CN101763911B - Preparation method of nanometer conductive carbon black suspension, battery anode and battery - Google Patents
Preparation method of nanometer conductive carbon black suspension, battery anode and battery Download PDFInfo
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- CN101763911B CN101763911B CN2008101894010A CN200810189401A CN101763911B CN 101763911 B CN101763911 B CN 101763911B CN 2008101894010 A CN2008101894010 A CN 2008101894010A CN 200810189401 A CN200810189401 A CN 200810189401A CN 101763911 B CN101763911 B CN 101763911B
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- China
- Prior art keywords
- carbon black
- conductive carbon
- weight
- nanometer conductive
- preparation
- Prior art date
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Links
- 239000000725 suspension Substances 0.000 title claims abstract description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000010008 shearing Methods 0.000 claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000002563 ionic surfactant Substances 0.000 claims description 11
- 238000005553 drilling Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920006243 acrylic copolymer Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 150000005846 sugar alcohols 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
- 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
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 229940049964 oleate Drugs 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000004062 sedimentation Methods 0.000 abstract description 5
- 239000000498 cooling water Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 11
- 235000019241 carbon black Nutrition 0.000 description 11
- -1 alkyl pyridine hydrochloride Chemical compound 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 159000000002 lithium salts Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000001294 alanine derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridine hydrochloride Substances [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for preparing a nanometer conductive carbon black suspension, comprising: adding nanometer conductive carbon black and surfactants into solvent to be stirred, shearing, dispersing and carrying out ltrasonic dispersion. The invention also provides a preparation method of an lithium ion battery anode and the preparation method of the lithium ion battery. The nanometer conductive carbon black suspension prepared with the method of the invention can be stably placed for more than 5 days at constant temperature without agglomeration or sedimentation. The volume and the cycle performance of the lithium ion battery prepared by the method of the invention are both improved.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer conductive carbon black suspension and the preparation method of lithium ion cell positive and lithium ion battery.
Background technology
Since sony corporation of japan since nineteen ninety begins commercialization and produces lithium ion battery; Lithium ion battery because have the energy density height, have extended cycle life, series of advantages such as open circuit voltage height, memory-less effect, safety non-pollution, be applied in widely on communication product such as mobile phone, notebook computer and the electronic product.Yet anode active material of lithium ion secondary battery is semi-conducting material, and its conductivity is very poor, and (its conductivity is generally all 10
-1-10
-7S/cm), directly application will make that the internal resistance of electrode is bigger, and depth of discharge is not enough, and the result causes the utilance of active material low, and the residual capacity of electrode is big, is unfavorable for giving full play to of battery performance.For improving between positive electrode active materials and the collector and the conductivity between the active particle, has good conductivity through in positive electrode, adding usually, density is little, the nanometer conductive carbon black of Stability Analysis of Structures and stable chemical performance improves the conductivity of active material.
The conductive agent particle is more little, and conductive capability is good more, therefore, in order to improve electric conductivity as much as possible, just must adopt the little nanometer carbon black of particle diameter as conductive agent as far as possible.As everyone knows, nano material has the surface energy of the specific area and the superelevation of super large, and agglomeration is remarkable unusually, and the more little agglomeration of particle diameter is obvious more, disperses more difficult.Disperse bad nanometer conductive carbon black not only can not bring into play its conducting function well, and restricted the raising of battery performance, for example, quicken the anode sizing agent caking, influence stability of slurry; Reduce the battery capacity performance; Reduce the cycle life of battery; Influence the consistency of the consistency of battery, particularly battery pack.
At present; Commercial production generally all adopts churned mechanically mode that conductive carbon black is disperseed; This method has limitation to the dispersion of conductive carbon black very much, is micrometer level such as being merely able to the aggregate depolymerization, secondary agglomeration will take place after shelving several hrs; And then flocculating setting, the sedimentation rate in a week reaches more than the 50 weight %.A large amount of experiments shows that the nanometer carbon black that does not disperse in the positive pole is the one of the main reasons that causes its poor stability; Therefore; A kind of preparation method of nanometer conductive carbon black of difficult generation sedimentation need be provided; With the stability of raising electrode slurry, and then the chemical property of raising battery, for example battery capacity, cycle performance etc.
Summary of the invention
The objective of the invention is to overcome the method for preparing nanometer conductive carbon black suspension in the prior art is difficult for nanometer carbon black is disperseed; And the shortcoming of secondary agglomeration takes place easily; Providing a kind of can and the method for preparing the high-dispersion nano conductive carbon black suspension of secondary agglomeration be difficult for take place with the nanometer conductive carbon black high degree of dispersion, and the lithium ion cell positive preparation method and the preparation method of lithium ion battery that use this method.
The invention provides a kind of preparation method of nanometer conductive carbon black suspension, wherein, this method comprises nanometer conductive carbon black and surfactant is joined in the solvent, stirs, and shears then and disperses and ultrasonic dispersing.
The present invention also provides a kind of preparation method of lithium ion cell positive; This method comprises positive active material, nanometer conductive carbon black suspension, adhesive and solvent, processes anode sizing agent, and anode sizing agent is coated on the plus plate current-collecting body; Dry; Roll or do not roll, wherein, said nanometer conductive carbon black suspension makes through the preparation method of nanometer conductive carbon black suspension provided by the invention.
The present invention also provides a kind of preparation method of lithium ion battery; This method comprises with anodal, barrier film and negative pole and prepares the electrode group; Then electrode group and electrolyte are sealed in the battery container, wherein, said positive pole makes through anode preparation method provided by the invention.
Use the nanometer conductive carbon black suspension of method of the present invention preparation stablize at normal temperatures to place more than 5 days and reunion or sedimentation do not take place.The capacity and the cycle performance of the lithium ion battery that the lithium ion cell positive that uses method of the present invention to prepare makes all are improved.
Embodiment
The preparation method of nanometer conductive carbon black suspension provided by the invention comprises nanometer conductive carbon black and surfactant is joined in the solvent, stirs, and shears then and disperses and ultrasonic dispersing.
According to method provided by the invention, wherein, said surfactant can be the various surfactants of routine.A preferred embodiment of the invention, said surfactant comprises nonionic surface active agent and ionic surfactant; Total weight with this surfactant is a benchmark, and the content of said nonionic surface active agent can be 60-90 weight %, is preferably 70-90 weight %, and the content of said ionic surfactant can be 10-40 weight %, is preferably 10-30 weight %.According to this preferred implementation; Not only change the pH value of suspension system through ionic surfactant; With the absolute value of increase dispersed particle surface Zeta potential, and then the surface charge density of raising particle, utilize electrostatic repulsion forces to prevent the secondary agglomeration of dispersed particle; And adopt of the coating of the non-ionic surfactant of long strand to the dispersed particle surface, utilize its space steric effect to improve the dispersed and stable of suspension.Wherein, said Zeta potential is that colloidal particle is dispersed in the system a kind of surface potential that forms naturally, it can the indicator particle between the size of repulsion ability each other, the absolute value of Zeta potential is big more, stability is good more.
Said nonionic surface active agent can be any nonionic surface active agent known in the field; Be preferably the nonionic surface active agent of polyalcohols, most preferably one or more in polyethylene glycol, polyvinyl alcohol, polyacrylamide and the polyvinylpyrrolidone.
Said ionic surfactant can be any ionic surfactant known in the field, for example, and cationic surfactant, anionic surfactant, amphoteric surfactant.Consideration from present cost of material and toxicity aspect is preferably anionic surfactant.Said cationic surfactant can be the derivative of machine amine, mainly contains quaternary ammonium salt, alkyl pyridine hydrochloride.Said anionic surfactant comprises, carboxylic acid and salt (RCOO thereof
-M
+), alkyl sulfate salt (ROSO
3 -M
+), alkyl phosphate salt (ROPO
3 -M
+), alkylsulfonate (RSO
3 -M
+); Optimization acid and salt thereof; One or more in citric acid, oleic acid, acrylamide and acrylic acid copolymer, propene sulfonic acid-different propene phosphoric acid-acrylic copolymer, alkene sulfonic acid-acrylic copolymer, maleic acid-butyl acrylate-acrylic copolymer, citrate and the oleate more preferably; Most preferably be in citric acid, oleic acid, citrate and the oleate one or more.Said citrate can be natrium citricum and/or potassium citrate; Said oleate can be enuatrol and/or potassium oleate.Said amphoteric surfactant comprises betaines [RN
+(CH
3) 2CH
2COO
-], alanine class (RN
+H
2CH
2CH
2COO
-), taurine class [RN
+(CH
3)
2(CH
2) 2SO
3-] and imidazolines.Above-mentioned these surfactants all can be through being purchased acquisition.
A kind of preferred embodiment in, the nonionic surface active agent of said polyalcohols is polyethylene glycol and/or polyvinylpyrrolidone; Anionic surfactant is citric acid and/or citrate, and the content of said nonionic surface active agent is 70-90 weight %, and the content of said ionic surfactant is 10-30 weight %.In this execution mode, it is particularly remarkable that method provided by the invention is improved the dispersive property of nanometer conductive carbon black.
Said nonionic surface active agent and ionic surfactant can be placed apart separately, also may be combined in together.
According to method provided by the invention; Wherein, Said solvent can be in N-methyl pyrrolidone, dimethyl formamide, DEF, dimethyl sulfoxide (DMSO), oxolane, water and the alcohol one or more; Be preferably in N-methyl pyrrolidone, oxolane and the alcohol one or more, more preferably the N-methyl pyrrolidone.
Total weight with said nanometer conductive carbon black suspension is a benchmark, and the content of said conductive carbon black can be 0.1-9.99 weight %, is preferably 0.5-6 weight %; The content of said surfactant can be 0.01-0.15 weight %, is preferably 0.015-0.1 weight %, and the content of said solvent can be preferably 95-99% for 90-99 weight %.
According to method provided by the invention, wherein, said shearing is separated into uses the shearing dispersion machine to disperse, and the condition of dispersion can comprise that the rotating speed of shearing dispersion machine is 1000-10000 rev/min, and the time of dispersion is 5-120 minute.According to of the present invention preferred embodiment a kind of, cause solvent evaporates in order to prevent that suspension heats up in the process that high speed shear is disperseed, can under the protection of recirculated cooling water, shear dispersion.
According to method provided by the invention, wherein, said ultrasonic dispersing is disperseed for using ultrasonic drilling machine, and the condition of dispersion can comprise that the frequency of ultrasonic drilling machine is the 50-200 kilohertz, and the time of dispersion is 20-180 minute.According to of the present invention preferred embodiment a kind of, cause solvent evaporates in order to prevent that suspension heats up in the process of ultrasonic dispersing, can under the protection of recirculated cooling water, carry out ultrasonic dispersing.
The preparation method of the lithium ion cell positive that the present invention also provides comprises positive active material, nanometer conductive carbon black suspension, adhesive and solvent; Process anode sizing agent; Anode sizing agent is coated on the plus plate current-collecting body, and drying is rolled or is not rolled; Wherein, said nanometer conductive carbon black suspension makes through the preparation method of nanometer conductive carbon black suspension provided by the invention.
The present invention can be the positive active material of conventional the embedded removal lithium embedded in this area, one or more in the preferred following material: Li to the not special restriction of said positive active material
xNi
1-yCoO
2, Li
1 + aM
bMn
2-bO
4, Li
mMn
2-nB
nO
2And LiFePO
4(wherein, 0.9≤x≤1.1,0≤y≤1.0;-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur; B is one or more in the transition metal, 0.9≤m≤1.1,0≤n≤1.0).
According to anode preparation method provided by the invention, wherein, the feasible weight with said positive active material of the consumption of said nanometer conductive carbon black suspension is benchmark, and the consumption of nanometer conductive carbon black is 1-15 weight %, is preferably 2-10 weight %.
Said adhesive can be used adhesive for the lithium ion cell positive of routine, is preferably in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and the butadiene-styrene rubber (SBR) one or more.Weight with positive active material is benchmark, and adhesive consumption can be 0.01-8 weight %, is preferably 0.02-5 weight %.
Said solvent can be for being used to prepare all kinds of solvents of lithium ion cell positive in the prior art, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), DEF (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of solvent can be coated on the said conducting base said positive electrode composition and gets final product.In general, it is 40-90 weight % that the consumption of solvent makes the content of positive active material in the slurry, is preferably 50-85 weight %.
Said plus plate current-collecting body can be plus plate current-collecting body known in those skilled in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
The temperature of said drying can be 80-150 ℃, and can be 2-10 hour drying time.The method of said calendering and condition are conventionally known to one of skill in the art.
The preparation method of the lithium ion battery that the present invention also provides comprises with anodal, barrier film and negative pole and prepares the electrode group, then electrode group and electrolyte is sealed in the battery container, and wherein, said positive pole makes through anode preparation method provided by the invention.
The preparation method of said negative pole can adopt conventional preparation method.For example, with negative material and solvent, be coated on the negative current collector, drying is rolled or is not rolled, and can obtain said negative pole.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Anticathode material of the present invention has no particular limits, and said negative material can comprise negative electrode active material and adhesive.
The not special restriction of said negative electrode active material; Can use the negative electrode active material that disengages lithium that embeds of this area routine; Material with carbon element for example, said material with carbon element be selected from non-graphitized charcoal, graphite or the charcoal that obtains through high-temperature oxydation by polyyne family macromolecule material or pyrolytic carbon, coke, organic polymer sinter, active carbon in one or more.Said organic polymer sinter can be through with products therefrom after sintering such as phenolic resins, epoxy resin and the charing.
The kind of said negative pole binding agent and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR) and the sodium carboxymethylcellulose (CMC).In general, according to the difference of used binding agent kind, be benchmark with the weight of negative electrode active material, the consumption of negative pole binding agent can be 0.005-8 weight %, is preferably 0.008-5 weight %.
Said negative current collector can adopt the various collectors that are used for lithium ion battery negative in the prior art, like stamped metal, metal forming, net metal and foamed metal, and preferred Copper Foil.
Said negative material can also comprise that conductive agent to increase the conductivity of electrode, reduces the internal resistance of cell.The not special restriction of said conductive agent can be the conventional cathode conductive agent in this area, for example one or more in carbon black, nickel powder, the copper powder.Weight with negative electrode active material is benchmark, and the content of said conductive agent can be 0-12 weight %, is preferably 0.1-3 weight %.
According to the preparation method of lithium ion battery provided by the invention, said membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability ability.Said membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium ion battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
According to the preparation method of lithium ion battery provided by the invention, said electrolyte can be the electrolyte of various routines, for example nonaqueous electrolytic solution.Said nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.The concentration of said lithium salts in electrolyte can be the 0.3-4 mol, is preferably the 0.5-2 mol.
According to the preparation method of lithium ion battery provided by the invention, the method for packing of this battery is as well known to those skilled in the art, in general, comprises the electrode group is inserted in the battery case, adds electrolyte, and sealing obtains lithium ion battery then.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.
Below, will carry out detailed description to the present invention through embodiment.
Embodiment 1
Present embodiment is used to explain the preparation method of nanometer conductive carbon black suspension provided by the invention.
(1) be to mix at 4: 1 polyethylene glycol (molecular weight 2000, Chemical Reagent Co., Ltd., Sinopharm Group) and citric acid (Shanghai Ling Feng chemical reagent Co., Ltd) according to weight ratio.With 0.03 restrain mixture join in the 199 gram N-methyl pyrrolidones, add 1 gram nanometer conductive carbon black (special close high HC2 type) then.
(2) under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) suspension that step (1) obtains is sheared dispersion 30 minutes with the rotating speed of 5000r/min.
(3) under the condition of recirculated cooling water protection; (go up Umihiko ultrasonic instrument Co., Ltd with ultrasonic drilling machine; Model: the ultrasonic dispersion of suspension that LUCKY) step (2) is obtained with the frequency of 100KHz 120 minutes, can make nanometer conductive carbon black suspension of the present invention, note is made A1.
Embodiment 2
Present embodiment is used to explain the preparation method of nanometer conductive carbon black suspension provided by the invention.
(1) with 4 gram nanometer conductive carbon blacks (special close high SP type), 0.08 gram polyvinylpyrrolidone (K17; Jiaozhuo Mei Da Fine Chemical Co., Ltd), 0.03 gram citric acid (Shanghai Ling Feng chemical reagent Co., Ltd) and 196 restrains the N-methyl pyrrolidones and mixes, and is made into suspension.
(2) under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) suspension that step (1) obtains is sheared dispersion 30 minutes with the rotating speed of 4000r/min.
(3) under the condition of recirculated cooling water protection; (go up Umihiko ultrasonic instrument Co., Ltd with ultrasonic drilling machine; Model: the ultrasonic dispersion of suspension that LUCKY) step (2) is obtained with the frequency of 80KHz 90 minutes, can make nanometer conductive carbon black suspension of the present invention, note is made A2.
Embodiment 3
Present embodiment is used to explain the preparation method of nanometer conductive carbon black suspension provided by the invention.
(1) with 6 gram nanometer conductive carbon blacks (special close high AB type), 0.06 gram polyvinyl alcohol (model: 1799; Chongqing chemical reagent factory), 0.06 gram polyvinylpyrrolidone (K17; Jiaozhuo Mei Da Fine Chemical Co., Ltd), 0.08 gram triethanolamine (Guangzhou Chemical Reagent Factory) and 194 restrains the N-methyl pyrrolidones and mixes, and is made into suspension.
(2) under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) suspension that step (1) obtains is sheared dispersion 100 minutes with the rotating speed of 2000r/min.
(3) under the condition of recirculated cooling water protection; (go up Umihiko ultrasonic instrument Co., Ltd with ultrasonic drilling machine; Model: the ultrasonic dispersion of suspension that LUCKY) step (2) is obtained with the frequency of 90KHz 100 minutes, can make nanometer conductive carbon black suspension of the present invention, note is made A3.
Embodiment 4
Present embodiment is used to explain the preparation method of nanometer conductive carbon black suspension provided by the invention.
(1) with 3 gram nanometer conductive carbon blacks (special close high SP type), 0.03 gram polyvinyl alcohol (model: 1799; Chongqing chemical reagent factory), 0.03 gram polyacrylamide (model: AN1; Jiangsu China silicon ceramic technology Co., Ltd), 0.03 gram acrylamide and acrylic acid copolymer (model: AM1; Jiangsu China silicon ceramic technology Co., Ltd), 0.01 gram oleic acid (Guangzhou Chemical Reagent Factory) and 197 restrains the N-methyl pyrrolidones and mixes, and is made into suspension.
(2) under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) suspension that step (1) obtains is sheared dispersion 10 minutes with the rotating speed of 9000r/min.
(3) under the condition of recirculated cooling water protection; (go up Umihiko ultrasonic instrument Co., Ltd with ultrasonic drilling machine; Model: the ultrasonic dispersion of suspension that LUCKY) step (2) is obtained with the frequency of 150KHz 40 minutes, can make high-dispersion nano conductive carbon black suspension of the present invention, note is made A4.
Embodiment 5
Present embodiment is used to explain the preparation method of nanometer conductive carbon black suspension provided by the invention.
(1) 3 gram nanometer conductive carbon blacks (special close high SP type), 0.12 gram citric acid (Shanghai Ling Feng chemical reagent Co., Ltd) and 197 gram N-methyl pyrrolidones are mixed, be made into suspension.
(2) under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) suspension that step (1) obtains is sheared dispersion 10 minutes with the rotating speed of 9000r/min.
(3) under the condition of recirculated cooling water protection; (go up Umihiko ultrasonic instrument Co., Ltd with ultrasonic drilling machine; Model: the ultrasonic dispersion of suspension that LUCKY) step (2) is obtained with the frequency of 150KHz 40 minutes, can make high-dispersion nano conductive carbon black suspension of the present invention, note is made A5.
Embodiment 6
Present embodiment is used to explain the preparation method of nanometer conductive carbon black suspension provided by the invention.
(1) 3 gram nanometer conductive carbon blacks (special close high SP type), 0.03 gram polyethylene glycol (molecular weight 2000, Chemical Reagent Co., Ltd., Sinopharm Group) and 194 gram N-methyl pyrrolidones are mixed, be made into suspension.
(2) under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) suspension that step (1) obtains is sheared dispersion 30 minutes with the rotating speed of 5000r/min.
(3) under the condition of recirculated cooling water protection; (go up Umihiko ultrasonic instrument Co., Ltd with ultrasonic drilling machine; Model: the ultrasonic dispersion of suspension that LUCKY) step (2) is obtained with the frequency of 100KHz 120 minutes, can make nanometer conductive carbon black suspension of the present invention, note is made A6.
Embodiment 7-12
Embodiment 7-12 is used to explain the preparation method of lithium ion cell positive provided by the invention.
With LiFePO
4, the high-dispersion nano conductive carbon black suspension that makes with embodiment 1-6 respectively of PVDF is by weight being to mix at 100: 5: 100, processes anode sizing agent.This anode sizing agent is coated in two surfaces that thickness is 16 microns aluminium foil equably.Under 90 ℃, dry, roll, rolling cut becomes positive plate, pole piece is of a size of 48.5cm (length) * 4.4cm (wide) * 0.015cm (thickness), LiFePO
4Content is 5.5 grams, and note is made B1-B6 respectively.
Embodiment 13-18
Embodiment 13-18 is used to explain the preparation method of lithium ion battery provided by the invention.
Negative pole: is that 100: 4: 1.6 waters mix with Delanium, CMC and SBR according to weight ratio, makes cathode size, and this cathode size is coated in two surfaces that thickness is 12 microns Copper Foil equably.90 ℃ of oven dry down, roll, rolling cut becomes negative plate, and pole piece is of a size of 48cm (length) * 4.5cm (wide) * 0.01cm (thickness), and negative electrode active material graphite weighs 2.5 grams.
Barrier film: the PE film that adopts 20 micron thick.
The lithium-ion electric core of the positive pole that respectively embodiment 7-12 is made, the above-mentioned negative pole that makes and a square of membrane coil coiled also is received in the rectangular cell shell, injects 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, the lithium ion battery of 053450 type is processed in sealing, and note is made D1-D6 respectively.
Comparative Examples 1
This Comparative Examples is used to explain the preparation method of existing nanometer conductive carbon black suspension.
6 gram nanometer conductive carbon blacks (special close high AB type) and 194 gram n-formyl sarcolysine base pyrrolidones are made into suspension.Under the condition of recirculated cooling water protection, with shear dispersion machine (producer: FLUKO, model: ULTRA50NIC) will prewired suspension dispersed with stirring 120 minutes, rotating speed is 2500r/min, makes nanometer conductive carbon black suspension, remembers and makes C1.
Comparative Examples 2
This Comparative Examples is used to explain the preparation method of existing nanometer conductive carbon black suspension.
3 gram nanometer conductive carbon blacks (special close high SP type) and 197 gram n-formyl sarcolysine base pyrrolidones are made into suspension.Under the condition of recirculated cooling water protection, with shearing dispersion machine (producer: FLUKO, model: ULTRA50NIC) the above-mentioned suspension of step is sheared dispersion 30 minutes with the rotating speed of 5000r/min., making nanometer conductive carbon black suspension, note is made C2.
Comparative Examples 3 and 4
Comparative Examples 3 and 4 is used to explain the preparation method of existing lithium ion cell positive.
Method according to identical with embodiment 7-12 prepares lithium ion cell positive; Different is; Replace the high-dispersion nano conductive carbon black suspension of embodiment 1-6 preparation, the positive pole that makes to remember respectively with the nanometer conductive carbon black suspension of Comparative Examples 1 and 2 preparations and make E1 and E2.
Comparative Examples 5 and 6
To preparing lithium ion battery according to the method identical with embodiment 13-18, different is, replaces the lithium ion cell positive of embodiment 7-12 preparation, the lithium ion battery that makes to remember respectively with the lithium ion cell positive of Comparative Examples 3 and 4 preparations and makes F1 and F2.
The dispersive property of nanometer conductive carbon black suspension
Just the suspension that makes of embodiment 1-6 and Comparative Examples 1-2 is placed at normal temperatures.The time that deposition in above-mentioned suspension, occurs is as shown in table 1; The percentage of gained deposition is through sucking-off upper strata suspension at first; Sediment was obtained solid matter down in dry 2 hours at 150 ℃, and the ratio of the solid matter of calculating gained and the total amount of nanometer conductive carbon black draws.
Table 1
Battery performance test
1, the test of capacity
Under the room temperature, the battery that embodiment 1-6 and Comparative Examples 1-2 are made is respectively with 1C current charges to 4.2 volt, and after voltage rose to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current was 0.05C, shelved 5 minutes; Then battery is lied prostrate with 1C current discharge to 3.0 respectively, obtain the capacity of battery normal temperature 1C current discharge to 3.0 volt.The result who records is listed in the table 2.
2, the mensuration of cycle performance
Under 45 ℃; The battery that embodiment 1-6 and Comparative Examples 1-2 are made is respectively with 1C current charges to 4.2 volt, after voltage rises to 4.2 volts, with 4.2 volts of constant-potential charges; Cut-off current is 0.05C; Shelved 5 minutes, and then battery was lied prostrate with 1C current discharge to 3.0 respectively, write down the discharge capacity of each battery respectively; Repeat the above-mentioned step that discharges and recharges then.Said cycle-index is the number of times that capacitance drops to circulation in 80% o'clock of initial capacity, and the result who records is listed in the table 2.
Table 2
| Conductive agent | Anodal numbering | The battery numbering | 1C discharge capacity (MAH) | Capability retention (%) after the 1C circulation 1000 times |
| A1 | B1 | D1 | 710 | 95％ |
| A2 | B2 | D2 | 700 | 92％ |
| A3 | B3 | D3 | 695 | 92％ |
| A4 | B4 | D4 | 702 | 93％ |
| A5 | B5 | D5 | 686 | 90％ |
| A6 | B6 | D6 | 681 | 89％ |
| C1 | E1 | F1 | 650 | 82％ |
| C2 | E2 | F2 | 656 | 80％ |
Can find out through the data in table 1 and the table 2, use the nanometer conductive carbon black suspension of method of the present invention preparation stablize at normal temperatures to place more than 5 days and reunion or sedimentation do not take place.The capacity and the cycle performance of the lithium ion battery that the lithium ion cell positive that uses method of the present invention to prepare makes all are improved.
Claims (9)
1. the preparation method of a nanometer conductive carbon black suspension; It is characterized in that; This method comprises nanometer conductive carbon black and surfactant is joined in the solvent; Stir, shear then and disperse and ultrasonic dispersing, said surfactant comprises nonionic surface active agent and ionic surfactant; Total weight with this surfactant is a benchmark, and the content of said nonionic surface active agent is 60-90 weight %, and the content of said ionic surfactant is 10-40 weight %.
2. method according to claim 1 wherein, is a benchmark with the total weight of said nanometer conductive carbon black suspension, and the content of said nanometer conductive carbon black is 0.1-9.99 weight %; The content of said surfactant is 0.01-0.015 weight %, and the content of said solvent is 90-99 weight %.
3. method according to claim 1, wherein, said nonionic surface active agent is the nonionic surface active agent of polyalcohols; Said ionic surfactant is an anionic surfactant.
4. method according to claim 3, wherein, the nonionic surface active agent of said polyalcohols is one or more in polyethylene glycol, polyvinyl alcohol, polyacrylamide and the polyvinylpyrrolidone; Said anionic surfactant is one or more in citric acid, oleic acid, acrylamide and acrylic acid copolymer, propene sulfonic acid-different propene phosphoric acid-acrylic copolymer, alkene sulfonic acid-acrylic copolymer, maleic acid-butyl acrylate-acrylic copolymer, citrate and the oleate.
5. according to claim 3 or 4 described methods, wherein, the nonionic surface active agent of said polyalcohols is polyethylene glycol and/or polyvinylpyrrolidone; Said anionic surfactant is citric acid and/or citrate, and the content of said nonionic surface active agent is 70-90 weight %, and the content of said ionic surfactant is 10-30 weight %.
6. method according to claim 1, wherein, said solvent is one or more in N-methyl pyrrolidone, dimethyl formamide, DEF, dimethyl sulfoxide (DMSO), oxolane, water and the alcohol.
7. method according to claim 1, wherein, said shearing is separated into uses the shearing dispersion machine to disperse, and the condition of dispersion comprises that the rotating speed of shearing dispersion machine is 1000-10000 rev/min, and the time of dispersion is 5-120 minute; Said ultrasonic dispersing is disperseed for using ultrasonic drilling machine, and the condition of dispersion comprises that the frequency of ultrasonic drilling machine is the 50-200 kilohertz, and the time of dispersion is 20-180 minute.
8. the preparation method of a lithium ion cell positive; This method comprises positive active material, nanometer conductive carbon black suspension, adhesive and solvent, processes anode sizing agent, and anode sizing agent is coated on the plus plate current-collecting body; Dry; Roll or do not roll, it is characterized in that said nanometer conductive carbon black suspension makes through any described method among the claim 1-7.
9. the preparation method of a lithium ion battery, this method comprise with anodal, barrier film and negative pole and prepare the electrode group, then electrode group and electrolyte are sealed in the battery container, it is characterized in that said positive pole makes through the described method of claim 8.
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| CN104868125B (en) * | 2015-04-21 | 2017-03-22 | 深圳市三顺中科新材料有限公司 | Carbon nano tube and carbon black composite dispersing liquid and preparation method thereof |
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| CN1349669A (en) * | 1999-03-23 | 2002-05-15 | 化合价技术股份有限公司 | Lithium-containing phosphate active materials |
| CN101154038A (en) * | 2006-09-29 | 2008-04-02 | 富士胶片株式会社 | Curing colouration composition, color filtering device and liquid crystal display using the color filtering device |
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| CN1349669A (en) * | 1999-03-23 | 2002-05-15 | 化合价技术股份有限公司 | Lithium-containing phosphate active materials |
| CN101154038A (en) * | 2006-09-29 | 2008-04-02 | 富士胶片株式会社 | Curing colouration composition, color filtering device and liquid crystal display using the color filtering device |
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