CN117862488A - Silver powder with surface modified by silver carboxylate and preparation method thereof - Google Patents
Silver powder with surface modified by silver carboxylate and preparation method thereof Download PDFInfo
- Publication number
- CN117862488A CN117862488A CN202311769630.0A CN202311769630A CN117862488A CN 117862488 A CN117862488 A CN 117862488A CN 202311769630 A CN202311769630 A CN 202311769630A CN 117862488 A CN117862488 A CN 117862488A
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- China
- Prior art keywords
- silver
- silver powder
- carboxylate
- powder
- modified
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 95
- 239000004332 silver Substances 0.000 title claims abstract description 95
- -1 silver carboxylate Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 52
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- XNRABACJWNCNEQ-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.[Ag+].[O-][N+]([O-])=O XNRABACJWNCNEQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 19
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 84
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 32
- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- 230000005660 hydrophilic surface Effects 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 17
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 239000011259 mixed solution Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000004048 modification Effects 0.000 description 18
- 238000012986 modification Methods 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 229960002446 octanoic acid Drugs 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical group [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 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
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XQZMWLZYCUTNKX-UHFFFAOYSA-N hexadecanoic acid;silver Chemical compound [Ag].CCCCCCCCCCCCCCCC(O)=O XQZMWLZYCUTNKX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229940098695 palmitic acid Drugs 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides silver powder with silver carboxylate modified surface and a preparation method thereof, and relates to the technical field of silver powder preparation. According to the invention, the silver carboxylate is coated on the surface of the silver powder by reacting the organic carboxylic acid with the silver nitrate ammonia water complex in the alcohol washing stage, so that the silver powder with the surface modified by the silver carboxylate is obtained, and the silver powder with the surface modified is spherical particles, has submicron-to-micron particle size, uniform morphology, good dispersibility, high tap density, low sintering temperature, low series resistance and good conductivity, and improves the application performance of the silver powder in electronic slurry.
Description
Technical Field
The invention relates to the technical field of silver powder preparation, in particular to silver powder with surface modified by silver carboxylate and a preparation method thereof.
Background
The metal silver has excellent electric and heat conducting properties, and is widely applied to the fields of thick film electric conducting paste, high and low temperature electric conducting glue, electromagnetic shielding and other electronic paste. Silver powder is used as a conductive filler, is an important component of electronic paste, is a key material for determining the performance of the paste, and is therefore a noble metal powder material which is most widely used and has the greatest dosage at present. As an important component of the electronic paste, the morphology, particle size, dispersibility, specific surface area and other basic powder characteristics of silver powder play an important role in the electrical performance, flowability, printability and the like of the electronic paste. The dispersion performance of the silver powder determines whether the silver powder can be uniformly dispersed in the electronic paste, and the excellent dispersion performance can ensure that the silver powder is uniformly distributed in the electronic paste, so that the conductivity and the stability of the electronic paste are improved. The sintering performance of the silver powder determines the stability and the forming effect of the electronic paste under the high-temperature condition, and the good sintering performance can ensure that the electronic paste forms a compact conductive layer in the sintering process, so that the performance and the reliability of an electronic device are improved. Therefore, the conductivity, dispersion and sintering properties of silver powder play a decisive role in the electronic paste.
In the field of solar cells, electronic paste generally requires high sphericity, narrow fluidity, narrow particle size distribution, high tap density and the like of silver powder, and people generally pay attention to particle size, tap density, specific surface, surface morphology and the like of the silver powder in the process of synthesizing and modifying the silver powder, so that the surface modification of the silver powder is often studied very little. But the surface modification of silver powder can improve the bonding strength of silver powder and a substrate material, improve the uniformity and compactness of sintering by changing the surface property, morphology, introducing functional materials and the like, and introduce other functional materials to improve the sintering performance.
In order to adapt to the rapid firing process of the crystalline silicon solar cell, performance requirements of high sintering activity are put forward on silver powder forming front silver paste, and particularly with development of novel efficient cell technologies such as PERC, HJT and the like, the silver powder is required to have higher sintering activity at lower temperature. The application of the nano silver powder solves one selection of the application problems, and the comprehensive performance requirements of the front silver paste of the crystalline silicon solar cell on the aspects of screen printability, sintering activity, electrical performance and the like can be met through the compound use of the micro crystal silver powder and a small amount of nano silver powder. However, the use of the nano silver powder may cause an increase in the cost of the paste, and operational complexity and quality risks in terms of whether the nano silver powder can be uniformly dispersed in the paste, and the like.
Disclosure of Invention
The invention aims to provide silver powder with silver carboxylate modified surface and a preparation method thereof, aiming at the defects of the prior art. According to the silver powder, the silver carboxylate is coated on the surface of the silver powder through the reaction of the organic carboxylic acid and the silver nitrate ammonia water complex, and the silver powder after surface modification is spherical particles, and has the advantages of submicron-to-micron particle size, uniform appearance, good dispersibility, high tap density, excellent sintering performance, low series resistance and good conductivity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect, a method for preparing silver powder with silver carboxylate modified surface comprises the following steps:
dispersing silver powder with ethanol, adding silver nitrate ammonia water complex, dispersing uniformly, adding organic silver carboxylate, stirring to react to generate silver carboxylate, and coating the silver carboxylate on the surface of the silver powder to obtain the silver carboxylate surface modified silver powder.
Further, the silver powder is in the form of a sphere-like shape having a particle diameter of 0.5 to 4.0. Mu.m, preferably 1.0 to 3.0. Mu.m.
Further, in the silver nitrate ammonia water complex, the use amount of the silver nitrate is 0.01-5% of the mass of the silver powder, and preferably 0.05-1%; the dosage of the ammonia water is 2-3 times of the molar weight of the silver nitrate.
Further, the organic carboxylic acid is at least one selected from octanoic acid, dodecanoic acid, stearic acid, oleic acid and soft ester acid; the amount of the organic carboxylic acid is 1 to 1.1 times, preferably 1 to 1.05 times the molar amount of silver nitrate in the silver nitrate ammonia water complex.
Further, the conditions of the stirring reaction are as follows: stirring at the room temperature at the speed of 2000-4000 r/min for 3-10 min; preferably, the conditions of the stirring reaction are: stirring speed at room temperature is 3000r/min, and stirring time is 5min.
Further, the steps comprise solid-liquid separation, ethanol washing and drying.
Further, the silver powder is prepared by the following method:
mixing nano silver colloid with a dispersing agent, then dripping a silver nitrate solution and a reducing agent solution into the dispersing agent in a parallel flow manner under a stirring state, adding a surfactant and a pH regulator after dripping, regulating the pH to 5-6, stirring for reaction, and finally obtaining silver powder through solid-liquid separation, washing and drying.
Preferably, the dispersing agent is selected from at least one of polyethylene glycol, polyvinyl alcohol, gelatin, sodium dodecyl benzene sulfonate, tween 80, polyvinylpyrrolidone (PVP) and gum arabic; the dispersing agent is firstly dissolved in water to prepare a solution, and the concentration of the dispersing agent in the dispersing agent solution is 100-600 g/L, more preferably 250g/L; the dosage of the dispersing agent is 8-15 times, more preferably 10 times of the mass of the nano silver colloid.
Preferably, the reducing agent is at least one selected from glucose, sodium borohydride, formaldehyde, ascorbic acid, hydrazine hydrate, hydroquinone, alkanolamine and hydrogen peroxide; the concentration of the reducing agent in the reducing agent solution is 0.1-5 mol/L, more preferably 1.5mol/L; the consumption of the reducing agent is 10-20 times, more preferably 17 times of the mass of the nano silver colloid.
Preferably, the surfactant is at least one selected from oleic acid, sodium oleate, palmitic acid, caprylic acid, stearic acid and the like, and the amount of the surfactant is 1-5% of the mass of the silver powder to be produced, and more preferably 3%.
Preferably, the pH adjuster includes, but is not limited to, at least one of nitric acid, citric acid, ammonia, sodium hydroxide, sodium carbonate solution.
Preferably, the concentration of silver nitrate in the silver nitrate solution is 0.1-3 mol/L, more preferably 1mol/L; the dosage of the silver nitrate is 10-20 times, more preferably 15 times of the mass of the nano silver colloid.
Preferably, the particle size of silver particles in the nano silver colloid is 50-300 nm, the content of silver particles is 0.5-4%, and the silver particles have hydrophilic surfaces. As long as the above conditions are satisfied, the nano silver paste can be used as the seed crystal of the present invention.
In another aspect, a silver powder having a surface modified with silver carboxylate is prepared by the method described above.
Further, in the silver powder modified by the surface silver carboxylate, the silver carboxylate accounts for 0.1 to 0.6 percent of the total mass of the silver powder modified by the surface silver carboxylate.
The invention also provides application of the silver powder with the nano surface to silver paste for solar cells and/or electrode silver paste for electronic components.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the organic carboxylic acid and the silver nitrate ammonia water complex react to generate the silver carboxylate and coat the silver carboxylate on the surface of the silver powder, and the silver simple substance is decomposed from the silver carboxylate on the surface of the silver powder during sintering, so that the silver powder is directly welded together, a conductive network is easier to form, the series resistance is lower, and the conductivity is better; in addition, the silver powder modified by the surface carboxylic acid is low in decomposition temperature of the silver carboxylate, the surface sintering activity is improved, during the sintering process, the silver powder is welded together due to the fact that the silver carboxylate decomposes silver, the printed lines cannot collapse along with the volatilization decomposition of an organic carrier, the line-shaped storage is better, the high-aspect ratio is achieved, and the conversion efficiency of the battery is improved.
2. According to the method disclosed by the invention, silver carboxylate on the surface of silver powder with the particle size range of 0.5-4.0 mu m can be modified, the particle size distribution of the modified silver powder is unchanged, the dispersibility is high, the tap density is high, and better rheological property and thixotropic property are still kept.
3. The method has the advantages of simple equipment and process, mild reaction condition, short production period, easy operation, good repeatability, energy conservation and environmental protection, and is suitable for industrial amplification and industrialized application.
Drawings
FIG. 1 is an SEM image (15000 times) of the surface-modified silver powder obtained in example 3 of the present invention;
FIG. 2 is an SEM image (15000 times) of the surface-modified silver powder obtained in comparative example 1 of the present invention;
FIG. 3 is a graph showing the thermal weight loss of the surface-modified silver powder obtained in example 3 and comparative example 1 of the present invention.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely exemplary of the scope of the invention as claimed and many variations and modifications of the invention will be apparent to those skilled in the art in light of the disclosure, which are intended to be within the scope of the invention as claimed.
The invention uses nano silver colloid as seed crystal, the grain diameter of silver particles in the nano silver colloid is 50-300 nm, the content of silver particles is 0.5-4%, and the silver particles have hydrophilic surfaces. As long as the above conditions are satisfied, the nano silver paste can be used as a seed crystal of the present application. Specifically, the nano silver colloid can be prepared by the following method:
(1) Firstly, dissolving a dispersing agent I and silver nitrate into water to form a mixed solution I with the concentration of silver nitrate of 0.01-20.0 mmol/L, then adding a solution of a reducing agent I under stirring, and continuing stirring reaction to form nano silver seed crystals;
wherein the dispersing agent I is at least one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, sodium oleate and sodium dodecyl benzene sulfonate; the reducing agent I is at least one of sodium borohydride, hydrazine hydrate, ascorbic acid or hydrogen peroxide; the mol ratio of the reducer I to the silver nitrate is 0.2-3:1;
(2) Dissolving a complexing agent and silver nitrate in water to form a mixed solution II with the concentration of 0.1-2.0 mol/L of silver nitrate, then adding a dispersing agent II, a precipitator and nano silver crystal seeds into the water to form a mixed solution III, adding the mixed solution II into the mixed solution III under stirring, and stirring for reaction to form uniform silver-containing precursor precipitate;
wherein the dispersing agent II is at least one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, sodium oleate and sodium dodecyl benzene sulfonate; the precipitant is at least one of oxalic acid, sodium oxalate, ammonium bicarbonate, sodium carbonate, phosphoric acid, sodium phosphate, hydrochloric acid, sodium chloride, sodium hydroxide, sulfuric acid and ammonium sulfate;
(3) Adding a dispersing agent III and a reducing agent II into water according to the molar ratio of 0.1-10:1 to dissolve to form a mixed solution IV, adding the dispersing agent IV and a reaction speed control agent into water to dissolve to form a mixed solution V, adding the mixed solution IV and the mixed solution V into the silver-containing precursor precipitate prepared in the step (2) at equal speed, and stirring to react to generate nano silver colloid;
wherein the dispersing agent III is at least one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, sodium oleate and sodium dodecyl benzene sulfonate, and the reducing agent II is at least one of sodium borohydride, hydrazine hydrate, ascorbic acid and hydrogen peroxide; the dispersing agent IV is at least one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, sodium oleate and sodium dodecyl benzene sulfonate; the reaction speed control agent is at least one of ammonia water, nitric acid and sodium hydroxide; the molar ratio of the dosage of the dispersing agent IV to the reducing agent II in the mixed solution IV is 0.1-10:1; the mol ratio of the dosage of the reaction speed control agent to the reducing agent II in the mixed solution IV is 0.1-10:1; the concentration of the reaction rate controlling agent in the mixed solution V is 0.05 to 3.0mol/L.
The invention is further illustrated by means of the following specific examples. The various chemical reagents used in the examples of the present invention were obtained by conventional commercial means unless otherwise specified.
Example 1: preparation of surface silver stearate modified silver powder having particle size of 1.0 μm
(1) Silver powder synthesis
Preparing 2.2kg PVP into a solution PVP solution with the concentration of 250g/L, and adding 210g of nano silver colloid (the particle size of silver particles is 100nm and the content of silver particles is about 2 g) to uniformly disperse to obtain a mixed solution;
3.16kg of silver nitrate is dissolved in water to prepare 1mol/L silver nitrate solution, and a pH regulator is added to regulate the pH to 2; weighing 3.5kg of ascorbic acid to prepare a reducing agent solution with the concentration of 1.5mol/L, and adding a pH regulator to adjust the pH to 5;
then, the silver nitrate solution and the reducing agent solution are added into the mixed solution in parallel, after the dripping is finished, surfactant oleic acid accounting for 3 percent of the mass of the silver powder is added, and the pH is regulated to 5 by a pH regulator, so that the silver powder with the particle size of 1 mu m can be obtained;
(2) Silver carboxylate surface modification
Naturally settling the silver powder synthesized in the step (1), washing with deionized water for 2 times, and dispersing with ethanol to obtain silver powder ethanol mixed solution;
dissolving 2.6 silver nitrate in 5g of deionized water, adding 3g of ammonia water (ammonia gas content 25%) and uniformly mixing to prepare a silver nitrate ammonia water complex;
adding silver nitrate ammonia water complex into silver powder ethanol mixed solution under stirring, uniformly mixing, then adding 4.7g of stearic acid (stearic acid is added after being dissolved in 100g of ethanol), stirring for 5min, and then carrying out solid-liquid separation, ethanol washing and drying to obtain silver powder with silver carboxylate modified surface. Wherein the silver nitrate dosage is 0.13 percent of the mass fraction of the silver powder, and the mass of the silver stearate with the surface modified silver powder is 0.3 percent of the mass of the silver powder.
Example 2: preparation of silver powder modified with silver oleate on surface with particle size of 1.0 μm
(1) Silver powder synthesis
Preparing 2.2kg PVP into a solution PVP solution with the concentration of 250g/L, and adding 210g of nano silver colloid (the particle size of silver particles is 100nm and the content of silver particles is about 2 g) to uniformly disperse to obtain a mixed solution;
3.16kg of silver nitrate is dissolved in water to prepare 1mol/L silver nitrate solution, and a pH regulator is added to regulate the pH to 2; weighing 3.5kg of ascorbic acid to prepare a reducing agent solution with the concentration of 1.5mol/L, and adding a pH regulator to adjust the pH to 5;
then, the silver nitrate solution and the reducing agent solution are added into the mixed solution in parallel, after the dripping is finished, surfactant oleic acid accounting for 3 percent of the mass of the silver powder is added, and the pH is regulated to 5 by a pH regulator, so that the silver powder with the particle size of 1 mu m can be obtained;
(2) Silver carboxylate surface modification
Naturally settling the silver powder synthesized in the step 1), washing with deionized water for 2 times, and dispersing with ethanol to obtain silver powder ethanol mixed solution;
dissolving 2.6 silver nitrate in 5g of deionized water, adding 3g of ammonia water (ammonia gas content 25%) and uniformly mixing to prepare a silver nitrate ammonia water complex;
adding silver nitrate ammonia water complex into silver powder ethanol mixed solution under stirring, uniformly mixing, adding 4.7g of oleic acid, stirring for 5min, performing solid-liquid separation, washing with ethanol, and drying to obtain silver powder with surface modified by silver carboxylate. Wherein the silver nitrate dosage is 0.17% of the silver powder, and the silver oleate quality of the silver powder surface modification is 0.4% of the silver powder quality.
Example 3: preparation of silver powder modified with surface silver octoate having particle size of 2.0 μm
(1) Silver powder synthesis
Preparing 2.2kg PVP into a solution PVP solution with the concentration of 250g/L, adding 105g of nano silver colloid (the particle size of silver particles is 200nm, and the content of silver particles is about 2 g), and uniformly dispersing to obtain a mixed solution;
3.16kg of silver nitrate is dissolved in water to prepare 1mol/L silver nitrate solution, and a pH regulator is added to regulate the pH to 2; weighing 3.5kg of ascorbic acid to prepare a reducing agent solution with the concentration of 1.5mol/L, and adding a pH regulator to adjust the pH to 5;
then, the silver nitrate solution and the reducing agent solution are added into the mixed solution in parallel, after the dripping is finished, surfactant oleic acid accounting for 3 percent of the mass of the silver powder is added, and the pH value is regulated to 5 by a pH regulator, so that the silver powder with the particle size of 2 mu m can be obtained;
(2) Silver carboxylate surface modification
Naturally settling the silver powder synthesized in the step 1), washing with deionized water for 2 times, and dispersing with ethanol to obtain silver powder ethanol mixed solution;
dissolving 6.75g of silver nitrate in 6g of deionized water, adding 8g of ammonia water (ammonia gas content 25%) and uniformly mixing to prepare a silver nitrate ammonia water complex;
adding silver nitrate ammonia water complex into silver powder ethanol mixed solution under stirring, uniformly mixing, then adding 6g of octanoic acid, stirring for 5min, performing solid-liquid separation, washing with ethanol, and drying to obtain silver powder with surface modified by silver carboxylate. Wherein the silver nitrate dosage is 0.338% of the silver powder, and the silver octoate of which the silver powder surface is modified is 0.5% of the silver powder.
Example 4: preparation of silver powder modified with surface palmitic acid silver having particle size of 3.0 μm
(1) Silver powder synthesis
Preparing 2.2kg PVP into a solution PVP solution with the concentration of 250g/L, and adding 70g of nano silver colloid (the particle size of silver particles is 300nm and the content of silver particles is about 2 g) to uniformly disperse to obtain a mixed solution;
3.16kg of silver nitrate is dissolved in water to prepare 1mol/L silver nitrate solution, and a pH regulator is added to regulate the pH to 2; weighing 3.5kg of ascorbic acid to prepare a reducing agent solution with the concentration of 1.5mol/L, and adding a pH regulator to adjust the pH to 5;
then, the silver nitrate solution and the reducing agent solution are added into the mixed solution in parallel, after the dripping is finished, surfactant oleic acid accounting for 3 percent of the mass of the silver powder is added, and the pH value is regulated to 5 by a pH regulator, so that the silver powder with the particle size of 3 mu m can be obtained;
(2) Silver carboxylate surface modification
Naturally settling the silver powder synthesized in the step 1), washing with deionized water for 2 times, and dispersing with ethanol to obtain silver powder ethanol mixed solution;
dissolving 4.5g of silver nitrate in 5g of deionized water, adding 5g of ammonia water (ammonia gas content 25%) and uniformly mixing to prepare a silver nitrate ammonia water complex;
adding silver nitrate ammonia water complex into silver powder ethanol mixed solution under stirring, uniformly mixing, then adding 7.22g of palmitic acid (the palmitic acid is dissolved in 100g of ethanol), stirring for 5min, and then carrying out solid-liquid separation, ethanol washing and drying to obtain silver powder with silver carboxylate modified surface. Wherein the silver nitrate dosage is 0.225% of the silver powder, and the silver palmitate quality of silver powder surface modification is 0.59% of the silver powder quality.
Comparative example 1: preparation of silver powder modified with addition of silver nitrate Ammonia Water Complex alone having particle size of 2.0 μm
(1) Silver powder synthesis
Preparing 2.2kg PVP into a solution PVP solution with the concentration of 250g/L, adding 105g of nano silver colloid (the particle size of silver particles is 200nm, and the content of silver particles is about 2 g), and uniformly dispersing to obtain a mixed solution;
3.16kg of silver nitrate is dissolved in water to prepare 1mol/L silver nitrate solution, and a pH regulator is added to regulate the pH to 2; weighing 3.5kg of ascorbic acid to prepare a reducing agent solution with the concentration of 1.5mol/L, and adding a pH regulator to adjust the pH to 5;
then, the silver nitrate solution and the reducing agent solution are added into the mixed solution in parallel, after the dripping is finished, surfactant oleic acid accounting for 3 percent of the mass of the silver powder is added, and the pH value is regulated to 5 by a pH regulator, so that the silver powder with the particle size of 2 mu m can be obtained;
(2) During the alcohol washing of silver powder, silver nitrate ammonia complex is added
Naturally settling the silver powder synthesized in the step (1), washing with deionized water for 2 times, and dispersing with ethanol to obtain silver powder ethanol mixed solution;
dissolving 6.75g of silver nitrate in 6g of deionized water, adding 8g of ammonia water (ammonia gas content 25%) and uniformly mixing to prepare a silver nitrate ammonia water complex;
adding silver nitrate ammonia water complex into silver powder ethanol mixed solution under stirring, uniformly mixing, stirring for 5min, and then carrying out solid-liquid separation, ethanol washing and drying to obtain silver powder with silver carboxylate modified surface.
Comparative example 2: preparation of silver powder modified with stearic acid alone having particle size of 1.0 μm
(1) Silver powder synthesis
Preparing 2.2kg PVP into a solution PVP solution with the concentration of 250g/L, and adding 210g of nano silver colloid (the particle size of silver particles is 100nm and the content of silver particles is about 2 g) to uniformly disperse to obtain a mixed solution;
3.16kg of silver nitrate is dissolved in water to prepare 1mol/L silver nitrate solution, and a pH regulator is added to regulate the pH to 2; weighing 3.5kg of ascorbic acid to prepare a reducing agent solution with the concentration of 1.5mol/L, and adding a pH regulator to adjust the pH to 5;
then, the silver nitrate solution and the reducing agent solution are added into the mixed solution in parallel, after the dripping is finished, surfactant oleic acid accounting for 3 percent of the mass of the silver powder is added, and the pH is regulated to 5 by a pH regulator, so that the silver powder with the particle size of 1 mu m can be obtained;
2) Adding stearic acid during alcohol washing of silver powder
Naturally settling the silver powder synthesized in the step 1), washing with deionized water for 2 times, and dispersing with ethanol to obtain silver powder ethanol mixed solution;
adding 4.7g of stearic acid (stearic acid is dissolved in 100g of ethanol) into the silver powder ethanol mixed solution under the stirring condition, and after stirring for 5min, carrying out solid-liquid separation, ethanol washing and drying to obtain the silver powder with the surface modified by silver carboxylate.
Test example 1
The microscopic morphology of the surface-modified silver powder obtained in example 3 and comparative example 1 above was observed by scanning electron microscopy, and SEM was measured as shown in fig. 1 and 2.
As shown in fig. 2, fig. 1 is the silver powder modified by adding only the silver nitrate ammonia water complex in comparative example 1, and fig. 1 is the silver powder modified by the surface silver octoate in example 3, and it can be seen from comparison between fig. 1 and fig. 2 that the silver powder before and after the surface silver carboxylate modification has a spherical structure, and has better dispersibility and uniform morphology.
Test example 2
Particle size, specific surface area, tap density and loss on ignition of the silver powder before and after surface modification were measured and the results are shown in table 1 below.
TABLE 1 parameters of silver powder after surface modification
The result shows that compared with the comparative example, the silver powder surface is not modified by silver carboxylate, and the specific surface area of the silver powder prepared in the embodiment of the application is almost unchanged after the silver carboxylate on the surface is modified, which means that the silver carboxylate coated on the silver powder surface has small size, has no influence on the viscosity of the slurry, and the burning loss is increased, and the increase can be found by calculation, and the loss amount of the silver carboxylate is consistent with the quality of organic carboxylate in the silver carboxylate on the silver powder surface, which means that the silver carboxylate prepared in the alcohol washing stage is coated on the silver powder surface.
Test example 3
Silver paste was prepared using silver powder before and after surface modification as conductive particles in the same ratio and the same carrier, respectively, and then viscosity, rheological properties, and electrical properties were tested. The preparation method of the silver paste comprises the following steps: uniformly mixing 92% of silver powder in parts by weight with 6% of carrier and 2% of glass powder, and rolling by three rollers to obtain silver paste; wherein the carrier formulation is as follows: 5% of ethyl cellulose, 10% of JH180 thixotropic agent, 20% of dibutyl phthalate, 20% of diethylene glycol butyl ether acetate, 20% of diethylene glycol butyl ether, 15% of terpineol and 10% of dodecanol ester.
Viscosity test: the test was carried out using a BROOKFIELD DV-II+Pro viscometer at 25℃with rotational speeds of 10rmp, 30rmp, 50rmp and 100rmp, respectively, for a test time of 1min.
Rheological property test: the rheological data are tested by using a BROOKFIELD R/S plus rheometer, the testing temperature is 25 ℃, and the testing method is as follows: the shear rate is continuously increased from 0 to 60/s for 60s, the deceleration curve is time 60s, the shear rate is reduced from 60/s to 0, and readings at 1s, 10s, 60s and 120s are selected.
And (3) testing electrical properties: and printing silver paste on the battery piece by adopting a screen printing process, preparing a solar battery piece sample by adopting a quick firing process, and testing the serial electronic and other electrical properties of the sample by adopting a solar battery testing system.
The results are shown in tables 2 and 3 below.
TABLE 2 viscosity and rheological Properties of surface modified silver powder
The front side silver paste needs to have good thixotropic properties so that it can pass through the screen when printed and the printed grid lines are not easily collapsed. From the viscosity and rheological data in the table, the viscosity and rheological change of the silver powder after the surface silver carboxylate modification are small, and good rheology and thixotropy still remain, which indicates that the printing line of the silver powder obtained in the example is not degraded due to the surface modification.
TABLE 3 silver paste string resistance and aspect ratio
| Group of | String resistance Rs/Ohm | Aspect ratio |
| Example 1 | 1.04 | 0.29 |
| Example 2 | 1.03 | 0.30 |
| Example 3 | 1.05 | 0.28 |
| Example 4 | 1.07 | 0.27 |
| Comparative example 1 | 1.23 | 0.24 |
| Comparative example 2 | 1.11 | 0.26 |
As can be seen from the series resistance data in the table, the series resistance of the comparative example 1 is higher than that of the example 3, which shows that under the rapid firing process, the silver powder modified by the surface silver carboxylate decomposes silver simple substance due to the silver carboxylate during sintering, so that the silver powder is directly welded together, a conductive network is easier to form, the series resistance is lower, and the conductive performance is better. According to the data of the aspect ratio, the silver powder modified by the surface carboxylic acid is welded together because of the low decomposition temperature of the silver carboxylate and the high surface sintering activity, and the printed line shape cannot collapse along with the volatilization and decomposition of the organic carrier, so that the line shape is better in preservation and has better aspect ratio.
Test example 4
The surface-modified silver powders obtained in example 3 and comparative example 1 were characterized by a thermogravimetric analyzer, and the thermogravimetric curves were measured as shown in fig. 3. As can be seen from fig. 3, the temperature at which the thermal weight loss starts in example 3 is significantly lower than in comparative example 1, which is that the silver carboxylate modified on the surface of the silver powder can be thermally decomposed to form elemental silver, which shortens the sintering temperature of the silver powder.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the silver powder with the surface modified by the silver carboxylate is characterized by comprising the following steps of:
dispersing silver powder with ethanol, adding silver nitrate ammonia water complex, dispersing uniformly, adding organic silver carboxylate, reacting to generate silver carboxylate, and coating the silver carboxylate on the surface of the silver powder to obtain the silver carboxylate surface modified silver powder.
2. The preparation method according to claim 1, wherein the silver powder is in the form of a spheroid having a particle diameter of 0.5 to 4.0 μm, preferably 1.0 to 3.0 μm.
3. The preparation method according to claim 1, wherein the silver nitrate ammonia water complex is used in an amount of 0.01 to 5% by mass, preferably 0.05 to 1% by mass, of silver powder; the dosage of the ammonia water is 2-3 times of the molar weight of the silver nitrate.
4. The method according to claim 1, wherein the organic carboxylic acid is at least one selected from the group consisting of octanoic acid, dodecanoic acid, stearic acid, oleic acid, and a soft ester acid; the amount of the organic carboxylic acid is 1 to 1.1 times, preferably 1 to 1.05 times the molar amount of silver nitrate in the silver nitrate ammonia water complex.
5. The method according to claim 1, wherein the conditions of the stirring reaction are: stirring at the room temperature at the speed of 2000-4000 r/min for 3-10 min; preferably, the conditions of the stirring reaction are: stirring speed at room temperature is 3000r/min, and stirring time is 5min.
6. The preparation method according to claim 1, wherein the silver powder is prepared by the following method:
mixing nano silver colloid with a dispersing agent, then dripping a silver nitrate solution and a reducing agent solution into the dispersing agent in a parallel flow manner under a stirring state, adding a surfactant and a pH regulator after dripping, regulating the pH to 5-6, stirring for reaction, and finally obtaining silver powder through solid-liquid separation, washing and drying.
7. The method according to claim 6, wherein the dispersant is at least one selected from the group consisting of polyethylene glycol, polyvinyl alcohol, gelatin, sodium dodecylbenzenesulfonate, tween 80, polyvinylpyrrolidone and gum arabic; the reducing agent is at least one selected from glucose, sodium borohydride, formaldehyde, ascorbic acid, hydrazine hydrate, hydroquinone, alkanolamine and hydrogen peroxide.
8. The method according to claim 6, wherein the particle size of silver particles in the nano silver paste is 50 to 300nm, the content of silver particles is 0.5 to 4%, and the silver particles have a hydrophilic surface.
9. Silver powder modified with silver carboxylate surface, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. The surface silver carboxylate modified silver powder of claim 9, wherein the silver carboxylate is 0.1 to 0.6% of the total mass of the surface silver carboxylate modified silver powder.
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