | 昆明理工大学 | Lead-free glass powder and preparation method thereof |
| CN103117109A (en) * | 2012-12-07 | 2013-05-22 | 蚌埠市智峰科技有限公司 | Lead-free solar cell silver aluminum copper powder mixed paste containing graphite powder |
| CN105255422A (en) * | 2015-11-17 | 2016-01-20 | 张建刚 | Electrically conductive and thermally conductive graphene slurry and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105810759A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105810759B (en) | A kind of silver-colored aluminum slurry used for solar batteries | |
| US9230709B2 (en) | Paste composition for electrode of solar cell and solar cell including the same | |
| CN102136308B (en) | Organic carrier for silver paste and preparation method thereof as well as silver paste containing organic carrier and solar cell manufactured from silver paste | |
| TWI496755B (en) | Glass frit, paste composition, and solar cell | |
| CN105679410B (en) | High-adhesion-stability silver-aluminum slurry for solar battery | |
| CN105655005A (en) | Electrode silver slurry for crystalline silicon solar cell | |
| CN106098144A (en) | A kind of glass dust and with its solar cell front side silver paste prepared and preparation method thereof | |
| CN102496418B (en) | Crystalline silicon solar cell back surface field aluminum alloy slurry and preparation method thereof | |
| CN101950600A (en) | Transparent dielectric paste | |
| CN103165214B (en) | A kind of aluminum conductive electric slurry used for solar batteries and preparation method thereof | |
| CN104376894A (en) | Solar cell conductive positive silver pulp | |
| CN108198648A (en) | A kind of back of the body passivation rear surface of solar cell silver paste | |
| WO2020252829A1 (en) | Low-temperature sintered back-surface silver paste for all-aluminum back-surface-field crystalline silicon solar cell | |
| CN104700923B (en) | A kind of rear surface of solar cell silver paste of high electricity conversion and preparation method thereof | |
| US10424418B2 (en) | Back surface field aluminum paste for point contacts of efficient bifacial crystalline silicon solar cells and preparation method thereof | |
| CN105118873B (en) | Crystal silicon solar energy battery front electrode silver slurry | |
| CN102103895B (en) | Silver paste used for positive electrodes of solar batteries and grid lines, preparation method thereof and solar battery containing same | |
| CN109215837A (en) | A kind of conductive silver slurry used for solar batteries and preparation method thereof | |
| CN105810288A (en) | Silver-aluminum paste easy to sinter for solar cell | |
| US11833584B2 (en) | Alloy aluminum paste for use on rear of PERC solar cell | |
| CN105741907B (en) | A kind of unleaded silver paste used for solar batteries | |
| CN110060794A (en) | PERC silver paste based on granularity compounding | |
| CN102651247B (en) | Novel conductive sizing agent for front-electrode of solar photovoltaic cell | |
| CN101560060A (en) | Surface treatment method of low temperature glass for solar cell conductive slurry | |
| CN104751939A (en) | Aluminum conductive slurry applicable to crystalline silicon solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |