CN109638252A - Dissaving polymer electrode active material and preparation method thereof - Google Patents
Dissaving polymer electrode active material and preparation method thereof Download PDFInfo
- Publication number
- CN109638252A CN109638252A CN201811534442.9A CN201811534442A CN109638252A CN 109638252 A CN109638252 A CN 109638252A CN 201811534442 A CN201811534442 A CN 201811534442A CN 109638252 A CN109638252 A CN 109638252A
- Authority
- CN
- China
- Prior art keywords
- dissaving polymer
- electrode active
- active material
- carbon
- preparation
- 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
- 239000007772 electrode material Substances 0.000 title claims abstract description 61
- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- 239000002861 polymer material Substances 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229920002396 Polyurea Polymers 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- -1 siloxane polyol Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical class N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- IOQPXSWSBADKKW-UHFFFAOYSA-N CC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.N=C=O.N=C=O.N=C=O.N=C=O IOQPXSWSBADKKW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 235000019766 L-Lysine Nutrition 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 229940031098 ethanolamine Drugs 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- RJDVGKCBHFINOK-UHFFFAOYSA-N tris(2-methylphenoxy)-sulfanylidene-$l^{5}-phosphane Chemical group CC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RJDVGKCBHFINOK-UHFFFAOYSA-N 0.000 claims description 2
- 229960000281 trometamol Drugs 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 claims 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XCGWUIXOGKKOEY-UHFFFAOYSA-N (carbamoylamino) carbamate Chemical compound NC(=O)NOC(N)=O XCGWUIXOGKKOEY-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides dissaving polymer electrode active material and preparation method, the dissaving polymer electrode active material is pure branched polymer material or dissaving polymer/carbon composite, and dissaving polymer/carbon composite is that pure dissaving polymer is combined with carbon nanomaterial.Preparation method includes: that multicomponent isocyanate, material I, solvent are mixed the pure branched polymer material for being reacted to obtain as electrode active material；Or multicomponent isocyanate, material I, carbon nanomaterial, solvent are mixed to the dissaving polymer/carbon composite for being reacted to obtain as electrode active material, wherein material I is polyamine, polyalcohol, any one in polyhydric alcohol amine.The present invention prepares dissaving polymer and its composite material with good chemical property, and the dissaving polymer for keeping tradition low value-added can be used as the electrode active material of the metal ions battery such as lithium, sodium, and energy electrode material cost is effectively reduced.
Description
Technical field
The invention belongs to electrode material fields, and in particular to a kind of dissaving polymer electrode active material and its preparation side
Method.
Background technique
With the continuous development of society, energy demand is also increasing, and energy problem becomes the focus of social concerns instantly.
However, the non-renewable fossil energy such as coal, petroleum, natural gas largely uses, resource is petered out, while also having been caused complete
The serious environmental problem such as ball greenhouse effects.The clean energy resourcies such as solar energy, tide energy, wind energy are increasingly becoming Present Global energy knot
The important component of structure.Efficiently energy storage device is the storage for improving clean energy resource for lithium/sodium-ion battery and supercapacitor etc.
With the key of utilization efficiency, the performance of lithium-ion electric pool equipment is heavily dependent on the property of internal electrode material, and mesh
Preceding lithium/sodium ion battery electrode material is mainly carbon material (graphite etc.) and containing transition metal oxide (LiFePO4 etc.) two classes
Inorganic electrode material.Since the mineral resources such as graphite and transition metal oxide belong to nonrenewable resources, reserves are limited, because
This, the reproducible electrode material of Development of Novel is beneficial to the health of using energy source, sustainable development.
Organic electrode materials have renewable, various structures, can design, is cheap, environmental-friendly and good processing
Property the advantages that, be expected to develop " green " lithium/sodium-ion battery of new generation.Conventional organic pole material in lithium/sodium-ion battery at present
It is conjugated compound that material is most of, such as the organic carbonyl compound containing big conjugated system, passes through the disconnected of carbonyl C=O bond
It splits and constitutes a charge and discharge process with reconstruction, and conjugated system structure does not change, and the electricity for being conjugated big pi bond only has occurred
Sub- cloud is reset, and preferable chemical property is also therefore shown.Organic electrode materials are as a kind of emerging electrochemical energy storage
Material becomes the research hotspot of the organic positive electrodes of metal ions battery such as lithium, sodium.
Before this, unconjugated organic material is from electrode material is not used as, one is because being free of conventional organic pole material
Conjugated structure in material.Second, non-conjugated material is a kind of electrical insulator.Meanwhile usually linear organic polymer exists largely
Entanglement, porosity is low, is easy to happen crystallization, and glass transition temperature is higher, these features make its in electrochemical reaction process from
The transmission and diffusion rate of son are slower, and the utilization rate of ionic conductivity and electroactive material is lower, and then leads to high score sub-electrode
The high rate performance of material, specific capacity are lower, limit its commercial applications.In addition, organic electrode materials there is also charging slowly,
Property is unstable, the problems such as short that are easy to be dissolved in electrolyte, cycle life.
Summary of the invention
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide having good high rate performance and circulation steady
The dissaving polymer electrode active material and preparation method thereof of qualitative energy.
The present invention to achieve the goals above, uses following scheme:
<electrode active material>
The present invention provides dissaving polymer electrode active material, it is characterised in that: dissaving polymer electrode activity material
Material is pure branched polymer material or dissaving polymer/carbon composite, and dissaving polymer/carbon composite is pure super
Branched polymer is combined with carbon nanomaterial.
Preferably, dissaving polymer electrode active material provided by the invention, can also have the feature that pure over-expense
Fluidized polymer material is at least one of hyperbranched polyureas, super branched polyurethane and hyperbranched poly (urea-urethane).
Preferably, dissaving polymer electrode active material provided by the invention, can also have the feature that hyperbranched
Polyureas is reacted to obtain by multicomponent isocyanate with polyamine, such as:
；Super branched polyurethane is obtained by multicomponent isocyanate and polyol reaction, such as:
Hyperbranched poly (urea-urethane) is reacted to obtain by multicomponent isocyanate with polyhydric alcohol amine, such as:
Preferably, dissaving polymer electrode active material provided by the invention can also have the feature that wherein,
Multicomponent isocyanate is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), 1,6- hexa-methylene two are different
Cyanate (HDI), 4,4'- dicyclohexyl methyl hydride diisocyanate (HMDI), hydrogenation methylenebis phenyl isocyanate (H12MDI),
1,5- naphthalene diisocyanate, trimethyl -1,6- hexamethylene diisocyanate (TMHDI), isophorone diisocyanate
(IPDI), 4,4', 4 " triphenylmethane triisocyanates (TPMDI), tri o cresyl thiophosphate phenyl isocyanate, L-lysine three are different
Any one in cyanate, methyl triphenyl methane tetraisocyanate, polyamine be ethylenediamine, propane diamine, hexamethylene diamine, to benzene
Diamines, benzidine, melamine, bis- (hexa-methylene) triamines, triethylene tetramine, N- (2- amido ethyl) -1,3- propane diamine
At least one of, polyalcohol is ethylene glycol, 1,4-butanediol, propylene glycol, neopentyl glycol, polyethylene glycol, polytetrahydrofuran two
Alcohol, glycerine, trimethylolpropane, triethanolamine, trimethylolethane, pentaerythrite, dipentaerythritol, vegetable oil are polynary
At least one of alcohol, polyether polyol, polyester polyol, siloxane polyol, polyetherdiol, polycarbonate glycol, it is polynary
Hydramine be for containing an amino and one (or more) compound of hydroxyl, specially diethanol amine, ethanol amine, trihydroxy methyl
Aminomethane, bis- (2- methylols) amino-three (methylol) methane, tromethamine, -2 ethyl -1,3- propylene glycol of 2- amino, two
At least one of isopropanolamine.
Preferably, dissaving polymer electrode active material provided by the invention can also have the feature that carbon nanometer
Material is at least one of graphene, expanded graphite, acetylene black, carbon nanotube, active carbon, carbon fiber, carbon aerogels.
Preferably, dissaving polymer electrode active material provided by the invention can also have the feature that hyperbranched
In polymer/carbon composite electrode material, the mass percent of carbon nanomaterial is 1~30%.
<preparation method>
The present invention also provides the preparation methods of dissaving polymer electrode active material, it is characterised in that: by polynary isocyanide
Acid esters, material I, solvent mix the pure branched polymer material for being reacted to obtain as electrode active material；Or it will
Multicomponent isocyanate, material I, carbon nanomaterial, solvent, which mix, to be reacted to obtain as the hyperbranched of electrode active material
Polymer/carbon composite, wherein material I is polyamine, polyalcohol, any one in polyhydric alcohol amine.
Preferably, the preparation method of dissaving polymer electrode active material provided by the invention can also have following spy
Sign: the preparation method of pure branched polymer material specifically: multicomponent isocyanate is added to 5~30min of ultrasound in solvent
To be uniformly dispersed, it is then slowly added into material I, reacts 1~12h at -10~30 DEG C under magnetic stirring；Then 50 are warming up to
~120 DEG C, the reaction was continued 6~48h；Entire reaction carries out in nitrogen or argon atmosphere；Reactant is imported after completion of the reaction
It fills and is precipitated in the beaker of a large amount of water, it is dry after filtering, washing.Dissaving polymer/carbon composite preparation method is specific
Are as follows: carbon nanomaterial is placed in acid with strong oxidizing property, handles 4 at 30~100 DEG C~for 24 hours, it is rear washing, dry；It then will be sour
Change that treated that carbon nanomaterial 10~120min of ultrasound in solvent makes it be uniformly dispersed, addition multicomponent isocyanate simultaneously continues
5~30min of ultrasound then reacts 1~12h to be uniformly mixed at -10~30 DEG C under magnetic stirring；It is slowly added to material I,
The reaction was continued 1~12h；50~120 DEG C are then heated to, the reaction was continued 6~for 24 hours；Entire reaction is in nitrogen or argon atmosphere
It carries out；Reactant is imported in the beaker for filling a large amount of water after completion of the reaction and is precipitated, it is dry after filtering, washing.
Preferably, the preparation method of dissaving polymer electrode active material provided by the invention can also have following spy
Sign: at least one of the acid with strong oxidizing property concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide, potassium permanganate, potassium peroxydisulfate, solvent are N- methyl
At least one of pyrrolidones, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride, 1,4- dioxane.
Preferably, the preparation method of dissaving polymer electrode active material provided by the invention can also have following spy
Sign: being additionally added initiator while material I is added or auxiliary agent participates in reaction, contains isocyanate groups and alkene in auxiliary molecules
Base unsaturated group, structural formula are as follows:Such as:
The action and effect of invention
The present invention has prepared can be as the dissaving polymer of lithium/sodium-ion battery electrode active material and its multiple
Condensation material, the dissaving polymer for keeping tradition low value-added can be applied to green energy resource field, and effectively reducing can source electrode
The cost of material reduces the use of the non-renewable mineral resources such as transition metal oxide, is conducive to holding for energy and environment
Supervention exhibition.
Importantly, there are a large amount of cavities at the branch point of dissaving polymer, unique three-D space structure makes it
With low viscosity, good iontophoresis, the transmission rate of ion in the electrodes can be significantly improved, to improve lithium/sodium
The high rate performance and specific capacity of ion battery.In addition, introducing oxygen-containing functional group on its surface by acidification carbon nanomaterial
(such as hydroxyl) can react with isocyanates, improve dissaving polymer in the load capacity and phase on carbon nanomaterial surface
Interaction, and then improve the electron conduction of dissaving polymer and the high rate performance of battery, while inhibiting macromolecule in charge and discharge
Volume change in electric process effectively promotes the cyclical stability of material.In addition, crosslinking or hole can be formed by introducing auxiliary agent
Hole structure can effectively promote the utilization efficiency and cyclical stability of active material.
Detailed description of the invention
Fig. 1 is cyclic voltammetric (CV) figure of hyperbranched poly (urea-urethane) electrode material prepared in embodiment one；
Fig. 2 is constant current charge-discharge (GCD) curve of hyperbranched poly (urea-urethane) electrode material prepared in embodiment one
Figure；
Fig. 3 is the high rate performance curve graph of hyperbranched poly (urea-urethane) electrode material prepared in embodiment one；
Fig. 4 is the cyclical stability curve graph of hyperbranched poly (urea-urethane) electrode material prepared in embodiment one.
Specific embodiment
It is carried out below in conjunction with specific embodiment of the attached drawing to dissaving polymer electrode active material of the present invention
It explains in detail.
It is hyperbranched poly (urea-urethane) electrode active material and preparation method thereof in the present embodiment one.
Preparation method:
1) it weighs 3.48g toluene di-isocyanate(TDI) (TDI) to be dissolved in 40mL n,N-Dimethylformamide (DMF), ultrasound
Disperse 20min.In addition it weighs 2.10g diethanol amine (DEOA) to be dissolved in 25mL DMF, ultrasonic disperse 5min.
2) DEOA solution is slowly dropped in TDI solution, in 0 DEG C of reaction 12h under mechanical stirring, then heats to 50 DEG C
Successive reaction 48h, entire reaction carry out in nitrogen or argon atmosphere.
3) reaction mixture is directly poured into the beaker for containing a large amount of water and is precipitated, sediment filtered, then in vacuum
It is dried in vacuo in drying box, drying temperature is 80 DEG C, drying time 12h, and the pure hyperbranched poly (urea-of white is obtained after dry
Urethane).
Performance characterization:
Resulting pure hyperbranched poly (urea-urethane) a series of electrochemical property tests are subjected to, by the cyclic voltammetric of Fig. 1
(CV) figure, which can be seen that, carries out cyclic voltammetry in 0.01V~2.5V voltage window, in 0.32V when material first lap discharges
Place forms SEI film, reduction peak and oxidation peak occurs respectively in 0.8V and 1V voltage location.
It can be seen that from the constant current charge-discharge curve graph of Fig. 2, first three the circle charge and discharge of material under 100mA/g current density are bent
Line, platform appearance position is also substantially corresponding with CV curve, and first circle specific discharge capacity reaches 168.5mAh/g.
Find out from the test of the high rate performance of Fig. 3, when current density is respectively 20,40,80,100,200,400mA/g
Specific discharge capacity slowly reduces, and as current density 400mA/g, specific discharge capacity still has 95mAh/g or more, opposite 20mA/g electricity
When current density, capacity retention ratio is up to 78.4%.
From the stable circulation linearity curve of Fig. 4 it can be seen that the specific volume that discharges after 110 circle of circulation under 100mA/g current density
Amount still has 142.6mAh/g, and conservation rate embodies very excellent stable circulation performance up to 84.6%.
<embodiment two>
It is super branched polyurethane electrode active material and preparation method thereof in the present embodiment two.
Preparation method:
1) it weighs 4,4', 4 " triphenylmethane triisocyanate (TPMDI) of 7.34g and is dissolved in 100mL N, N- dimethyl
In formamide (DMF), ultrasonic disperse 30min.In addition it weighs 2.28g 1,3-PD and is dissolved in 25mL DMF, ultrasound point
Dissipate 15min.
2) propylene glycol solution is slowly dropped in TPMDI solution, under mechanical stirring for 24 hours in 0 DEG C of reaction, is then heated to
60 DEG C of successive reaction 36h, entire reaction carry out in nitrogen or argon atmosphere.
3) 0.65g is weighedIt is dissolved in the DMF solvent of 20mL as auxiliary agent, is added drop-wise to
In solution described in step 2,60 DEG C of reaction 12h are warming up to 80 DEG C, the reaction was continued for 24 hours, and olefin end group is made to crosslink reaction.
4) reaction mixture is directly poured into the beaker for containing a large amount of water and is precipitated, sediment filtered, then in vacuum
It is dried in vacuo in drying box, drying temperature is 80 DEG C, drying time 12h, and the pure hyperbranched poly (urea-of white is obtained after dry
Urethane).
<embodiment three>
It is carbon nanotube/hyperbranched polyureas composite electrode active material and preparation method thereof in the present embodiment three.
Preparation method:
1) 1.0g carbon nanotube is weighed, is dispersed in the 200mL concentrated sulfuric acid/concentrated nitric acid (V/V=3/1), at 50 DEG C of ultrasounds
Reason for 24 hours, is gradually diluted with 400mL deionized water after being cooled to room temperature, is then filtered, washed to neutrality, and vacuum is dry at 100 DEG C
It is dry, obtain acidification carbon nanotube.
2) above-mentioned acidification carbon nanotube 0.1g is weighed, is dispersed in 10mL N-Methyl pyrrolidone (NMP), ultrasonic disperse
10min is added dropwise under nitrogen protection in the nmp solution of 40mL TDI containing 3.48g, ultrasonic disperse 5min, in 20 DEG C under magnetic agitation
Lower reaction 10h.
3) it in addition weighs 2.5g melamine to be dissolved in 25mL NMP, ultrasonic disperse 10min.Melamine solution is delayed
Slowly it is added drop-wise in carbon nanotube/TDI mixed solution, in 10 DEG C of reaction 12h under mechanical stirring, then heats to 60 DEG C of successive reactions
36h, entire reaction carry out in nitrogen or argon atmosphere.
4) reaction mixture is directly poured into the beaker for containing a large amount of water and is precipitated, sediment is filtered, washed repeatedly with NMP
It washs, is then dried in vacuo in a vacuum drying oven, drying temperature is 80 DEG C, drying time 12h, and the super of grey is obtained after dry
Branching polyureas/carbon nano-tube combination electrode active material.
<example IV>
It is poly- (urea-urethane)/carbon nano-tube combination electrode active material and preparation method thereof in the present embodiment four.
Preparation method:
1) 1.0g carbon nanotube is weighed, is dispersed in the 200mL concentrated sulfuric acid/concentrated nitric acid (V/V=3/1), at 50 DEG C of ultrasounds
Reason for 24 hours, is gradually diluted with 400mL deionized water after being cooled to room temperature, is then filtered, washed to neutrality, and vacuum is dry at 100 DEG C
It is dry, obtain acidification carbon nanotube.
2) above-mentioned acidification carbon nanotube 0.15g is weighed, is dispersed in 10mL NMP, ultrasonic disperse 30min, under nitrogen protection
Be added dropwise in the nmp solution of 40mL isophorone diisocyanate containing 6.67g (IPDI), ultrasonic disperse 5min, under magnetic agitation in
10h is reacted at 20 DEG C.
3) it in addition weighs 2.53g diisopropanolamine (DIPA) and 0.92g glycerine is dissolved in 25mL NMP, ultrasonic disperse 30min.
Diisopropanolamine (DIPA) and glycerine mixed solution are slowly dropped in carbon nanotube/IPDI mixed solution, in 0 DEG C under mechanical stirring
Reaction for 24 hours, then heats to 60 DEG C of successive reactions for 24 hours.
4) weigh 0.61g'sAs auxiliary agent, ultrasonic disperse dissolution
It in the nmp solution of 20mL, is slowly dropped in the mixed solution of step 3,60 DEG C of reaction 12h, is warming up to 100 DEG C and continues instead
Answer 12h.Entire reaction carries out in nitrogen or argon atmosphere.
4) reaction mixture is directly poured into the beaker for containing a large amount of water and is precipitated, sediment is filtered, washed repeatedly with NMP
It washs, is then dried in vacuo in a vacuum drying oven, drying temperature is 80 DEG C, drying time 12h, obtains hyperbranched poly after dry
(urea-urethane)/carbon nano-tube combination electrode active material.
<embodiment five>
It is super branched polyurethane/graphene combination electrode active material and preparation method thereof in the present embodiment five.
Preparation method:
1) 2g graphene is weighed, 5g potassium peroxydisulfate is dispersed in the 100mL concentrated sulfuric acid, ultrasonic treatment 2h, then at 80 DEG C
Mechanic whirl-nett reaction for 24 hours, is gradually diluted after being cooled to room temperature with 400mL deionized water, is then filtered, washed to neutrality, and 100 DEG C
Lower vacuum drying, obtains acidifying graphite.
2) above-mentioned acidifying graphite alkene 0.1g is weighed, is dispersed in 10mL DMF, ultrasonic disperse 60min drips under nitrogen protection
In the DMF solution for adding 40mL methyl diphenylene diisocyanate containing 5.0g (MDI), ultrasonic disperse 30min, in 10 under magnetic agitation
12h is reacted at DEG C.
3) it in addition weighs 1.78g trimethylolpropane to be dissolved in 25mL DMF, ultrasonic disperse 10min.By trihydroxy methyl
Propane solution is slowly dropped in acidifying graphite/MDI mixed solution, in 10 DEG C of reaction 12h under mechanical stirring, then heats to 80
For 24 hours, entire reaction carries out in nitrogen or argon atmosphere for DEG C successive reaction.
4) reaction mixture is directly poured into the beaker for containing a large amount of water and is precipitated, sediment is filtered, washed repeatedly with DMF
It washs, is then dried in vacuo in a vacuum drying oven, drying temperature is 100 DEG C, drying time 10h, is obtained after dry hyperbranched
Polyurethane/graphite composite electrode active material.
Above embodiments are only the illustration done to technical solution of the present invention.Hyperbranched poly according to the present invention
It closes object electrode active material and preparation method thereof and is not merely defined in described content in the embodiment above, but with power
Benefit requires subject to limited range.Any modification that those skilled in the art of the invention are made on the basis of the embodiment
Supplement or equivalence replacement, all in claim range claimed of the invention.
Claims (10)
1. dissaving polymer electrode active material, it is characterised in that:
The dissaving polymer electrode active material is pure branched polymer material or dissaving polymer/carbon composite wood
Material,
Dissaving polymer/the carbon composite is that the pure dissaving polymer is combined with carbon nanomaterial.
2. dissaving polymer electrode active material according to claim 1, it is characterised in that:
Wherein, the pure branched polymer material is in hyperbranched polyureas, super branched polyurethane and hyperbranched poly (urea-urethane)
At least one.
3. dissaving polymer electrode active material according to claim 2, it is characterised in that:
Wherein, the hyperbranched polyureas is reacted to obtain by multicomponent isocyanate with polyamine；
The super branched polyurethane is obtained by multicomponent isocyanate and polyol reaction；
The hyperbranched poly (urea-urethane) is reacted to obtain by multicomponent isocyanate with polyhydric alcohol amine.
4. dissaving polymer electrode active material according to claim 3, it is characterised in that:
Wherein, the multicomponent isocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,6- hexa-methylene two
Isocyanates, 4,4'- dicyclohexyl methyl hydride diisocyanate, hydrogenation methylenebis phenyl isocyanate, 1,5- naphthalene diisocyanate,
Trimethyl -1,6- hexamethylene diisocyanate, isophorone diisocyanate, 4,4', 4 " triphenylmethane triisocyanates,
It is tri o cresyl thiophosphate phenyl isocyanate, L-lysine triisocyanate, any one in methyl triphenyl methane tetraisocyanate
Kind,
The polyamine is ethylenediamine, propane diamine, hexamethylene diamine, p-phenylenediamine, benzidine, melamine, bis- (hexa-methylenes)
At least one of triamine, triethylene tetramine, N- (2- amido ethyl) -1,3- propane diamine,
The polyalcohol is ethylene glycol, 1,4- butanediol, propylene glycol, neopentyl glycol, polyethylene glycol, polytetrahydrofuran diol, third
Triol, trimethylolpropane, triethanolamine, trimethylolethane, pentaerythrite, dipentaerythritol, vegetable oil polyol, polyethers
At least one of polyalcohol, polyester polyol, siloxane polyol, polyetherdiol, polycarbonate glycol,
The polyhydric alcohol amine is diethanol amine, ethanol amine, trishydroxymethylaminomethane, bis- (2- methylol) (hydroxyl first of amino-three
Base) methane, tromethamine, -2 ethyl -1,3- propylene glycol of 2- amino, at least one of diisopropanolamine (DIPA).
5. dissaving polymer electrode active material according to claim 1, it is characterised in that:
Wherein, the carbon nanomaterial is graphene, expanded graphite, acetylene black, carbon nanotube, active carbon, carbon fiber, carbon airsetting
At least one of glue.
6. dissaving polymer electrode active material according to claim 1, it is characterised in that:
Wherein, in the dissaving polymer/carbon composite electrode material, the mass percent of the carbon nanomaterial is 1~
30%.
7. the preparation method of dissaving polymer electrode active material, which comprises the steps of:
Multicomponent isocyanate, material I, solvent are mixed to the pure hyperbranched polymerization for being reacted to obtain as electrode active material
Object material；Or multicomponent isocyanate, material I, carbon nanomaterial, solvent are mixed and reacted to obtain as electrode activity
Dissaving polymer/carbon composite of material,
Wherein, the material I is polyamine, polyalcohol, any one in polyhydric alcohol amine.
8. the preparation method of dissaving polymer electrode active material according to claim 7, it is characterised in that:
Wherein, the preparation method of the pure branched polymer material specifically: multicomponent isocyanate is added in solvent and is surpassed
5~30min of sound is then slowly added into material I to be uniformly dispersed, and reacts 1~12h at -10~30 DEG C under magnetic stirring；It connects
Be warming up to 50~120 DEG C, the reaction was continued 6~48h；Entire reaction carries out in an inert atmosphere；After completion of the reaction by reactant
Precipitating filters, is dry after washing,
The preparation method of the dissaving polymer/carbon composite specifically: carbon nanomaterial is placed in acid with strong oxidizing property,
The processing 4~for 24 hours at 30~100 DEG C, it is rear washing, dry；It is then that the carbon nanomaterial after acidification is ultrasonic in solvent
10~120min makes it be uniformly dispersed, and multicomponent isocyanate is added and continues 5~30min of ultrasound to be uniformly mixed, then in magnetic
1~12h is reacted at -10~30 DEG C under power stirring；It is slowly added to material I, the reaction was continued 1~12h；Then heat to 50~
120 DEG C, the reaction was continued 6~for 24 hours；Entire reaction carries out in an inert atmosphere；Reactant is precipitated after completion of the reaction, filter, is washed
It is dry after washing.
9. the preparation method of dissaving polymer electrode active material according to claim 7, it is characterised in that:
Wherein, at least one of the acid with strong oxidizing property concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide, potassium permanganate, potassium peroxydisulfate,
The solvent is N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride, 1,4-
At least one of dioxane.
10. the preparation method of dissaving polymer electrode active material according to claim 8, it is characterised in that:
Wherein, it is additionally added initiator while the material I is added or auxiliary agent participates in reaction, contains in the auxiliary molecules different
Cyanate group and alkenyl unsaturated group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811534442.9A CN109638252A (en) | 2018-12-14 | 2018-12-14 | Dissaving polymer electrode active material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811534442.9A CN109638252A (en) | 2018-12-14 | 2018-12-14 | Dissaving polymer electrode active material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109638252A true CN109638252A (en) | 2019-04-16 |
Family
ID=66074173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811534442.9A Pending CN109638252A (en) | 2018-12-14 | 2018-12-14 | Dissaving polymer electrode active material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109638252A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527479A (en) * | 2019-08-19 | 2019-12-03 | 济南大学 | A kind of hyperbranched type thermoplastic polyurethane adhesive and its application in fire hose |
| CN111326739A (en) * | 2020-02-28 | 2020-06-23 | 浙江克能新能源科技有限公司 | Soft-package lithium manganate battery and manufacturing method thereof |
| CN111524718A (en) * | 2020-04-11 | 2020-08-11 | 中南民族大学 | Method for preparing asymmetric supercapacitor by using hydrophilic carbon nanotube film and hyperbranched polymer as double templates |
| CN113355918A (en) * | 2021-06-07 | 2021-09-07 | 晋江瑞碧科技有限公司 | Microporous carbon fiber grafted polyaniline/CoNi2S4Preparation method and application of composite material |
| CN113725435A (en) * | 2021-08-06 | 2021-11-30 | 武汉工程大学 | Three-dimensional conductive carbon negative electrode material modified by organic lithium-philic coating, and preparation method and application thereof |
| CN115368578A (en) * | 2021-05-19 | 2022-11-22 | 黄建发 | A kind of preparation method of nano silicon dioxide with core-shell structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101163463A (en) * | 2005-02-21 | 2008-04-16 | 巴斯福股份公司 | Active substance composition comprising at least one nitrogen atom-containing, hyperbranched polymer |
| US20100249350A1 (en) * | 2007-10-26 | 2010-09-30 | Nissan Chemical Industries, Ltd. | Hyperbranched polymer having nitroxyl group |
| TW201542651A (en) * | 2014-03-31 | 2015-11-16 | Dow Global Technologies Llc | Crosslinkable polymerizable composition having diallyl isocyanurate crosslinking assistant, method for producing the same, and article made therefrom |
| CN108376773A (en) * | 2018-02-07 | 2018-08-07 | 成都新柯力化工科技有限公司 | A kind of the lithium-sulfur cell sulfur electrode material and preparation method of dissaving polymer network |
-
2018
- 2018-12-14 CN CN201811534442.9A patent/CN109638252A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101163463A (en) * | 2005-02-21 | 2008-04-16 | 巴斯福股份公司 | Active substance composition comprising at least one nitrogen atom-containing, hyperbranched polymer |
| US20100249350A1 (en) * | 2007-10-26 | 2010-09-30 | Nissan Chemical Industries, Ltd. | Hyperbranched polymer having nitroxyl group |
| TW201542651A (en) * | 2014-03-31 | 2015-11-16 | Dow Global Technologies Llc | Crosslinkable polymerizable composition having diallyl isocyanurate crosslinking assistant, method for producing the same, and article made therefrom |
| CN108376773A (en) * | 2018-02-07 | 2018-08-07 | 成都新柯力化工科技有限公司 | A kind of the lithium-sulfur cell sulfur electrode material and preparation method of dissaving polymer network |
Non-Patent Citations (2)
| Title |
|---|
| WANG X等: "Polymer-Functionalized Multiwalled Carbon Nanotubes as Lithium Intercalation Hosts", 《JOURNAL OF PHYSICAL CHEMISTRY B》 * |
| 杨应奎: "聚合物修饰多壁碳纳米管的合成、结构与性质", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527479A (en) * | 2019-08-19 | 2019-12-03 | 济南大学 | A kind of hyperbranched type thermoplastic polyurethane adhesive and its application in fire hose |
| CN110527479B (en) * | 2019-08-19 | 2021-05-18 | 济南大学 | Hyperbranched thermoplastic polyurethane adhesive and application thereof in fire hose |
| CN111326739A (en) * | 2020-02-28 | 2020-06-23 | 浙江克能新能源科技有限公司 | Soft-package lithium manganate battery and manufacturing method thereof |
| CN111524718A (en) * | 2020-04-11 | 2020-08-11 | 中南民族大学 | Method for preparing asymmetric supercapacitor by using hydrophilic carbon nanotube film and hyperbranched polymer as double templates |
| CN111524718B (en) * | 2020-04-11 | 2021-07-13 | 中南民族大学 | Method for preparing asymmetric supercapacitor by using hydrophilic carbon nanotube film and hyperbranched polymer as double templates |
| CN115368578A (en) * | 2021-05-19 | 2022-11-22 | 黄建发 | A kind of preparation method of nano silicon dioxide with core-shell structure |
| CN115368578B (en) * | 2021-05-19 | 2024-11-08 | 内蒙古天壹成信环保科技有限公司 | Preparation method of nano silicon dioxide with core-shell structure |
| CN113355918A (en) * | 2021-06-07 | 2021-09-07 | 晋江瑞碧科技有限公司 | Microporous carbon fiber grafted polyaniline/CoNi2S4Preparation method and application of composite material |
| CN113355918B (en) * | 2021-06-07 | 2022-07-29 | 晋江瑞碧科技有限公司 | Preparation method and application of microporous carbon fiber grafted polyaniline/CoNi2S4 composite material |
| CN113725435A (en) * | 2021-08-06 | 2021-11-30 | 武汉工程大学 | Three-dimensional conductive carbon negative electrode material modified by organic lithium-philic coating, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109638252A (en) | Dissaving polymer electrode active material and preparation method thereof | |
| CN109659605B (en) | Self-healing polymer electrolyte matrix and preparation method thereof, self-healing polymer electrolyte, lithium ion battery and application thereof | |
| Tang et al. | A novel cross-linked nanocomposite solid-state electrolyte with super flexibility and performance for lithium metal battery | |
| Zhang et al. | Flexible and stretchable lithium‐ion batteries and supercapacitors based on electrically conducting carbon nanotube fiber springs | |
| Mu et al. | A Spidroin‐Inspired Hierarchical‐Structure Binder Achieves Highly Integrated Silicon‐Based Electrodes | |
| CN106848202B (en) | Preparation method of lithium ion battery negative plate | |
| CN105489848A (en) | Lead-carbon battery negative electrode and preparation method therefor | |
| Wei et al. | A flexible, highly conductive, tough ionogel electrolyte containing LiTFSI salt and ionic liquid [EMIM][TFSI] based on PVDF-HFP for high-performance supercapacitors | |
| CN111769322B (en) | A kind of solvent-free all-solid polymer electrolyte and preparation method thereof | |
| CN111518279B (en) | Polysiloxane based on aromatic disulfide bond and application thereof | |
| CN102088075A (en) | Electrode material of conductive polyaniline composite membrane and preparation method thereof | |
| CN113611545B (en) | Stretchable, compressible and anti-freezing organic hydrogel electrolyte-based supercapacitor and preparation method thereof | |
| CN104681300B (en) | Polyaniline-sulfonated graphene composite electrode material and preparation method thereof | |
| CN111613795A (en) | A kind of multifunctional binder for positive electrode of lithium-sulfur battery and preparation method thereof | |
| CN112952204A (en) | Preparation method of symmetric polymer-based electrode lithium ion full battery | |
| CN114479002A (en) | A kind of bifunctional elastic polyurea adhesive and its preparation method and application | |
| CN113346130A (en) | Wide-temperature self-healing electrolyte, preparation method thereof and lithium battery | |
| Zhang et al. | Design of co-continuous structure of cellulose/PAA-based alkaline solid polyelectrolyte for flexible zinc-air battery | |
| CN111900335B (en) | Silicon-based negative electrode with self-repairing property and preparation method and application thereof | |
| CN117577948A (en) | Halloysite nanotube-polymer matrix hybrid solid electrolyte membrane and preparation method thereof | |
| Li et al. | Ion-conductive and mechanically robust chitosan-based network binder for silicon/graphite anode | |
| Liu et al. | High temperature all-solid flexible supercapacitor based on novel cross-linked polybenzimidazole electrolyte | |
| CN102637891A (en) | Vanadium cell nafion proton membrane and preparation method thereof | |
| Sun et al. | Advanced-design cross-linked binder enables high-performance silicon-based anodes through in-situ crosslinking based on sodium carboxymethyl cellulose and poly-lysine | |
| Wang et al. | Polyaniline/graphene oxide nanocomposite as an innovative cathode for high energy density aqueous zinc-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190416 |