CN115376722A - Copper-aluminum particle powder containing coating layer, preparation method and application thereof - Google Patents
Copper-aluminum particle powder containing coating layer, preparation method and application thereof Download PDFInfo
- Publication number
- CN115376722A CN115376722A CN202210916203.XA CN202210916203A CN115376722A CN 115376722 A CN115376722 A CN 115376722A CN 202210916203 A CN202210916203 A CN 202210916203A CN 115376722 A CN115376722 A CN 115376722A
- Authority
- CN
- China
- Prior art keywords
- copper
- aluminum
- particle powder
- aluminum particle
- coating
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 212
- 239000002245 particle Substances 0.000 title claims description 295
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims description 261
- 239000011247 coating layer Substances 0.000 title claims description 96
- 238000002360 preparation method Methods 0.000 title abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 83
- 238000005260 corrosion Methods 0.000 claims abstract description 56
- 230000007797 corrosion Effects 0.000 claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003112 inhibitor Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- 239000004411 aluminium Substances 0.000 claims abstract description 20
- 238000005253 cladding Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005639 Lauric acid Substances 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 29
- 239000004332 silver Substances 0.000 abstract description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 28
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- 239000008187 granular material Substances 0.000 abstract description 19
- 239000007788 liquid Substances 0.000 abstract description 17
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 25
- 238000009835 boiling Methods 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 239000003822 epoxy resin Substances 0.000 description 21
- 229920000647 polyepoxide Polymers 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000004593 Epoxy Substances 0.000 description 19
- 239000003960 organic solvent Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001723 curing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000005096 rolling process Methods 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229920002545 silicone oil Polymers 0.000 description 11
- 239000013008 thixotropic agent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- -1 hydrogen ions Chemical class 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical group CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical group CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- QKVROWZQJVDFSO-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanamine Chemical compound CC1=NC=CN1CCN QKVROWZQJVDFSO-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000012257 stirred material Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 208000034699 Vitreous floaters Diseases 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect 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
- H01B7/00—Insulated conductors or cables characterised by their form
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of 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
- 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
- H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/0009—Details relating to the conductive cores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2813—Protection against damage caused by electrical, chemical or water tree deterioration
-
- 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
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Dispersion Chemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Powder Metallurgy (AREA)
Abstract
The application discloses copper aluminium granule powder, preparation method and application that contain the coating, the inner zone of the granule of the copper aluminium granule powder that contains the coating is the copper aluminium granule, and the top layer is the coating, the coating contains cladding agent and corrosion inhibitor, the copper aluminium granule powder that contains the coating be arranged in the copper aluminium thick liquid, its contact resistance is low, the line resistance is low, and under the high temperature and high humidity resistant environment, the resistance attenuation rate is less than or equal to 8%, long-term reliability is good, and the cost is 1/10 of silver thick liquid.
Description
Technical Field
The application relates to the technical field of solar cell metallization, in particular to copper-aluminum particle powder containing a coating layer, a preparation method and application thereof.
Background
Low-temperature silver paste is adopted on two sides of the HJT (Heterojunction with Intrinsic Thin Layer) battery, so that the consumption of the silver paste is huge, the price is high, and the reason why the HJT cost is high is also considered. According to CPIA, the consumption of HJT battery double-sided low-temperature silver paste in 2020 is about 223.3 mg/piece, and the equivalent reduction is 25.6%. Although the consumption of silver paste is still large, the silver paste consumption is greatly improved and improved in 2020 and 2019. Currently, the consumption of the low-temperature silver paste is reduced by various technical improvements to reduce the production cost of the HJT battery, and the consumption of the HJT low-temperature silver paste is predicted to be reduced to 135 mg/sheet by 2030, which is 39.5% lower than that by 2020. The silicon wafer is the core material of the HJT cell, and occupies about 45% of the cost structure of the HJT cell. The cost of the silicon chip is removed, silver paste is taken as a core auxiliary material in a non-silicon material, the proportion is about 59%, and the quality of a heterojunction electrode influences hole and electron transmission and has great influence on the conversion efficiency of the battery. On the basis, the heterojunction low-temperature curing type slurry becomes a key material.
The use of base metal instead of silver can greatly reduce the cost of the electrode in the non-silicon material to 7-8%, reduce the cost of a single watt by 0.15 yuan, and basically keep the same with the cost of PERC.
Copper is the closest to silver in the existing metals. The advantages and disadvantages of the copper electroplating technology are obvious, the greatest advantage is that copper is used for replacing part or all of metal silver, the material cost is low, and double-sided metallization can be completed simultaneously. The disadvantages are that the process flow is longer than the traditional screen printing process, more equipment cost and labor cost are needed, copper is easy to oxidize at high temperature, the chemical property is not easy to control, a great amount of harmful chemical substances exist in electroplating solution, the treatment is troublesome, and the environmental protection cost is higher.
In addition, in the power generation process of the traditional silver paste used for the heterojunction battery, under a high-humidity environment, water molecules deeply permeate into the surface of the silver conductor to be electrolyzed to form hydrogen ions and hydroxyl ions, and silver is dissociated to generate silver ions under the action of an electric field and the hydroxyl ions. The migration of silver ions causes the formation of a bypass between the conductors without electrical connection, causing a decrease in insulation and even a short circuit, which may cause the component to fire in severe cases, and furthermore, silver costs 5000+ yuan/kg, which is relatively high.
Disclosure of Invention
In order to solve among the prior art traditional silver thick liquid and be used for among the heterojunction battery the power generation in-process silver ion's migration causes to form the bypass between the conductor that no electric appliance is connected, cause insulating decline and even short circuit and the higher problem of silver cost, this application provides a copper aluminium granule powder, preparation method and application that contain the coating, copper aluminium granule powder that contains the coating be used for among the copper aluminium thick liquid, its contact resistance is low, the line resistance is low, and under the high temperature and high humidity resistant environment, the resistance attenuation rate is less than or equal to 8%, long-term reliability is good, and the cost is 1/10 of silver thick liquid.
The specific technical scheme of the application is as follows:
1. the copper-aluminum particle powder containing the coating layer is characterized in that the copper-aluminum particles are arranged in the inner area of the particles of the copper-aluminum particle powder containing the coating layer, the coating layer is arranged on the surface layer of the particles, and the coating layer contains a coating agent and a corrosion inhibitor.
2. The copper-aluminum granular powder containing a coating according to item 1, wherein the granules of the copper-aluminum granular powder containing a coating comprise copper-aluminum granules, a corrosion inhibitor and a coating agent in this order from inside to outside.
3. The copper-aluminum granulated powder containing a coating layer according to item 1 or 2, wherein the specific surface area of the granules of the copper-aluminum granulated powder containing a coating layer is 0.7 to 1.8m 2 Preferably, the tap density is not less than 3.2g/ml.
4. The coated copper-aluminum particle powder according to any one of claims 1 to 3, wherein the coated copper-aluminum particle powder particlesAverage particle diameter D of 50 1.2-1.8 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 10 0.5-0.8 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 90 3.4-4.2 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 97 ≤10μm。
5. The copper-aluminum granular powder with a coating layer according to any one of items 1 to 4, wherein the coating agent is stearic acid, oleic acid, and/or lauric acid.
6. The clad-containing copper aluminum particle powder according to any one of claims 1 to 5, wherein the corrosion inhibitor is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3 。
7. The copper-aluminum particle powder with a coating according to any one of claims 1 to 6, wherein the coating has a thickness of 3 to 5nm.
8. A method of making copper aluminum particle powder with a coating comprising:
ball-milling and filtering the copper-aluminum particle powder to obtain slurry containing the copper-aluminum particle powder;
and mixing the slurry containing the copper-aluminum particle powder with a solution containing a coating agent and a corrosion inhibitor, and drying to obtain the copper-aluminum particle powder containing the coating.
9. The method according to item 8, wherein the copper-aluminum particle powder is ball-milled in the presence of a low boiling point organic solvent and zirconium balls, preferably, the mass ratio of the copper-aluminum particle powder, the low boiling point organic solvent and the zirconium balls is 0.9-1.2: 0.7-1.0.
10. The method according to item 9, wherein the low-boiling organic solvent is petroleum ether, ethanol, n-butanol, isobutanol, ethyl acetate, and/or tetrahydrofuran.
11. The method according to any one of items 8 to 10, wherein the copper is 65 to 80% and the aluminum is 20 to 35% by mass in the copper-aluminum particle powder.
12. The method according to any one of items 8-11, wherein the specific surface area of the particles in the copper aluminum particle powder is 0.8-1.5m 2 The tap density is more than or equal to 3.2g/ml, and the average particle diameter D of the particles of the copper-aluminum particle powder 50 Is 0.9-1.5 μm.
13. The method according to any one of items 8 to 12, wherein the mass ratio of the slurry containing the copper aluminum particle powder and the solution containing the coating agent and the corrosion inhibitor is 1.
14. The method of any of claims 8-13, wherein the capping agent is stearic acid, oleic acid, and/or lauric acid;
preferably, the corrosion inhibitor is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3 。
15. The method of any of claims 8-14, wherein the solution comprising a coating agent and a corrosion inhibitor is an aqueous solution comprising a coating agent, a corrosion inhibitor, and a low boiling organic solvent; preferably, the mass ratio of the coating agent, the low-boiling-point organic solvent, the corrosion inhibitor and the water is 0.01-0.2.
16. Copper-aluminum paste comprising the clad-containing copper-aluminum particle powder described in any one of items 1 to 7 or the clad-containing copper-aluminum particle powder produced by the method described in any one of items 8 to 15.
17. The copper aluminum paste of claim 16, wherein the copper aluminum paste further comprises an epoxy resin, a reactive diluent, a surfactant, an epoxy accelerator, a curing agent, a silicone oil, a thixotropic agent, and a solvent;
preferably, the copper-aluminum particle powder containing the coating layer comprises, by weight, 80-88 parts of copper-aluminum particle powder containing the coating layer, 2-5 parts of epoxy resin, 2-6 parts of reactive diluent, 0.1-1 part of surfactant, 0.2-3 parts of epoxy accelerator, 0.3-4 parts of curing agent, 0.2-1 part of silicone oil, 0.3-2 parts of thixotropic agent and 0.5-5 parts of solvent.
18. The copper aluminum paste of claim 17 wherein the epoxy resin is selected from one or more of bisphenol a, bisphenol F, hydrogenated bisphenol a, and urethane-modified epoxy resin;
preferably, the reactive diluent is selected from two or three of n-butyl glycidyl ether, glycidyl methacrylate and polypropylene glycol glycidyl ether;
preferably, the surfactant is selected from one or more of BYK204, BYK110, TEGO Wet270 and TEGO Dispers 740W;
preferably, the epoxy accelerator is selected from one or more than two of 1-aminoethyl-2-methylimidazole, triethanolamine, dimethylbenzylamine and DMP-30;
preferably, the curing agent is N, N-dimethylaniline, dicyandiamide and/or blocked isocyanate;
preferably, the silicone oil is PMX200-50CS, PMX200-500CS and/or PMX200-1000CS;
preferably, the thixotropic agent is selected from one or more of THIXATROL PLUS, BYK410, THIXCIN R and ST;
preferably, the solvent is butyl carbitol acetate, butyl carbitol and/or terpineol.
19. An electrode comprising the copper aluminum paste of any one of claims 16-18.
20. A battery comprising the electrode of item 19.
ADVANTAGEOUS EFFECTS OF INVENTION
The copper-aluminum particle powder containing the coating layer forms a compact protective film on the surface of the copper-aluminum particle powder, and the resistance change rate of the copper-aluminum slurry formed by the copper-aluminum particle powder containing the coating layer is less than or equal to 8 percent at 85 ℃ and 85 percent rh (relative humidity).
The copper-aluminum paste formed by the copper-aluminum particle powder containing the coating layer has low contact resistance, low line resistance and lower cost which is only 1/10 of that of silver paste.
1. The corrosion inhibitor selected by the application is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3 Inhibiting corrosion by forming a layer of metal oxides and hydroxides on the surface of copper aluminum particles. Since the cathode reaction of metal corrosion is the reduction reaction of oxygen, the pH value of the cathode area is increased, and rare earth metal ions are deposited on the cathode part in the form of hydroxide or oxide to hinder the corrosion reaction.
2. The conductive powder used in the invention is copper-aluminum particle powder. In the air, the activity of the copper-aluminum particle powder is greater than that of the copper powder, and compact aluminum oxide can be formed in the oxidation process of the aluminum powder, so that further corrosion reaction is hindered.
3. According to the invention, the coating agent mainly comprises lauric acid and stearic acid, and the coating agent mainly has the function of coating the surface of copper powder to prevent the copper powder from agglomerating in the vacuum drying process, so that the slurry prepared from copper and aluminum particle powder containing a coating layer has good dispersibility. Meanwhile, the wrappage can isolate oxygen, so that the copper powder is prevented from contacting air. Further preventing oxidation of the copper powder.
4. The invention adopts epoxy resin which is matched with bisphenol A, bisphenol F, hydrogenated bisphenol A and polyurethane modified epoxy resin, and can form a good compact film with copper-aluminum particle powder containing a coating layer after being cured, so that the copper-aluminum particle powder containing the coating layer is protected from being corroded, and the coating has weather resistance, solvent resistance and good film forming performance. The action principle is as follows: the resin contains a large amount of F-C bonds, the bond energy is 485KJ/mol, and the F-C bonds are difficult to break under the action of heat, light and the like to form a good protective film.
Detailed Description
In the prior art, silver-coated copper powder is used to replace silver powder in the preparation of the heterojunction battery to reduce the cost, but because the coating rate of the silver-coated copper powder is 70-80%, the silver-coated copper powder is coated by surface modification to prevent oxidation in the curing process, generally, a coating agent is an oil-soluble substance and can be dissolved in an organic solvent in slurry, so that the coating is ineffective, and the curing resistance is unstable in the air. In addition, because the silver content of the silver-coated copper powder is generally 20-50%, silver ion migration cannot be avoided essentially, and because the silver content of the silver-coated copper is high, and the manufacturing process is complex, the reduction range in cost is not large, and pure base metal is not large, in view of this, the application provides a copper-aluminum particle powder containing a coating layer, wherein the inside of the particle of the copper-aluminum particle powder containing the coating layer is a copper-aluminum particle, the surface layer is a coating layer, and the coating layer contains a coating agent and a corrosion inhibitor.
The particles in the copper-aluminum particle powder containing the coating layer form compact protective films on the surfaces of the copper-aluminum particles, so that corrosion can be inhibited.
In addition, the copper-aluminum particle powder is adopted as the conductive powder, and the copper-aluminum alloy particle powder is in the air, so that the activity of aluminum is greater than that of copper, and compact aluminum oxide can be formed in the aluminum oxidation process, and further corrosion reaction is hindered.
The coating agent and the corrosion inhibitor are used as coating layers, the coating agent is wrapped on the surfaces of copper and aluminum particles, copper and aluminum particle powder is prevented from being agglomerated in the vacuum drying process, and the copper and aluminum slurry prepared from the copper and aluminum particle powder containing the coating layers is good in dispersibility. Meanwhile, the coating layer can isolate oxygen, copper-aluminum particle powder containing the coating layer is prevented from contacting air, and oxidation of the copper-aluminum particle powder is further prevented. In addition, since the cathode reaction of metal corrosion is the reduction reaction of oxygen, the pH value of the cathode region is increased, and rare earth metal ions in the slow release agent are deposited on the cathode part in the form of hydroxide or oxide, so that the corrosion reaction can be hindered.
In some embodiments, the particles of the copper aluminum particle powder with a coating layer comprise, from inside to outside, copper aluminum particles, a corrosion inhibitor, and a coating agent.
In some embodiments, the particles of the copper aluminum particle powder with a coating layer have a specific surface area of 0.7 to 1.8m 2 Preferably, the tap density is 3.2g/ml or more, preferably 3.2 to 7g/ml.
For example, the specific surface area of the particles of the copper-aluminum particle powder containing a coating layer may be 0.7m 2 /g、0.8m 2 /g、 0.9m 2 /g、1.0m 2 /g、1.1m 2 /g、1.2m 2 /g、1.3m 2 /g、1.4m 2 /g、1.5m 2 /g、1.6m 2 /g、1.7m 2 /g、1.8m 2 And/g, etc.
Tap densities may be 3.2g/ml, 4g/ml, 5g/ml, 6g/ml, 7g/ml, and the like.
In the present application, the specific surface area of the particles of the copper-aluminum particle powder containing the coating layer can be measured by a method conventional in the art, for example, the specific surface area of the particles of the copper-aluminum particle powder containing the coating layer can be measured by a specific surface area tester commonly used in the art.
In the present application, the tap density can be determined by a method conventional in the art, for example, by measuring the tap density of particles of copper-aluminum particle powder containing a coating layer by a tap densitometer commonly used in the art.
In some embodiments, the average particle diameter D of the particles of the copper aluminum particle powder containing a coating layer 50 1.2-1.8 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 10 0.5-0.8 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 90 3.4-4.2 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 97 Less than or equal to 10 mu m, preferably between 4.2 and 10 mu m.
For example, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 50 Can be 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, etc.;
the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 10 Can be 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, etc.;
the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 90 Can be 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4.0 μm, 4.1 μm, 4.2 μm, etc.;
the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 90 May be 10 μm, 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4 μm, or the like.
In the present application, the average particle diameter D 10 Means 10% of the copper-aluminum particles in the coated copper-aluminum particlesThe particle size of the particles;
similarly, average particle diameter D 50 、D 90 And D 97 The particle size of 50% of the particles, 90% of the particles and 97% of the particles in the copper-aluminum particle powder containing the coating layer are referred to, respectively. For example, in the present application, the average particle diameter D of the particles of the copper-aluminum granulated powder containing the coating layer 50 1.2-1.8 μm, which means that of the particles of the copper-aluminum particle powder containing the coating layer, 50% of the particles have a particle diameter of 1.2-1.8 μm.
In the present application, the method for determining the average particle size is not limited in any way, and can be determined by a method conventional in the art, for example, the average particle size of the particles of copper-aluminum particle powder containing a coating layer can be measured by a laser particle sizer conventional in the art.
In some embodiments, the coating agent is stearic acid, oleic acid, and/or lauric acid.
This application uses the cladding agent to wrap up the granule in with copper aluminium granule powder, can prevent that copper powder from agglomerating at the vacuum drying in-process in the copper aluminium granule powder, and the copper aluminium thick liquid dispersibility that makes the preparation of the copper aluminium granule powder that contains the coating good, can completely cut off oxygen through using the cladding agent, avoids the well copper powder and the air contact of copper aluminium granule powder, further prevents the copper powder oxidation of copper aluminium granule powder.
In some embodiments, the corrosion inhibitor is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3
The corrosion inhibitor is coated on the surfaces of the copper-aluminum particle powder particles, and corrosion can be inhibited by forming a layer of metal oxide and hydroxide on the surfaces of the copper-aluminum particle powder particles.
In some embodiments, the cladding layer has a thickness of 3 to 5nm.
For example, the thickness of the coating layer may be 3nm, 4nm, 5nm, or the like.
In some embodiments, the particles of the copper-aluminum particle powder containing the coating layer have an inner region of copper-aluminum particles and a surface layer of coatingA coating comprising a coating agent and a corrosion inhibitor. In some embodiments, the particles of the copper aluminum particle powder with a coating layer comprise, from inside to outside, copper aluminum particles, a corrosion inhibitor, and a coating agent. In some embodiments, the particles of the copper aluminum particle powder with a coating layer have a specific surface area of 0.7 to 1.8m 2 Preferably, the tap density is not less than 3.2g/ml. In some embodiments, the average particle diameter D of the particles of the copper aluminum particle powder containing a coating layer 50 1.2-1.8 μm; preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 10 0.5-0.8 μm; preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 90 3.4-4.2 μm; preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 97 Less than or equal to 10 mu m. In some embodiments, the coating agent is stearic acid, oleic acid, and/or lauric acid. In some embodiments, the corrosion inhibitor is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3 . In some embodiments, the coating has a thickness of 3 to 5nm.
The copper-aluminum particle powder particle containing the coating layer has the advantages that the coating layer is formed on the surface of the copper-aluminum particle powder particle, the copper powder of the copper-aluminum particle powder can be prevented from contacting with air, the oxidation of the copper powder is prevented, the obtained copper-aluminum particle powder containing the coating layer is used in copper-aluminum slurry, the contact resistance is low, the line resistance is low, the high-temperature and high-humidity resistance environment is realized, and the long-term reliability is good, wherein the resistance attenuation rate is less than or equal to 8%.
The application provides a method for preparing copper-aluminum particle powder containing a coating layer, which comprises the following steps:
ball-milling and filtering the copper-aluminum particle powder to obtain slurry containing the copper-aluminum particle powder;
and mixing the slurry containing the copper-aluminum particle powder with a solvent containing a coating agent and a corrosion inhibitor, and drying to obtain the copper-aluminum particle powder containing the coating layer.
In some embodiments, the copper aluminum particle powder is ball milled in the presence of a low boiling point organic solvent and zirconium balls, preferably, the mass ratio of the copper aluminum particle powder, the low boiling point organic solvent and the zirconium balls is from 0.9 to 1.2. In some embodiments, a ball milling aid is added for ball milling, preferably, the addition amount of the ball milling aid is 0.01-1% of the total amount of the copper-aluminum particle powder, the low-boiling point solvent and the zirconium balls, for example, the addition amount of the ball milling aid may be 0.01%, 0.05%, 0.1%, 0.5%, 0.1%, and the like of the total amount of the copper-aluminum particle powder, the low-boiling point solvent and the zirconium balls; preferably, the ball milling aid is ethylene glycol, propylene glycol and/or polyacrylic acid.
In some embodiments, copper aluminum particle powder is ball milled in a ball milling apparatus in the presence of a low boiling point organic solvent and zirconium balls.
The ball milling apparatus is not limited in any way in this application and may be conventionally selected as needed, for example, ball milling may be performed in a ball mill commonly used in the art, preferably in a horizontal ball mill;
preferably, the rotation speed of the ball mill is 15-35rpm/min;
preferably, the ball milling time is 6-8h.
In some embodiments, the low boiling solvent is petroleum ether, ethanol, and/or n-butanol; preferably, a low boiling point solvent is added during the ball milling process to disperse the copper-aluminum particle powder, so that the copper-aluminum particle powder is fully ball milled.
In some embodiments, ball-milling and filtering the copper-aluminum particle powder to obtain the slurry containing the copper-aluminum particle powder further comprises centrifugally stirring the filtrate obtained after filtering with a low-boiling-point solvent, and then filtering to obtain the slurry containing the copper-aluminum particle powder; preferably, the low boiling point solvent is used to wash the ball milling aid to remove the ball milling aid.
In some embodiments, the rotational speed of the centrifugal stirring is 600-1000rpm/min, preferably, the stirring time is 5-20min; preferably, the steps are repeated for 3-5 times repeatedly, so that the pH value of the obtained slurry containing the copper-aluminum particle powder is 5-7.
In some embodiments, the copper is 65-80% and the aluminum is 20-35% by mass of the copper-aluminum particle powder.
For example, the copper may be 65%, 70%, 75%, 80%, etc. in mass percentage in the copper-aluminum particle powder;
the aluminum may be 20%, 25%, 30%, 35%, etc.
In some embodiments, the particles of the copper aluminum particle powder have a specific surface area of 0.8 to 1.5m 2 The tap density is more than or equal to 3.2g/ml, and the average grain diameter D50 of the copper-aluminum granular powder grains is 0.9-1.5 mu m.
For example, the specific surface area of the particles of the copper aluminum particle powder may be 0.8m 2 /g、0.9m 2 /g、1.0m 2 /g、1.1m 2 /g、 1.2m 2 /g、1.3m 2 /g、1.4m 2 /g、1.5m 2 (iv)/g, etc.;
the average particle diameter D of the particles of the copper-aluminum particle powder 50 It may be 0.9. Mu.m, 1.0. Mu.m, 1.1. Mu.m, 1.2. Mu.m, 1.3. Mu.m, 1.4. Mu.m, 1.5. Mu.m, or the like.
In some embodiments, the average particle diameter D of the particles of the copper aluminum particle powder 10 0.3-0.5 μm;
preferably, the average particle diameter D of the particles of the copper aluminum particle powder 90 2.5-3.2 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder 97 ≤6μm。
For example, the average particle diameter D of the particles of the copper-aluminum particle powder 10 Can be 0.3 μm, 0.4 μm, 0.5 μm, etc.;
the average particle diameter D of the particles of the copper-aluminum particle powder 90 May be 2.5. Mu.m, 2.6. Mu.m, 2.7. Mu.m, 2.8. Mu.m, 2.9. Mu.m, 3.0. Mu.m, 3.1. Mu.m, 3.2. Mu.m, etc.
In some embodiments, the solvent containing the coating agent and the buffer is an aqueous solution containing the coating agent, a low-boiling point solvent and a corrosion inhibitor, and preferably, the mass ratio of the coating agent, the low-boiling point organic solvent, the corrosion inhibitor and the water is 0.01-0.2.
For example, the coating agent, low-boiling organic solvent, corrosion inhibitor andmass ratio of water (m) Coating agent ：m Low boiling point solvent ：m Corrosion inhibitor ：m Water (W) ) 0.01.
The aqueous solution containing the coating agent, the low-boiling-point solvent and the corrosion inhibitor is obtained by adding the coating agent, the low-boiling-point solvent and the corrosion inhibitor into water and stirring, preferably, the stirring speed is 300-900rpm/min, preferably, the stirring time is 10-60min, and preferably, stirring is carried out at the temperature of 60-80 ℃.
In some embodiments, the capping agent is stearic acid, oleic acid, and/or lauric acid;
preferably, the corrosion inhibitor is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3 。
In some embodiments, the mass ratio of the slurry containing copper aluminum particle powder to the solution containing capping agent and corrosion inhibitor is 1.
For example, the mass ratio (m) of the slurry containing copper aluminum particle powder to the solution containing the coating agent and the corrosion inhibitor Slurry containing copper-aluminum particle powder :m Solution containing coating agent and corrosion inhibitor ) Can be from 1.
In some cases, mixing the slurry containing the copper-aluminum particle powder with a solution containing a coating agent and a corrosion inhibitor, and drying to obtain copper-aluminum particle powder containing a coating layer comprises stirring and mixing the slurry containing the copper-aluminum particle powder with a solution containing a coating agent and a corrosion inhibitor, and drying to obtain copper-aluminum particle powder containing a coating layer, wherein the stirring speed is preferably 600-1000rpm/min; preferably, the stirring time is 1-3h.
In some embodiments, a slurry containing copper aluminum particle powder is mixed with a solution containing a capping agent and a corrosion inhibitor at a temperature of 40 ℃ or less, preferably 20 to 40 ℃ with stirring.
In some embodiments, the drying is vacuum drying, preferably drying at 40-80 ℃ for 9-24h to obtain copper-aluminum particle powder containing the coating layer.
The application provides copper-aluminum paste which comprises the copper-aluminum particle powder containing the coating or the copper-aluminum particle powder containing the coating prepared by the method.
In some embodiments, the copper aluminum paste comprises an epoxy resin, a reactive diluent, a surfactant, an epoxy accelerator, a curing agent, a silicone oil, a thixotropic agent, and a solvent;
the epoxy resin is coated on the powder, and the ITO base material and the copper-aluminum particle powder containing the coating layer are bonded to provide adhesion;
the curing agent is used for causing the epoxy resin to generate reactions such as condensation, polymerization, addition, catalysis and the like to form a reticular three-dimensional polymer.
The reactive diluent contains epoxy group containing low molecular weight epoxy compounds which primarily reduce viscosity and increase resin toughness.
The epoxy accelerator is used to promote the curing of epoxy resins at low temperatures.
The silicone oil is used for improving the screening performance of the copper-aluminum paste and preventing virtual printing and grid breaking in the printing process.
The thixotropic agent is used for improving the thixotropic property of the copper-aluminum paste and the storage time of the copper-aluminum paste, and can keep good linearity under a narrow line width.
The solvent is used for reducing the viscosity of the copper-aluminum paste.
Preferably, the copper-aluminum particle powder containing the coating layer is 80-88 parts by weight, the epoxy resin is 2-5 parts by weight, the reactive diluent is 2-6 parts by weight, the surfactant is 0.1-1 part by weight, the epoxy accelerator is 0.2-3 parts by weight, the curing agent is 0.3-4 parts by weight, the silicone oil is 0.2-1 part by weight, the thixotropic agent is 0.3-2 parts by weight, and the solvent is 0.5-5 parts by weight.
For example, the copper-aluminum particle powder containing the coating layer may be 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, etc. in parts by weight;
the epoxy resin can be 2 parts, 3 parts, 4 parts, 5 parts and the like;
the reactive diluent can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts and the like;
the surfactant may be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc.;
the epoxy accelerator can be 0.2 part, 0.5 part, 0.8 part, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts and the like;
the curing agent can be 0.3, 0.5, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, etc.;
the silicone oil can be 0.2 part, 0.5 part, 0.8 part, 1.0 part, etc.;
the thixotropic agent can be 0.3, 0.5, 0.8, 1.0, 1.5, 2.0, etc.;
the solvent may be 0.5 parts, 0.8 parts, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, etc.
In some embodiments, the epoxy resin is selected from one or more of bisphenol a, bisphenol F, hydrogenated bisphenol a, and urethane-modified epoxy resin;
preferably, the reactive diluent is selected from two or three of n-butyl glycidyl ether, glycidyl methacrylate and polypropylene glycol glycidyl ether;
preferably, the surfactant is selected from one or more of BYK204, BYK110, TEGO Wet270 and TEGO Dispers 740W;
preferably, the epoxy accelerator is selected from one or more of 1-aminoethyl-2-methylimidazole, triethanolamine, dimethylbenzylamine, and 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30);
preferably, the curing agent is N, N-dimethylaniline, dicyandiamide and/or blocked isocyanate;
preferably, the silicone oil is PMX200-50CS, PMX200-500CS and/or PMX200-1000CS;
the PMX200-50CS means that the viscosity of PMX-200 is 50CS, and has the same meaning for PMX200-500CS and PMX200-1000CS, similarly.
Preferably, the thixotropic agent is selected from
One or more of BYK410, THIXCIN R and ST;
preferably, the solvent is butyl carbitol acetate, butyl carbitol and/or terpineol.
The epoxy value of bisphenol A is 0.38 to 0.54, and the epoxy value refers to the amount of substance containing epoxy groups in 100g of the epoxy resin.
The epoxy value of the bisphenol F is 0.55-0.625;
hydrogenated bisphenol A has an epoxy value of 0.42 to 0.47;
the epoxy value of the polyurethane modified epoxy resin is 0.47-0.56
The blocked isocyanate means that the end group is temporarily blocked by reaction, and isocyanate can be released at a certain temperature to play a role of cementing when in use.
The application copper aluminium thick liquid in contain epoxy and the copper aluminium granule powder that contains the coating, epoxy forms good compact membrane with the copper aluminium granule powder that contains the coating after the solidification, the protection contains the copper aluminium granule powder of coating not corroded, has weatherability, solvent resistance, good film forming properties, preferably, its mechanism of action is: the epoxy resin contains a large amount of F-C bonds, the bond energy is 485KJ/mol, and the F-C bonds are difficult to break under the action of heat, light and the like, so that a good protective film is formed with copper-aluminum particle powder containing a coating layer.
In the present application, the preparation method of the copper-aluminum paste is not limited in any way, and can be conventionally selected according to needs, for example, the copper-aluminum paste is obtained by mixing, stirring and rolling copper-aluminum particle powder containing a coating layer, epoxy resin, reactive diluent, surfactant, epoxy accelerator, curing agent, silicone oil, thixotropic agent and solvent.
In some embodiments, the mixture is first stirred at 20-40rpm/min for 20-30min and then stirred at 30-60rpm/min for 30-80min, preferably, the vacuum degree is not less than-0.6 MPa during stirring.
In some embodiments, the rolling is performed using methods conventional in the art, for example, the rolling is performed in the following manner:
TABLE 1 parameters of the Rolling Process
| Number of rolls | Gap between roller and gate | Rolling speed (rpm/min) |
| 1 | 0.1 | 200 |
| 2 | 0.15 | 300 |
| 3 | 0.19 | 400 |
| 4 | 0.45 | 400 |
| 5 | 0.65 | 400 |
| 6 | 0.65 | 400 |
| 7 | 0.3 | 400 |
In some embodiments, the fineness is measured after rolling to obtain a copper aluminum paste, preferably having a fineness of 6 μm or less.
For the determination of the fineness, the application is not limited at all, and it can be selected conventionally as required, and for example, a scraper fineness meter can be used for measurement.
In some embodiments, the rolling process further comprises a filtering step to remove foreign matters or bright flakes in the copper-aluminum paste, and preferably, the copper-aluminum paste is obtained by filtering with a 300-mesh sieve.
Examples
The materials used in the tests and the test methods are generally and/or specifically described in the present application and in the following examples,% means wt%, i.e. percent by weight, unless otherwise specified. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1-1 preparation of copper-aluminum particle powder with coating
(1) Taking the particle powder containing 70% of copper and 30% of aluminum (wherein D10:0.37 μm, D50:1.12 μm, D90:2.98 μm, D97:5.35 μm, and specific surface area is 0.91 m) in the copper-aluminum particle powder according to the proportion 2 (iv)/g, tap density: 3.6 g/ml): ethanol: the ratio of zirconium balls is 1:0.8:2.5, and then 0.15% of ethylene glycol in total is added. Placing into a ball milling tank, and using a horizontal ballThe mill was ball milled at 25rpm/min for 7h, then the slurry was freed of floaters and the clear solution was filtered using filter paper.
(2) Removing floating materials on the surface of the copper-aluminum particle powder slurry prepared in the step (2), filtering clear liquid by using filter paper, and then, carrying out separation on the clear liquid according to the weight ratio of 1:1, adding petroleum ether, then placing into a centrifuge tube, stirring for 8min at the rotating speed of 800rpm/min by using a magnetic stirrer, filtering clear liquid by using filter paper, and repeatedly operating for 4 times, wherein the pH value is 6.3 to obtain slurry containing copper-aluminum particle powder;
(3) According to the weight ratio of stearic acid: ethanol: laNO 3 : the water mass ratio is 0.06:0.5:0.3:1 mixing, stirring at a speed of 600rpm/min by using a magnetic stirrer at a temperature of 70 ℃ for 15min to obtain a mixture containing stearic acid, ethanol and LaNO 3 Then the slurry containing copper and aluminum particles obtained in the step (2) and the slurry containing stearic acid, ethanol and LaNO are mixed 3 The mass ratio of the aqueous solution of (1): 1, mixing, stirring at the rotating speed of 800rpm/min for 2 hours at the temperature of 25 ℃, filtering clear liquid by using filter paper, then putting the clear liquid into a vacuum drying oven, drying at the temperature of 65 ℃ for 14 hours to a dry state to obtain copper-aluminum particle powder containing a coating layer, wherein the index of the copper-aluminum particle powder containing the coating layer tested by using a laser particle sizer is D 10 ：0.63μm，D 50 ：1.52μm，D 90 ：3.83μm，D 97 :6.42 μm, and a specific surface area of 1.2m measured by using a specific surface area tester 2 (iv)/g, tap density measured using a tap densitometer: 3.5g/ml.
Examples 1-2 preparation of copper-aluminum particle powder with coating
(1) Taking copper-aluminum particle powder with 75 percent of copper and 25 percent of aluminum in the copper-aluminum particle powder according to the proportion (wherein D10:0.42 mu m, D50:0.93 mu m, D90:3.07 mu m, D97:4.78 mu m, and the specific surface area is 1.15m 2 (iv)/g, tap density: 3.9 g/ml): ethanol: the ratio of zirconium balls is 1:0.8:2.5, and then 0.1% of propylene glycol in total is added. Putting into a ball milling tank, ball milling at a speed of 17rpm/min for 7h by using a horizontal ball mill, removing floating materials in the slurry, and filtering the clear solution by using filter paper.
(2) Removing floating materials on the surface of the copper-aluminum particle powder slurry prepared in the step (2), filtering clear liquid by using filter paper, and then, carrying out separation on the clear liquid according to the weight ratio of 1:1, adding n-butyl alcohol, then placing into a centrifuge tube, stirring for 10min at the rotating speed of 800rpm/min by using a magnetic stirrer, filtering clear liquid by using filter paper, repeatedly operating for 4 times, and obtaining slurry containing copper-aluminum particle powder at the pH value of 6.6;
(3) According to the following percentage by weight of oleic acid: ethanol: ndCl: the water mass ratio is 0.1:0.5:0.25:1 mixing, stirring at a speed of 600rpm/min by using a magnetic stirrer at a temperature of 70 ℃ for 20min to obtain a mixture containing stearic acid, ethanol and LaNO 3 And (3) then mixing the slurry containing the copper-aluminum particle powder obtained in the step (2) and an aqueous solution containing stearic acid, ethanol and NdCl in a mass ratio of 1:1, stirring at the rotating speed of 800rpm/min for 2 hours at the temperature of 25 ℃, filtering clear liquid by using filter paper, then putting the clear liquid into a vacuum drying oven, drying at the temperature of 65 ℃ for 12 hours to a dry state to obtain copper-aluminum particle powder containing a coating layer, and measuring according to the method of the embodiment 1-1, wherein the index of the copper-aluminum particle powder containing the coating layer is D 10 ：0.68μm，D 50 ：1.35μm，D 90 ：4.24μm，D 97 5.42 μm, specific surface area 1.35m 2 (ii) a tap density of 3.7g/ml.
Examples 1-3 preparation of copper-aluminum particle powder with coating
Examples 1-3 differ from example 2 in the mass ratio of the slurry containing copper-aluminum particles and the solution containing a coating agent and a corrosion inhibitor, and the resulting copper-aluminum particles containing a coating layer was measured in the same manner as in example 1-1 and indicated by D 10 ：0.40μm，D 50 ：0.89μm，D 90 ：2.98μm，D 97 4.56 μm, specific surface area 1.27m 2 (ii) a tap density of 3.8g/ml.
Examples 1-4 preparation of copper-aluminum particle powder containing coating layer
Examples 1 to 4 differ from example 2 in the mass ratio of the slurry containing copper aluminum particles and the solution containing the coating agent and the corrosion inhibitor, and the obtained copper aluminum particles powder containing the coating layer was measured in the same manner as in example 1 to 1Index is D 10 ：0.38μm，D 50 ：0.85μm，D 90 ：2.85μm，D 97 4.32 μm, specific surface area 1.36m 2 (ii) a tap density of 3.5g/ml.
Examples 1-5 preparation of copper-aluminum particle powder with coating
Examples 1-5 differ from example 2 in the mass ratio of the coating agent, the low-boiling organic solvent, the corrosion inhibitor and water, and the resulting copper-aluminum powder particles containing a coating layer, measured in the same manner as in example 1-1, is designated as D 10 ：0.35μm，D 50 ：0.82μm，D 90 ：2.80μm，D 97 4.28 μm, specific surface area 1.48m 2 (ii)/g, tap density 3.9g/ml.
Examples 1-6 preparation of copper-aluminum particle powder containing coating layer
Examples 1-6 differ from example 2 in the mass ratio of the coating agent, the low-boiling organic solvent, the corrosion inhibitor and water, and the resulting copper-aluminum powder particles containing a coating layer, measured in the same manner as in example 1-1, is designated as D 10 ：0.37μm，D 50 ：0.85μm，D 90 ：2.86μm，D 97 4.32 μm, specific surface area 1.45m 2 (ii) a tap density of 4.1g/ml.
Examples 1-7 preparation of copper-aluminum particle powder with coating
Examples 1-7 differ from example 2 in the mass ratio of the coating agent, the low-boiling organic solvent, the corrosion inhibitor and water, and the resulting copper-aluminum powder particles containing a coating layer, measured in the same manner as in example 1-1, is designated as D 10 ：0.32μm，D 50 ：0.79μm，D 90 ：2.78μm，D 97 4.15 μm, specific surface area 1.62m 2 (ii) a tap density of 4.2g/ml.
Examples 1-8 preparation of copper-aluminum particle powder with coating
Examples 1 to 8 are different from example 2 in the mass ratio of the coating agent, the low boiling point organic solvent, the corrosion inhibitor and water, and the obtained copper-aluminum particle powder containing a coating layer was measured in the same manner as in example 1 to 1,it has an index of D 10 ：0.45μm，D 50 ：0.96μm，D 90 ：3.05μm，D 97 4.62 μm, specific surface area 1.18m 2 The tap density is 3.8g/ml.
Examples 1-9 preparation of copper-aluminum particle powder with coating
Examples 1 to 9 differ from example 2 in the mass ratio of the coating agent, the low-boiling organic solvent, the corrosion inhibitor and water, and the resulting copper-aluminum particle powder with a coating layer was measured in the same manner as in example 1 to 1 and indicated by D 10 ：0.41μm，D 50 ：0.90μm，D 90 ：2.99μm，D 97 4.60 μm, specific surface area 1.21m 2 The tap density is 3.4g/ml.
Examples 1-10 preparation of copper-aluminum particle powder with coating
Examples 1-10 differ from example 2 in the mass ratio of the coating agent, the low-boiling organic solvent, the corrosion inhibitor and water, and the resulting copper-aluminum powder particles containing a coating layer, measured in the same manner as in example 1-1, is designated as D 10 ：0.38μm，D 50 ：0.88μm，D 90 ：2.95μm，D 97 4.45 μm, specific surface area 1.31m 2 (ii) a tap density of 3.6g/ml.
Examples 1-11 preparation of copper-aluminum particle powder with coating
Examples 1 to 11 differ from example 2 in the mass ratio of the coating agent, the low-boiling organic solvent, the corrosion inhibitor and water, and the resulting copper-aluminum powder particles containing a coating layer, measured in the same manner as in example 1 to 1, was designated as D 10 ：0.40μm，D 50 ：0.91μm，D 90 ：2.95μm，D 97 4.55 μm, specific surface area 1.25m 2 (ii) a tap density of 3.4g/ml.
Comparative example 1 preparation of copper-aluminum granulated powder
The preparation was carried out in the same manner as in example 1, except that, without using a coating agent, the obtained copper-aluminum particle powder was measured in the same manner as in example 1, and the obtained copper-aluminum particle powder was characterized by: d 10 ：0.38μm， D 50 ：0.87μm，D 90 ：2.88μm，D 97 4.40 μm, specific surface area 1.42m 2 (ii) a tap density of 3.3g/ml.
TABLE 2 proportion table of various components of different examples and comparative examples
EXAMPLE 2-1 preparation of copper-aluminum paste
(1) 86g of the copper-aluminum particle powder containing a coating layer obtained in example 1-1, 2.8g of hydrogenated bisphenol A, 0.5g of bisphenol A E51, 2g of polypropylene glycol glycidyl ether, 3g of n-butyl glycidyl ether, 0.5g of a surfactant (BYK 204), 1.5g of an epoxy accelerator (DMP-30), 1.2g of a curing agent (dicyandiamide), 0.5g of a silicone oil (PMX 200-50 CS), and 0.8g of a thixotropic agent
And 1.2g of solvent (butyl carbitol) are put into a stirrer to be stirred at the rotating speed of 35rpm/min for 20min, then the stirrer is stopped to be scraped clean, the materials are stirred at the rotating speed of 45rpm/min for 60min to obtain materials, and the materials are vacuumized while being stirred, wherein the vacuum degree is-0.8 Mpa.
(2) And rolling the stirred materials, rolling according to the rolling process shown in the table 1, and filtering foreign matters or bright sheets of the rolled slurry by using a 300-mesh screen to obtain copper-aluminum slurry with the fineness of 3 microns.
Example 2-2 preparation of copper-aluminum paste
(1) 86g of the copper-aluminum particle powder containing the coating layer obtained in example 1-2, 2.3g of bisphenol F epoxy resin, 1g of polyurethane modified epoxy resin, 3g of glycidyl methacrylate, 2g of n-butyl glycidyl ether, 0.3g of surfactant (TEGO Wet 270), 1.5g of epoxy accelerator (dimethylbenzylamine), 1.8g of curing agent (blocked isocyanate), 0.5g of silicone oil (PMX 200-500 CS), 0.8g of thixotropic agent (BYK 410) and 0.8g of solvent (butyl carbitol) are put into a stirrer to be stirred at the rotating speed of 35rpm/min for 20min, then the stirrer is stopped to scrape the stirring paddle clean, the stirring paddle is stirred at the rotating speed of 45rpm/min for 60min to obtain a material, and the material is vacuumized while stirring, and the vacuum degree is-0.8 MPa.
(2) And rolling the stirred materials, rolling according to the rolling process shown in the table 1, and filtering foreign matters or bright sheets of the rolled slurry by using a 300-mesh screen to obtain copper-aluminum slurry with the fineness of 4 microns.
Examples 2-3 preparation of copper-aluminum pastes
Examples 2-3 and 2-2 differ in that the copper aluminum paste was prepared using the copper aluminum particle powder with a clad layer prepared in examples 1-3.
Examples 2-4 preparation of copper-aluminum pastes
Examples 2-4 are different from examples 2-2 in that copper aluminum paste is prepared using the copper aluminum particle powder containing a clad layer prepared in examples 1-4.
Examples 2-5 preparation of copper-aluminum pastes
Examples 2-5 differ from examples 2-2 in that copper aluminum pastes were prepared using the copper aluminum particle powders containing the clad layers prepared in examples 1-5.
Examples 2-6 preparation of copper-aluminum pastes
Examples 2-6 differ from examples 2-2 in that copper aluminum paste was prepared using the copper aluminum particle powder with a clad layer prepared in examples 1-6.
Examples 2-7 preparation of copper-aluminum pastes
Examples 2-7 differ from examples 2-2 in that copper aluminum pastes were prepared using the copper aluminum particle powders containing the clad layers prepared in examples 1-7.
Examples 2-8 preparation of copper-aluminum pastes
Examples 2-8 differ from examples 2-2 in that copper aluminum pastes were prepared using the copper aluminum particle powders containing the clad layers prepared in examples 1-8.
Examples 2-9 preparation of copper-aluminum pastes
Examples 2-9 differ from examples 2-2 in that copper aluminum pastes were prepared using the clad copper aluminum particle powders prepared in examples 1-9.
Examples 2-10 preparation of copper-aluminum pastes
Examples 2-10 and 2-2 differ in that copper aluminum paste was prepared using the clad-containing copper aluminum particle powder prepared in examples 1-10.
Examples 2-11 preparation of copper-aluminum pastes
Examples 2-11 differ from examples 2-2 in that copper aluminum pastes were prepared using the clad copper aluminum particle powders prepared in examples 1-11.
Examples 2-12 preparation of copper-aluminum pastes
Examples 2-12 are different from examples 2-2 in the amount of epoxy resin used to prepare the copper aluminum paste.
Examples 2-13 preparation of copper-aluminum pastes
Examples 2-13 differ from examples 2-2 in the amount of epoxy resin used to prepare the copper aluminum paste.
Examples 2-14 preparation of copper-aluminum pastes
Examples 2-14 differ from examples 2-2 in the amount of copper aluminum particle powder containing the clad layer used to prepare copper aluminum paste.
Comparative example 2 preparation of copper-aluminum paste
The preparation was carried out in the same manner as in example 2-1 except that the copper aluminum granulated powder obtained in comparative example 1 was used.
Comparative example 3 preparation of copper-aluminum paste
The production was carried out in the same manner as in example 2-1 except that the copper-aluminum alloy powder before the treatment of example 1-2 was used.
Table 3 composition table of copper aluminium paste of different examples and comparative examples
The copper aluminum pastes obtained in examples 2-1 to 2-14, comparative example 2 and copper aluminum paste obtained in comparative example 3 were printed on a silicon wafer by a screen printing process, measured in square resistivity at 85 ℃ RH using four probes, and the results are shown in Table 4:
TABLE 4 sheet resistance table of Cu-Al pastes obtained in different examples and comparative examples
As can be seen from the table, the sheet resistance of the copper-aluminum paste prepared by using the copper-aluminum particle powder containing the coating layer prepared in the examples 1-1 to 1-11 is relatively low, and after 56 days, the sheet resistance is 13.7m omega/\9633orless, while the sheet resistance of the copper-aluminum paste prepared in the comparative example is 32.5m omega/\9633ormore, which indicates that the copper-aluminum particle powder containing the coating layer prepared in the present application forms a compact protective film on the surface of the copper-aluminum alloy powder, and can hinder the progress of corrosion.
The foregoing is illustrative of the preferred embodiments of the present application and is not to be construed as limiting thereof, since other modifications and equivalents of the disclosed embodiments may be devised by those skilled in the art. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present application still belong to the protection scope of the technical solution of the present application.
Claims (10)
1. The copper-aluminum particle powder containing the coating layer is characterized in that the copper-aluminum particles are arranged in the inner area of the particles of the copper-aluminum particle powder containing the coating layer, the coating layer is arranged on the surface layer of the particles, and the coating layer contains a coating agent and a corrosion inhibitor.
2. The copper-aluminum particle powder with a coating as recited in claim 1, wherein the particles of the copper-aluminum particle powder with a coating comprise, in order from inside to outside, copper-aluminum particles, a corrosion inhibitor and a coating agent.
3. The coated copper aluminum particle powder of claim 1 or 2, wherein the coated copper aluminum particle powder isThe specific surface area of the particles is 0.7-1.8m 2 Preferably, the tap density is not less than 3.2g/ml.
4. The coated copper aluminum particle powder of any one of claims 1-3, wherein the coated copper aluminum particle powder particles have an average particle diameter D 50 1.2-1.8 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 10 0.5-0.8 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 90 3.4-4.2 μm;
preferably, the average particle diameter D of the particles of the copper-aluminum particle powder containing the coating layer 97 ≤10μm。
5. Copper aluminium particle powder with a coating according to any one of claims 1-4, wherein the coating agent is stearic acid, oleic acid and/or lauric acid.
6. The copper aluminum particle powder with cladding as recited in any one of claims 1-5, wherein the corrosion inhibitor is La (NO) 3 ) 3 、NdCl 3 And/or Ce (NO) 3 ) 3 。
7. A method of making a copper aluminum particle powder with a coating comprising:
ball-milling and filtering the copper-aluminum particle powder to obtain slurry containing the copper-aluminum particle powder;
and mixing the slurry containing the copper-aluminum particle powder with a solution containing a coating agent and a corrosion inhibitor, and drying to obtain the copper-aluminum particle powder containing the coating layer.
8. Copper-aluminum paste comprising the coated copper-aluminum particle powder of any one of claims 1 to 6 or the coated copper-aluminum particle powder produced by the method of claim 7.
9. An electrode comprising the copper aluminum paste of claim 8.
10. A battery comprising the electrode of claim 9.
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| PCT/CN2023/100869 WO2024027353A1 (en) | 2022-08-01 | 2023-06-16 | Copper-aluminum granular powder containing coating layer, and preparation method therefor and use thereof |
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| JP2001089878A (en) * | 1999-09-17 | 2001-04-03 | Nippon Shokubai Co Ltd | Metal corrosion preventive |
| JP2011034894A (en) * | 2009-08-05 | 2011-02-17 | Hitachi Chem Co Ltd | Cu-Al ALLOY POWDER, ALLOY PASTE USING IT, AND ELECTRONIC PARTS |
| CN108889939B (en) * | 2018-07-10 | 2020-04-03 | 山东格物新材料科技有限公司 | Corrosion-resistant powder material capable of absorbing microwaves and preparation method thereof |
| CN109301173A (en) * | 2018-09-29 | 2019-02-01 | 成都新柯力化工科技有限公司 | A method of improving zinc-air battery electrode corrosion resistance |
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| CN114101665B (en) * | 2021-11-15 | 2023-08-29 | 深圳市绚图新材科技有限公司 | Preparation method of silver-coated copper conductive powder |
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