CN117300148A - Nanometer silver powder and preparation method thereof - Google Patents
Nanometer silver powder and preparation method thereof Download PDFInfo
- Publication number
- CN117300148A CN117300148A CN202311605235.9A CN202311605235A CN117300148A CN 117300148 A CN117300148 A CN 117300148A CN 202311605235 A CN202311605235 A CN 202311605235A CN 117300148 A CN117300148 A CN 117300148A
- Authority
- CN
- China
- Prior art keywords
- solution
- nano silver
- silver powder
- reaction
- reducing
- 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 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000003638 chemical reducing agent Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 230000009467 reduction Effects 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- -1 silver ions Chemical class 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 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 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- 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 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 6
- 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 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000008103 glucose Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920003082 Povidone K 90 Polymers 0.000 claims description 4
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229920003081 Povidone K 30 Polymers 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000205 acacia gum Substances 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- VWCFCFOIUSKKSC-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound NCCN.OP1(=O)OCCCCO1 VWCFCFOIUSKKSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- 229940096017 silver fluoride Drugs 0.000 claims description 3
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 104
- 238000009826 distribution Methods 0.000 description 24
- 230000008569 process Effects 0.000 description 22
- 238000005054 agglomeration Methods 0.000 description 17
- 230000002776 aggregation Effects 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000011858 nanopowder Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000009776 industrial production Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000036632 reaction speed Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 102220043159 rs587780996 Human genes 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 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
- 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
-
- 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
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a preparation method of nanometer silver powder, which specifically comprises the following steps: preparing a first reducing solution; preparing a second reducing solution; preparing an oxidizing solution; preparing a dispersion protection liquid; mixing the four solutions, reacting, filtering and separating; further washing, separating, drying and grinding to obtain nano silver powder; the invention also provides the nano silver powder, which is obtained according to the preparation method of the nano silver powder. The method solves the problem of industrialized mass production of the nano silver powder, fills the blank of industrialization of the nano silver powder in China, and promotes rapid introduction of HJT battery technology.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to nano silver powder and a preparation method thereof.
Background
The nano silver powder has excellent thermal conductivity, electrical conductivity and lower-temperature sintering solidification property, and the special physical properties enable the nano silver powder to be widely applied to the fields of electronic intelligent equipment terminals and photovoltaic cells, wherein the fields of electronic equipment comprise computers, mobile phones, electronic watches, membrane switches and the like, the shadows of the nano silver powder materials are not separated, the solar battery is widely applied as a terminal carrier of an obtaining mode of zero-emission green energy source in recent years, the requirements on the silver powder materials are far greater than those of other electronic industry fields, and the requirements on the silver powder materials are more strict. In order to pursue a new battery structure with higher photoelectric conversion efficiency, particularly the Heterojunction (HJT) battery has been developed, so that the conversion efficiency of the photovoltaic battery is closer to the theoretical highest level of the battery, the development of the new technology puts higher demands on the preparation of raw material silver powder of conductive silver paste applied to grid line printing, such as smaller particle size, lower sintering or curing temperature and better dispersion performance. Therefore, the nanometer silver powder with excellent parameters is urgently required by photovoltaic slurry manufacturers,
however, the synthesis of nano silver powder and how to prevent the agglomeration effect thereof are always limited to be applied to various fields, and the main synthesis method is two kinds of physical methods and chemical methods, but the prepared nano silver has various non-ideal states, is too wide in distribution, has few large particles and poor in stability, and the problems limit the wide application of the nano silver powder in various fields, in particular the wide industrialized popularization and technology update of photovoltaic cells to the novel HJT battery technology.
Disclosure of Invention
Aiming at the technical problems, the invention provides the preparation method of the nano silver powder, which has the advantages of simple process, high production efficiency and good stability, is beneficial to stably producing nano powder in batches in industrial production, has accurate and controllable particle size for producing the nano silver powder, and overcomes the problems of fluctuation of particle size and poor powder agglomeration dispersibility among batches in the synthesis process of industrial production; the prepared nano silver powder has the characteristics of narrow particle size distribution, centralized particle distribution of single particle size, good monodispersity, high tap density and low organic burning loss residue; the invention also provides the nano silver powder which has the advantages of spherical or spheroidic shape, narrow particle size distribution, good dispersibility, high tap density, low organic burning loss residue and accurate and controllable particle size of 50-1000 nm.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the nano silver powder specifically comprises the following steps:
dissolving or diluting a first reducing agent by deionized water to prepare a first reducing solution, and keeping the first temperature for standby;
step (2) dissolving or diluting a second reducing agent by adopting a second solvent to prepare a second reducing solution, and keeping the second temperature for standby;
step (3) dissolving soluble silver salt by deionized water and/or ammonia water to prepare an oxidizing solution, and keeping the third temperature for standby;
step (4) dissolving or diluting the dispersing agent by adopting a third solvent to prepare a dispersion protection liquid, and keeping the fourth temperature for standby;
step (5) mixing the first reducing solution, the second reducing solution, the oxidizing solution and the dispersion protection solution for reaction, and obtaining a reaction solution containing nano silver particles after the reaction is completed;
and (6) filtering and separating the reaction solution containing the nano silver particles to obtain nano silver particles, and then washing, separating, drying and grinding the nano silver particles to obtain the nano silver powder.
According to the invention, two or more reducing agents are selected, so that silver ions are promoted to be reduced for two or more times under the action of the reducing agents with different reducing strengths, and the reducing speed is effectively controlled; the method can also carry out gradient reduction on silver ions by selecting reducing agents with different reduction speeds, so as to control the particle size and the particle size distribution of the silver ions; the method has the advantages of simple process, high production efficiency, good stability and high batch yield, and is beneficial to stable batch production of nano powder in industrial production; the method provided by the invention has the advantages that the particle size of the produced nano silver powder is accurate and controllable, and the problem that the particle size fluctuation and the powder agglomeration dispersibility are poor between batches in the industrial production and synthesis process is solved; the nano silver powder prepared by the method has excellent performance, is spherical or spheroid in shape, has narrow particle size distribution, is centralized in particle distribution of single particle size, and has the characteristics of good monodispersity, high tap density and low organic burning loss residue. The method solves the problem of industrialized mass production of the nano silver powder, fills the blank of industrialization of the nano silver powder in China, and promotes rapid introduction of HJT battery technology.
Further, in the step (1), the first reducing agent is one or more of ascorbic acid, citric acid, citrate, formaldehyde, formic acid, glucose and hydrazine hydrate, the concentration of the first reducing solution is 0.2-3.0mol/L, and the first temperature is 20-80 ℃.
The concentration of the first reducing agent is controlled to be 0.2-3.0mol/L, and the temperature is controlled to be 20-80 ℃, so that the reaction speed is higher in the reaction process of the method, the reaction intensity is moderate, the obtained nano silver powder has narrow particle size distribution, the steric hindrance space of the new particles is moderate, the new particles are not easy to collide and agglomerate, and meanwhile, the nano particle size particles are easy to obtain.
Further, the second reducing agent in the step (2) is one or more of citric acid, citrate, formaldehyde, formic acid, glucose, hydrazine hydrate, sulfite, phosphorous acid, ferrous chloride, hydroxylamine, sodium borohydride, potassium borohydride and ethylene glycol, and the concentration of the second reducing solution is 0.01-1.0mol/L;
the second solvent is one or more of deionized water, ethanol, isopropanol, diethyl ether, ethylene glycol monobutyl ether, propylene oxide, hexane, cyclohexane, methyl acetate, ethyl acetate, toluene, xylene, acetone, methyl isobutyl ketone, tetrahydrofuran, pyridine and morpholine, and the second temperature is 20-200 ℃.
The concentration of the second reducing agent is controlled to be 0.01-1.0mol/L, and the temperature is controlled to be 20-200 ℃, so that the reaction speed is higher in the reaction process of the method, the reaction intensity is moderate, the obtained nano silver powder has narrow particle size distribution, the steric hindrance space of the new particles is moderate, the collision agglomeration is not easy, and meanwhile, the nano particle size particles are also easy to obtain.
Preferably, the soluble silver salt in the step (3) is one or more of silver nitrate, silver carbonate, silver fluoride and silver chlorate; the oxidation solution contains free silver ions and/or silver ammonia complex ions, the concentration of the silver ions in the oxidation solution is 0.5-2.0mol/L or the mass concentration of the silver ammonia complex ions is 30-150g/L, and the third temperature is 20-80 ℃.
The concentration of silver ions in the oxidation liquid is controlled to be 0.5-2.0mol/L or the mass concentration of silver ammine complex ions is controlled to be 30-150g/L, and the temperature is controlled to be 20-80 ℃, so that the reaction speed is higher in the reaction process of the method, the reaction intensity is moderate, the particle size distribution of the obtained nano silver powder is narrow, the steric hindrance space of the new particles is moderate, the new particles are not easy to collide and agglomerate, and the nano particle size particles are easy to obtain.
Further, the dispersing agent in the step (4) is one or more of sodium dodecyl sulfate, polyethylene glycol, gelatin, gum arabic, xanthan gum, oleic acid, oleamide, polyacrylamide, fatty acid with carbon number between 4 and 18, succinic acid, PVP-K30, PVP-K90, tween-40, tween-80, castor oil, ethylcellulose, methylcellulose, ethylenediamine tetramethylene phosphate, hydroxyethylidene diphosphate and aminotrimethylene phosphate; the amount of the dispersing agent is 0.1-50 times of the mass of silver salt in the oxidation liquid, and the third solvent is one or more of deionized water, ethanol, isopropanol, diethyl ether, ethylene glycol monobutyl ether, propylene oxide, hexane, cyclohexane, methyl acetate, ethyl acetate, toluene, xylene, acetone, methyl isobutyl ketone, tetrahydrofuran, pyridine and morpholine; the concentration of the dispersion protection liquid is 0.1-50g/L, and the fourth temperature is 20-200 ℃.
The concentration of the dispersion protection liquid is controlled to be 0.1-50g/L, the temperature is controlled to be 20-200 ℃, so that the reaction speed is higher in the reaction process of the method, the reaction intensity is moderate, the obtained nano silver powder has narrow particle size distribution, the steric hindrance of the new particles is moderate, the new particles are not easy to collide and agglomerate, the nano particle size particles are also easy to obtain, the dispersion protection liquid under the concentration can not limit the displacement of the new particles, excessive organic dispersion substances can not be adsorbed on the surface, the post-treatment and the cleaning are convenient, and the burning loss residue of the nano silver powder is not influenced.
Further, the mixing in the step (5) adopts a first mixing mode or a second mixing mode; the first mixing mode is as follows: firstly adding the oxidation solution into the dispersion protection solution, uniformly mixing, adding the second reduction solution for reaction, and then adding the first reduction solution for continuous reaction after the reaction is finished.
The adoption of the mixing mode is more suitable for the stepwise reduction of the method.
Further, the second mixing mode is as follows: and adding the second reducing solution into the dispersion protection solution, then adding part of the oxidizing solution for reaction, and after the reaction is finished, adding the first reducing solution and the rest of the oxidizing solution for continuous reaction.
The adoption of the mixing mode is more suitable for the stepwise reduction of the method.
Further, ultrasonic dispersion is adopted in the washing process in the step (6), and the washing liquid adopted in the washing process is one or more of deionized water, ammonia water, ethylenediamine, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, hexane, toluene, xylene, styrene, chloroform, acetone and methyl butanone;
the soft agglomerated particles which have already been aggregated can be opened by ultrasonic dispersion and the nanoparticle re-agglomeration during the washing process is prevented, thus achieving better dispersibility. Because the molecular polarity of the washing solutions is smaller, the nano particles can be effectively prevented from agglomerating by adopting the washing solutions, and then hydrogen bond formation can be effectively reduced after the washing process is finished and the washing solutions enter a drying stage, so that hard agglomeration is prevented from being formed in the drying and dehydration process, and the agglomeration effect of nano powder in the drying treatment process is reduced; the method of the invention well overcomes the agglomeration effect of the nano powder in the process of reduction and growth and the process of post-treatment after the powder reduction by selecting the above materials and adopting ultrasonic dispersion assistance in the washing process.
Further, the drying mode in the step (6) is one or more of vacuum drying, freeze drying and spray drying.
By adopting one or more of the three drying modes, better dispersibility can be obtained, soft agglomeration or hard agglomeration of powder can be avoided in the drying treatment process, and if a conventional high-temperature baking mode is adopted, the moisture of the powder volatilizes rapidly, so that weak sintering effect is easily formed in the re-drying process of the nano powder, and the hard agglomeration is caused.
In order to further solve the technical problems, the invention also provides nano silver powder, which is obtained according to the preparation method of the nano silver powder.
The nanometer silver powder provided by the invention has the shape of sphere or spheroid, narrow particle size distribution, good monodispersity and tap density not lower than 4.0g/cm 3 The powder has good dispersibility, is easy to uniformly disperse during pulping, and is not easy to block a screen during printing; the organic burning loss residue at 538 ℃ is lower than 1.0%, the impurity residue of the slurry in the curing or quick burning process is low, the resistance is not increased, and the conductivity is excellent; the particle size is precisely controllable between 50nm and 1000nm, and the mass production stability is high.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention, as well as the preferred embodiments thereof, together with the following detailed description of the invention, given by way of illustration only, together with the accompanying drawings.
Drawings
FIG. 1 is an electron microscopic view of the nano silver powder prepared in example 1 of the present invention.
FIG. 2 is an electron microscopic view of the nano silver powder prepared in example 2 of the present invention.
FIG. 3 is an electron microscopic view of the nano silver powder prepared in example 3 of the present invention.
FIG. 4 is an electron microscopic view of the nano silver powder prepared in example 4 of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset purpose of the present invention, the following description refers to the specific implementation, structure, characteristics and effects of a method for preparing nano silver powder according to the present invention, which are described in detail below with reference to the accompanying drawings and preferred embodiments.
The preparation method of the nano silver powder specifically comprises the following steps:
dissolving or diluting a first reducing agent by deionized water to prepare a first reducing solution, and keeping the first temperature for standby;
step (2) dissolving or diluting a second reducing agent by adopting a second solvent to prepare a second reducing solution, and keeping the second temperature for standby;
step (3) dissolving soluble silver salt by deionized water and/or ammonia water to prepare an oxidizing solution, and keeping the third temperature for standby;
step (4) dissolving or diluting the dispersing agent by adopting a third solvent to prepare a dispersion protection liquid, and keeping the fourth temperature for standby;
step (5) mixing the first reducing solution, the second reducing solution, the oxidizing solution and the dispersion protection solution for reaction, and obtaining a reaction solution containing nano silver particles after the reaction is completed;
and (6) filtering and separating the reaction solution containing the nano silver particles to obtain nano silver particles, and then washing, separating, drying and grinding the nano silver particles to obtain the nano silver powder.
According to the invention, two or more reducing agents are selected, so that silver ions are promoted to be reduced for two or more times under the action of the reducing agents with different reducing strengths, and the reducing speed is effectively controlled; the method can also carry out gradient reduction on silver ions by selecting reducing agents with different reduction speeds, so as to control the particle size and the particle size distribution of the silver ions; the method has the advantages of simple process, high production efficiency, good stability and high batch yield, and is beneficial to stable batch production of nano powder in industrial production; the method provided by the invention has the advantages that the particle size of the produced nano silver powder is accurate and controllable, and the problem that the particle size fluctuation and the powder agglomeration dispersibility are poor between batches in the industrial production and synthesis process is solved; the nano silver powder prepared by the method has excellent performance, is spherical or spheroid in shape, has narrow particle size distribution, is centralized in particle distribution of single particle size, and has the characteristics of good monodispersity, high tap density and low organic burning loss residue. The method solves the problem of industrialized mass production of the nano silver powder, fills the blank of industrialization of the nano silver powder in China, and promotes rapid introduction of HJT battery technology.
In the preferred embodiment of the invention, the first reducing agent in the step (1) is one or more of ascorbic acid, citric acid, citrate, formaldehyde, formic acid, glucose and hydrazine hydrate, the concentration of the first reducing solution is 0.2-3.0mol/L, and the first temperature is 20-80 ℃; in the step (2), the second reducing agent is one or more of citric acid, citrate, formaldehyde, formic acid, glucose, hydrazine hydrate, sulfite, phosphorous acid, ferrous chloride, hydroxylamine, sodium borohydride, potassium borohydride and ethylene glycol, and the concentration of the second reducing solution is 0.01-1.0mol/L; the second solvent is one or more of deionized water, ethanol, isopropanol, diethyl ether, ethylene glycol monobutyl ether, propylene oxide, hexane, cyclohexane, methyl acetate, ethyl acetate, toluene, xylene, acetone, methyl isobutyl ketone, tetrahydrofuran, pyridine and morpholine, and the second temperature is 20-200 ℃;
the selection of two or more reducing agents can promote silver ions to be reduced for two or more times under the action of the reducing agents with different reducing strengths, the reducing speed can be effectively controlled, and compared with the reducing agents with low reducing speed, the reducing agents with high reducing speed can obtain smaller particle size; the reducing agent with mild or slow reducing speed can obtain more uniform particle size distribution, and the method can carry out gradient reduction on silver ions so as to better control the particle size and the particle size distribution.
In a preferred embodiment of the present invention, the soluble silver salt in step (3) is one or more selected from silver nitrate, silver carbonate, silver fluoride and silver chlorate; the oxidation solution contains free silver ions and/or silver ammonia complex ions, the concentration of the silver ions in the oxidation solution is 0.5-2.0mol/L or the mass concentration of the silver ammonia complex ions is 30-150g/L, and the third temperature is 20-80 ℃; in the step (4), the dispersing agent is one or more of sodium dodecyl sulfate, polyethylene glycol, gelatin, gum arabic, xanthan gum, oleic acid, oleamide, polyacrylamide, fatty acid with carbon number between 4 and 18, succinic acid, PVP-K30, PVP-K90, tween-40, tween-80, castor oil, ethylcellulose, methylcellulose, ethylenediamine tetramethylene phosphate, hydroxyethylidene diphosphate and aminotrimethylene phosphate; the amount of the dispersing agent is 0.1-50 times of the mass of silver salt in the oxidation solution, and the third solvent is one or more of deionized water, ethanol, isopropanol, diethyl ether, ethylene glycol monobutyl ether, propylene oxide, hexane, cyclohexane, methyl acetate, ethyl acetate, toluene, xylene, acetone, methyl isobutyl ketone, tetrahydrofuran, pyridine and morpholine; the concentration of the dispersion protection liquid is 0.1-50g/L, and the fourth temperature is 20-200 ℃.
The concentration and the temperature are means for assisting in controlling the reduction speed, the reduction temperature is low in concentration and temperature, the reaction is mild, the obtained powder has narrow particle size distribution, the steric hindrance space of the new particles is large, the new particles are not easy to collide and agglomerate, but the nanometer particle size particles are not easy to obtain, otherwise, the reduction speed is high, the reaction is severe, the obtained powder has different particle sizes, the distribution is wide, the steric hindrance space of the new particles is small, the new particles are easier to collide and agglomerate, but the nanometer particle size particles are easier to obtain. The method controls the reaction speed and the reaction intensity in the reaction process by controlling the concentration and the temperature of the first reducing agent, the second reducing agent, the oxidizing solution and the dispersion protection solution, so that the finally obtained nano silver powder has narrow particle size distribution, the steric hindrance space of the new particles is moderate, the new particles are not easy to collide and agglomerate, and the nano particle size particles are also easy to obtain; and the dispersion protection liquid under the concentration can not limit the displacement of the new particles, and the surface can not adsorb excessive organic dispersion substances, so that the after-treatment cleaning is convenient, and the burning loss residue of the nano silver powder is not influenced.
The mixing in the step (5) adopts a first mixing mode or a second mixing mode; the first mixing mode is as follows: firstly adding an oxidation solution into a dispersion protection solution, uniformly mixing, adding a second reduction solution for reaction, and then adding a first reduction solution for continuous reaction after the reaction is finished; the second mixing mode is as follows: and adding the second reducing solution into the dispersion protection solution, then adding part of the oxidizing solution for reaction, and after the reaction is finished, adding the first reducing solution and the rest of the oxidizing solution for continuous reaction.
The adoption of the two mixing modes can facilitate the distributed reduction in the reaction process, and other mixing modes are not suitable for the stepwise reduction.
In the preferred embodiment of the invention, ultrasonic dispersion is adopted for assisting in the washing process in the step (6), and one or more of deionized water, ammonia water, ethylenediamine, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, hexane, toluene, xylene, styrene, chloroform, acetone and methyl butanone are adopted as the washing liquid in the washing process;
the invention well overcomes the agglomeration effect of nano powder in the process of reduction and growth and in the process of post-treatment after powder reduction by improving the selection of the washing liquid and the washing mode; the soft agglomerated particles which have already been aggregated can be opened by ultrasonic dispersion and the nanoparticle re-agglomeration during the washing process is prevented, thus achieving better dispersibility. Because the molecular polarity of the washing solutions is smaller, the nano particles can be effectively prevented from agglomerating by adopting the washing solutions, and then hydrogen bond formation can be effectively reduced after the washing process is finished and the washing solutions enter a drying stage, so that hard agglomeration is prevented from being formed in the drying and dehydration process, and the agglomeration effect of nano powder in the drying treatment process is reduced; the method of the invention well overcomes the agglomeration effect of the nano powder in the process of reduction and growth and the process of post-treatment after the powder reduction by selecting the above materials and adopting ultrasonic dispersion assistance in the washing process.
Example 1
(1) Weighing 100g of hydrazine hydrate solution with the concentration of 55% as a first reducing agent, adding deionized water to dilute to the mass concentration of 12%, keeping the temperature at 50 ℃, and standing for later use as a first reducing solution;
(2) Weighing 32g of citric acid as a second reducing agent, dissolving the citric acid into isopropanol to ensure that the concentration of the solution is 0.30mol/L, heating to 50 ℃ and keeping the temperature, and standing for later use as a second reducing solution;
(3) Weighing 125g of silver nitrate, adding 400ml of deionized water and 40g of ammonia water to prepare silver-ammonia solution, and keeping the temperature at 50 ℃ for later use as an oxidizing solution;
(4) Weighing 0.5g of octanoic acid and 30g of aminotrimethylene phosphate as dispersing agents, adopting 200g of hexane for dissolution, keeping the temperature at 50 ℃, and standing for standby as dispersion protection liquid;
(5) Mixing the oxidation solution and the dispersion protection solution, and stirring for 5min; secondly, adding the second reducing solution into the reaction kettle, heating to 80 ℃, and reacting for 30min; then slowly adding the first reducing solution to continue the reaction for at least 60min; obtaining a reaction solution containing nano silver particles after the reaction is completed;
(6) Filtering the reaction solution containing the nano silver particles to separate the nano silver powder from the reaction waste liquid, and then using 3: and (3) cleaning the mixed solution of deionized water and isopropanol, adding ultrasonic auxiliary dispersion in the cleaning process, then centrifugally drying, freeze-drying and vacuum-drying, and crushing and grinding to obtain the nano silver powder 1.
D50=65 nm of the nano silver powder 1 prepared in the embodiment, and the tap density is 4.15g/cm 3 The organic burning loss residue at 538 ℃ is 0.67%; the scanning electron microscope analysis photograph of the nano silver powder 1 prepared in the embodiment is shown in fig. 1, the morphology of the obtained nano silver powder is similar to a sphere, the particle size distribution is uniform, the dispersibility is good, and most of the particle size is concentrated between 50nm and 80 nm.
Example 2
(1) Weighing 100g of hydrazine hydrate solution with the concentration of 55% as a first reducing agent, adding deionized water to dilute to the mass concentration of 10%, keeping the temperature at 20 ℃, and standing for later use as a first reducing solution;
(2) Weighing 20g of hydrazine hydrate solution with the concentration of 55% as a second reducing agent, dissolving the solution into cyclohexane to enable the concentration of the solution to be 0.10mol/L, heating to the temperature of 70 ℃ and keeping the temperature as a second reducing solution, and standing for later use;
(3) Weighing 145g of silver nitrate, adding 470ml of deionized water and 48g of ammonia water to prepare silver-ammonia solution, and keeping the temperature at 70 ℃ for later use as an oxidizing solution;
(4) Weighing 0.02g of myristic acid, 20g of PVP-K90 and 20g of Tween-80 as dispersing agents, dissolving by adopting 200g of cyclohexane, keeping the temperature at 50 ℃, and standing for later use as dispersion protection liquid;
(5) Mixing the oxidation solution and the dispersion protection solution, and stirring for 5min; secondly, adding the second reducing solution into the reaction kettle to react for 30min; then slowly adding the first reducing solution to continue the reaction for at least 60min; obtaining a reaction solution containing nano silver particles after the reaction is completed;
(6) Filtering the reaction solution containing the nano silver particles to separate the nano silver powder from the reaction waste liquid, and then using 1:1, cleaning a mixed solution of deionized water and acetone, adding ultrasonic auxiliary dispersion in the cleaning process, then centrifugally drying, and crushing and grinding to obtain the nano silver powder 2.
The nano silver powder 2 prepared in the embodiment has D50=150nm, tap density of 4.63g/cm < 3 >, and organic burning loss residue at 538 ℃ of 0.58%; the scanning electron microscope analysis photograph of the nano silver powder 2 prepared in the embodiment is shown in fig. 2, the morphology of the obtained nano silver powder is similar to a sphere, the particle size distribution is uniform, the dispersibility is good, and most of the particle size is concentrated between 100nm and 200 nm.
Example 3
(1) Weighing 50g of ascorbic acid as a first reducing agent, adding deionized water to prepare an ascorbic acid solution with the concentration of 2.0mol/L, keeping the temperature at 60 ℃, and standing for later use as a first reducing solution;
(2) 40g of formic acid is weighed as a second reducing agent and dissolved in xylene to ensure that the concentration of the solution is 0.15mol/L, and the solution is heated to 60 ℃ and kept as a second reducing solution for stand-by;
(3) Weighing 115g of silver nitrate, adding 427ml of deionized water and 44g of ammonia water to prepare silver-ammonia solution, keeping the temperature at 60 ℃ and keeping constant temperature as an oxidizing solution for standby;
(4) Weighing 125g of Tween-80 and 700g of hydroxyethylidene diphosphate as a dispersing agent, dissolving with 4800g of ethanol, keeping the temperature at 60 ℃, and standing for later use as a dispersion protection liquid;
(5) Mixing the second reducing solution and the dispersion protection solution, and after uniformly mixing, rapidly adding 10% of the prepared oxidizing solution for reaction for 20min; then the first reducing solution and the rest 90 percent of oxidizing solution are slowly added at the same time to continue the reaction, and the adding time is not less than 60 minutes; obtaining a reaction solution containing nano silver particles after the reaction is completed;
(6) Filtering the reaction solution containing the nano silver particles to separate the nano silver powder from the reaction waste liquid, and then using 2:1:0.5, adding ultrasonic auxiliary dispersion in the cleaning process, then centrifugally spin-drying, and crushing and grinding to obtain the nano silver powder 3.
The nano silver powder 2 prepared in the embodiment has D50=100 nm, tap density of 4.23g/cm3 and organic burning loss residue of 0.66 percent at 538 ℃; the scanning electron microscope analysis photograph of the nano silver powder 3 prepared by the embodiment is shown in fig. 3, the morphology of the obtained nano silver powder is similar to a sphere, the particle size distribution is uniform, the dispersibility is good, and most of particle size is concentrated between 70 nm and 150 nm.
Example 4
(1) Weighing 15kg of ascorbic acid as a first reducing agent, adding deionized water to prepare an ascorbic acid solution with the concentration of 1.6mol/L, keeping the temperature at 60 ℃, and standing for later use as a first reducing solution;
(2) Weighing 1.15kg of citric acid and 200g of sodium sulfite as a second reducing agent, dissolving into isopropanol to ensure that the concentration of the solution is 0.08mol/L, heating to 60 ℃ and keeping the temperature, and standing for later use as a second reducing solution;
(3) Weighing 35kg of silver nitrate, adding 128L of deionized water and 14kg of ammonia water to prepare silver-ammonia solution, and keeping the temperature at 60 ℃ for later use;
(4) Weighing 0.5g of oleic acid and 50g of polyethylene glycol as a dispersing agent, dissolving by adopting 200g of ethanol, keeping the temperature at 60 ℃, and standing for later use as a dispersion protection liquid;
(5) Mixing the second reducing solution and the dispersion protection solution, and after uniformly mixing, rapidly adding 25% of the prepared oxidizing solution for reaction for 10min; then the first reducing solution and the rest 75 percent of oxidizing solution are slowly added at the same time to continue the reaction, and the adding time is not less than 60 minutes; obtaining a reaction solution containing nano silver particles after the reaction is completed;
(6) Filtering the reaction solution containing the nano silver particles to separate the nano silver powder from the reaction waste liquid, and then using 1:1:0.5, adding ultrasonic auxiliary dispersion in the cleaning process, then centrifugally drying, freeze-drying and vacuum-drying, and crushing and grinding to obtain the nano silver powder 4.
D50=550 nm of the nano silver powder 4 prepared in the embodiment has tap density of 5.5g/cm < 3 >, and organic burning loss residue at 538 ℃ is 0.52%; the scanning electron microscope analysis photograph of the nano silver powder 4 prepared in the embodiment is shown in fig. 4, the morphology of the obtained nano silver powder is similar to a sphere, the particle size distribution is uniform, the dispersibility is good, and most of the particle size is concentrated between 400 nm and 600 nm.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the nano silver powder is characterized by comprising the following steps of:
dissolving or diluting a first reducing agent by deionized water to prepare a first reducing solution, and keeping the first temperature for standby;
step (2) dissolving or diluting a second reducing agent by adopting a second solvent to prepare a second reducing solution, and keeping the second temperature for standby;
step (3) dissolving soluble silver salt by deionized water and/or ammonia water to prepare an oxidizing solution, and keeping the third temperature for standby;
step (4) dissolving or diluting the dispersing agent by adopting a third solvent to prepare a dispersion protection liquid, and keeping the fourth temperature for standby;
step (5) mixing the first reducing solution, the second reducing solution, the oxidizing solution and the dispersion protection solution for reaction, and obtaining a reaction solution containing nano silver particles after the reaction is completed;
and (6) filtering and separating the reaction solution containing the nano silver particles to obtain nano silver particles, and then washing, separating, drying and grinding the nano silver particles to obtain the nano silver powder.
2. The method for preparing nano silver powder according to claim 1, wherein the first reducing agent in the step (1) is one or more of ascorbic acid, citric acid, citrate, formaldehyde, formic acid, glucose and hydrazine hydrate, the concentration of the first reducing solution is 0.2-3.0mol/L, and the first temperature is 20-80 ℃.
3. The method for preparing nano silver powder according to claim 2, wherein the second reducing agent in the step (2) is one or more of citric acid, citrate, formaldehyde, formic acid, glucose, hydrazine hydrate, sulfite, phosphorous acid, ferrous chloride, hydroxylamine, sodium borohydride, potassium borohydride and ethylene glycol, and the concentration of the second reducing solution is 0.01-1.0mol/L;
the second solvent is one or more of deionized water, ethanol, isopropanol, diethyl ether, ethylene glycol monobutyl ether, propylene oxide, hexane, cyclohexane, methyl acetate, ethyl acetate, toluene, xylene, acetone, methyl isobutyl ketone, tetrahydrofuran, pyridine and morpholine, and the second temperature is 20-200 ℃.
4. The method for preparing nano silver powder according to claim 1, wherein the soluble silver salt in the step (3) is one or more of silver nitrate, silver carbonate, silver fluoride and silver chlorate; the oxidation solution contains free silver ions and/or silver ammonia complex ions, the concentration of the silver ions in the oxidation solution is 0.5-2.0mol/L or the mass concentration of the silver ammonia complex ions is 30-150g/L, and the third temperature is 20-80 ℃.
5. The method for preparing nano silver powder according to claim 2, wherein the dispersing agent in the step (4) is one or more of sodium dodecyl sulfate, polyethylene glycol, gelatin, gum arabic, xanthan gum, oleic acid, oleamide, polyacrylamide, fatty acid with carbon number between 4 and 18, succinic acid, PVP-K30, PVP-K90, tween-40, tween-80, castor oil, ethylcellulose, methylcellulose, ethylenediamine tetramethylene phosphate, hydroxyethylidene diphosphate, aminotrimethylene phosphate; the amount of the dispersing agent is 0.1-50 times of the mass of silver salt in the oxidation liquid, and the third solvent is one or more of deionized water, ethanol, isopropanol, diethyl ether, ethylene glycol monobutyl ether, propylene oxide, hexane, cyclohexane, methyl acetate, ethyl acetate, toluene, xylene, acetone, methyl isobutyl ketone, tetrahydrofuran, pyridine and morpholine; the concentration of the dispersion protection liquid is 0.1-50g/L, and the fourth temperature is 20-200 ℃.
6. The method for preparing nano silver powder according to claim 2, wherein the mixing mode in the step (5) is as follows: firstly adding the oxidation solution into the dispersion protection solution, uniformly mixing, adding the second reduction solution for reaction, and then adding the first reduction solution for continuous reaction after the reaction is finished.
7. The method for preparing nano silver powder according to claim 1, wherein the mixing mode in the step (5) is as follows: and adding the second reducing solution into the dispersion protection solution, then adding part of the oxidizing solution for reaction, and after the reaction is finished, adding the first reducing solution and the rest of the oxidizing solution for continuous reaction.
8. The method for preparing nano silver powder according to claim 1, wherein the washing process in the step (6) is assisted by ultrasonic dispersion, and the washing liquid used in the washing process is one or more of deionized water, ammonia water, ethylenediamine, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, hexane, toluene, xylene, styrene, chloroform, acetone and methyl butanone.
9. The method for preparing nano silver powder according to claim 1, wherein the drying mode in the step (6) is one or more of vacuum drying, freeze drying and spray drying.
10. A nano silver powder, characterized in that the nano silver powder is obtained according to the method for producing a nano silver powder according to any one of claims 1 to 9.
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