CN107251278A - 用于具有有机电解质的电化学元件的电极、包含该电极和聚合材料的电化学元件及聚合材料作为电极活性材料或电极粘结剂的用途 - Google Patents
用于具有有机电解质的电化学元件的电极、包含该电极和聚合材料的电化学元件及聚合材料作为电极活性材料或电极粘结剂的用途 Download PDFInfo
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- CN107251278A CN107251278A CN201580067282.XA CN201580067282A CN107251278A CN 107251278 A CN107251278 A CN 107251278A CN 201580067282 A CN201580067282 A CN 201580067282A CN 107251278 A CN107251278 A CN 107251278A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000011883 electrode binding agent Substances 0.000 title description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001336 alkenes Chemical class 0.000 claims abstract description 3
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000003990 capacitor Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 230000005611 electricity Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- DVQWNQBEUKXONL-UHFFFAOYSA-N 1-iodo-2-methoxybenzene Chemical compound COC1=CC=CC=C1I DVQWNQBEUKXONL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 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 group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 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
- 230000006837 decompression Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003623 enhancer 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
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- HXEACLLIILLPRG-RXMQYKEDSA-N l-pipecolic acid Natural products OC(=O)[C@H]1CCCCN1 HXEACLLIILLPRG-RXMQYKEDSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- HXEACLLIILLPRG-UHFFFAOYSA-N pipecolic acid Chemical compound OC(=O)C1CCCCN1 HXEACLLIILLPRG-UHFFFAOYSA-N 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 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
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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract
公开了包含聚合材料的电极，所述聚合材料含有根据通式(I)和(II)的亚单元或由其组成，其中在这些结构(I)和(II)中，n为不小于2的整数，Y表示酰胺基团(‑NH‑CO‑或‑CO‑NH‑)、酯基(‑O‑CO‑或‑CO‑O‑)或氨基甲酸酯基(‑NH‑CO‑O‑或‑O‑CO‑NH‑)，R1、R2、R3和R4各自独立地表示H、烷基(优选‑CH3、‑C2H5)、烷氧基‑(优选‑OCH3、‑OC2H5)、‑卤素或‑CN，Ar1和Ar4独立地表示桥连芳基，Ar2和Ar3独立地表示非桥连芳基，和R5是桥连烷基、烯烃或芳基。此外，公开了一种具有这种电极的锂离子电池和超级电容器，以及所述聚合材料在电池的电极或超级电容器的电极中作为电极活性材料和/或作为电极粘结剂的用途。 (I)
Description
本发明涉及一种用于具有有机电解质的电化学元件的电极、包含该电极和聚合材料的能够储存电能的电化学元件及聚合材料作为电极中的电极活性材料或电极粘结剂的用途。
术语“电池”最初是指在壳体中串联连接的多个电化学单电池。然而，即使单个电化学单电池，现在常常被称为电池。在电化学单电池放电期间，发生由两个电耦合但空间分隔的部分反应组成的能量供应化学反应。在相对低的氧化还原电位下发生的部分反应在负极进行，且部分反应在正极的相对较高的氧化还原电位下发生。在放电期间，电子通过负极的氧化过程释放，导致电子流经由外部负载流向正极，正极吸收相应量的电子。因此，在正极上进行还原过程。同时，对应于电极反应的离子流在电池内流动。该离子流通过离子传导电解质来确保。在二次单电池和电池中，这种放电反应是可逆的，即可以使放电期间发生的化学能向电能的转变逆转。在上下文中使用术语“阳极”和“阴极”的情况下，电极通常根据放电期间其功能来命名。因此，这种单电池中的负极为阳极，而正极为阴极。
各个电极包括至少一种电极活性材料和电化学惰性组分。电极活性材料在充电和放电期间经历化学转化，特别是氧化或还原(上述氧化和还原过程)。相比之下，电化学惰性组分在充电和放电过程中基本上是不受影响的。电极的电化学惰性组分的实例是电极粘结剂、集电器、电源出口引线和电导率改进添加剂。电子通过电源出口引线从电极提供或传导出。电极粘结剂确保电极的机械稳定性和电化学活性材料的颗粒彼此接触和与电源出口引线接触。电导率改进添加剂有助于改进电化学活性颗粒与电源出口引线之间的电连接。
锂离子电池是便携式电子设备中最常用的二次电池。电荷储存的机理是基于锂离子通常在金属氧化物(阴极侧的电极活性材料)和碳(阳极侧的电极活性材料)中的嵌入/脱插。锂离子电池表现出良好的能量密度和循环稳定性，但由于电极反应速率慢，导致低的功率密度，因此在更高的电流密度下具有适度的功能或容量保持。
相比之下，超级电容器(以前称为双电层电容器)可以在高功率密度下提供高脉冲电流。然而，根据电容器的性质，双电层电容器的容量受到限制。此外，像所有电容器一样，超级电容器具有下降电压特性。
利用有机化合物作为电极活性材料的电池单池能够显示比锂离子电池更高的功率密度以及更高的比重能量密度。一个实例是利用可逆的氧化/还原反应，即含有稳定自由基如氮氧自由基的化合物的反应。例如EP 2 025 689 A1公开了含氮氧自由基的聚合物作为二次电池中的电极活性材料的用途，所述二次电池在更高的电流倍率(高功率密度)和循环稳定性下显示非常好的容量保持。
然而，许多有机电极材料，例如导电聚合物或还有一些多自由基，在循环到较高电位并保持在较高电位时开始分解，例如在相对于Li/Li+接近或高于4V的电位下。
含有N,N,N',N'-四取代-1,4-苯二胺单元的化合物用于光电子设备，例如有机发光设备(OLED)或电致变色设备。作为电致变色材料的用途已经例如在Liou, G.；Chang，C.Macromolecules 2008,41,1667-1674中描述。描述了含有N,N,N',N'-四苯基-1,4-苯二胺单元的聚酰胺的制备。作为另一个实例，US 8 304 514 A公开了含有N,N,N',N'-四苯基-对苯二胺单元的聚芴化合物及其作为电致变色材料的用途。
含有N,N,N',N'-四烷基化-1,4-苯二胺单元的聚(3,4-亚乙基二氧噻吩)作为电储能材料的用途已经在Conte，S.；Rodríguez-Calero，G.G.；Burkhardt，S.E.; Lowe，M.A.;Abruña，H. D. RSC Advances 2013，3，1957-1964中描述。含有N,N,N',N'-四苯基-1,4-苯二胺单元的聚合物作为锂离子电池的阴极材料的用途已经在 Chang Su; Fang Yang;LvLv Ji; Lihuan Xu; Cheng Zhang, J. Mater. Chem. A 2014, 2, 20083-20088中描述。
根据上述，主要目标在于制造在高电流密度或高功率密度下具有良好容量保持的金属氧化物电极的Li离子电池。另一方面，双电层电容器显示高功率密度但能量密度低。
上述问题可以通过利用由通式(I)和/或(II)表示的含有N,N,N',N'-四苯基-1,4-苯二胺亚单元的聚合物作为Li离子电池中的电极活性材料来解决。基于这些聚合物且例如在二次Li离子电池中利用的电极材料显示高比重能量密度以及高功率密度。
根据本发明，提供了一种电极，其适合作为用于具有有机电解质的电化学元件的电极，特别是用于具有有机电解质的电池和超电容器。优选地，电极是正极，例如锂离子电池的正极或超级电容器的正极。电极包含优选作为电极活性材料的聚合材料，其含有根据通式(I)和/或(II)的亚单元或由其组成：
(I) (II)
在这些结构(I)和(II)中
n为整数≥2，优选≥20，
Y表示酰胺基团(-NH-CO-或-CO-NH-)、酯基(-O-CO-或-CO-O-)或氨基甲酸酯基(-NH-CO-O-或-O-CO-NH-)，
R1、R2、R3和R4各自独立地表示H、烷基(优选-CH3、-C2H5)、烷氧基-(优选-OCH3、-OC2H5)、-卤素或-CN，
Ar1和Ar4独立地表示桥连芳基，
Ar2和Ar3独立地表示非桥连芳基，和
R5是桥连烷基、烯烃或芳基。
桥连基团Ar1、Ar4和R5特别重要。结构(I)和(II)中的Ar1和Ar4独立地表示式(IIIa)、(IIIb)或(IIIc)的桥连芳基，
(IIIa), (IIIb), (IIIc)
在这些结构(IIIa)至(IIIc)
*标记连接点
R6、R7、R8和R9各自独立地表示H、烷基(优选-CH3、-C2H5)、烷氧基-(优选-OCH3、-OC2H5)、-卤素或-CN
R5表示式(IVa)至(IVq)基团中的一个，
(IVa), (IVb), (IVc), (IVd)
(IVe), (IVf), (IVg),
(IVh), (IVi),(IVj),
(IVk), (IVl),
(IVm), (IVn),
(IVo), (IVp),(IVq)
其中，
*标记连接点，
m = 1-20，
R1、R2、R3、R4、R6、R7、R8、R9、Ar1、Ar2、Ar3和Ar4具有与上文相同的含义。
因此，根据本发明的聚合材料是聚酰胺或聚酯或聚氨酯。包含所述聚酰胺或聚酯或聚氨基甲酸酯作为电极活性材料的Li离子电池的循环稳定性与电容器相当，并且在循环到高电位并保持在高电位下也给出优异的电化学稳定性。
在优选的实施方案中，结构(I)和(II)中的Ar2和Ar3独立地表示式(V)的非桥连芳基，
(V)
其中，
R10、R11、R12、R13和R14各自独立地表示H、烷基(优选-CH3、-C2H5)、烷氧基-(优选-OCH3、-OC2H5)、卤素、CN或式(VIa)和(VIb)的基团之一
(VIa), (VIb)
其中，
*标记连接点
X表示O或NH。
在具有有机电解质的电化学元件中，含有由通式(I)和(II)表示的聚合物作为电极活性材料，储能机理是根据方案1的N,N,N',N'-四苯基-1,4-苯二胺单元的可逆氧化/还原：
方案1
在该方案中，A-是源自电解质盐的阴离子，可以是例如衍生自LiPF6、LiClO4、LiBF4、LiN(SO2CF3)或NaCl的阴离子。
聚合物化合物也可以携带稳定的氮氧自由基。储能的潜在机理是根据方案2的氮氧自由基的可逆氧化/还原，代表性显示2,2,6,6-四甲基哌啶-1-氧基(TEMPO)的氧化还原电对：
方案2
在该方案中，A-具有与之前相同的含义，且C+是衍生自电解质盐的阳离子，并且可以是例如Li+或Na+。
聚合物实例
具有由通式(I)和(II)表示的结构的单种化合物的非限制性实例由下式1-16表示。理论比容量(Ah/kg)在括号中显示，并使用等式1计算。
理论比容量= F/[3.6×(M/z)] (等式1)
F =法拉第常数= 96485 C/mol
M =重复单元的分子量
z =各个重复单元转移的电子
(1)
(93.6 Ah/kg)
(2)
(93.6 Ah/kg)
(3)
(84.7 Ah/kg)
(4)
(117.7 Ah/kg)
(5)
(117.4 Ah/kg)
(6)
(105 Ah/kg)
(7)
(102.2 Ah/kg)
(8)
(126.3 Ah/kg)
(9)
(131.9 Ah/kg)
(10)
(138.9 Ah/kg)
(11)
(93.3 Ah/kg)
(12)
(101.8 Ah/kg)
(13)
(118.2 Ah/kg)
(14)
(118.2 Ah/kg)
(15)
(108.7 Ah/g)
(16)
(77.1 Ah/kg)
聚合材料优选具有2.5mPas至50mPas的动态粘度(在NMP中在20℃和2重量%的浓度下测量)。
优选地，聚合材料的平均分子量为200.000g/mol至400.000g/mol范围。
电极可以包括集电器，特别是由铝或铜制成的集电器。
优选地，除了根据通式(I)和(II)的聚合材料或上述优选的实施方案之外，电极还包含至少一种选自炭黑、石墨、活性炭、碳纳米管和石墨烯的碳材料，特别地作为电导率改进添加剂。
优选地，碳材料以0.1重量%至99.9重量%，更优选25重量%至95重量%，特别是45重量%至75重量%的量包含在电极中。
聚合电极材料优选以0.1重量%至99.9重量%，更优选25重量%至95重量%，特别是45重量%至75重量%的量包含在电极中。
在另一个优选的实施方案中，电极包括至少一种电极粘结剂。所有已知的用于锂离子电池的粘结剂适用作为根据本发明的电极的粘结剂，然而，特别优选的粘结剂选自基于纤维素的粘结剂、基于聚丙烯酸酯的粘结剂和基于聚乙烯的粘结剂(特别是聚偏氟乙烯和聚偏二氟乙烯)。
电极粘结剂优选以0.1重量%至20重量%，更优选0.1重量%至10重量%，特别是1重量%至10重量%的量包含在电极中。甚至更优选的是1重量%和7.5重量%之间的量。
令人惊奇地发现，上述聚合材料本身具有粘结性质。因此，可以使用聚合材料作为反应性电极粘结剂。根据本发明的电极的优选实施方案不包含任何另外的电极粘结剂。这些电极可以由聚合电极材料和碳材料组成。
包含上述电极或含有根据上述通式(I)和(II)的亚单元或由其构成的聚合电极材料的各个锂离子电池被要求作为本发明的一部分。优选所要求保护的锂离子电池是二次电池。
在优选的实施方案中，所要求保护的锂离子电池包含上述作为正极的电极。
在另一个优选的实施方案中，所要求保护的锂离子电池的正极包含至少一种作为活性材料的金属氧化物，特别是至少一种选自锂-钴氧化物(LiCoO2)、LiMn2O4尖晶石、锂-铁磷酸盐(LiFePO4)和衍生物如LiNi1/3Mn1/3Co1/3O2或LiMnPO4的氧化物，以及包含作为电极粘结剂的根据上述通式(I)和(II)的亚单元或由其构成的聚合电极材料。在这种情况下，聚合材料优选以0.1重量%至20重量%，更优选0.1重量%至10重量%，特别是1重量%至10重量%的量包含在电极中。
所要求保护的电池的负极可以含有金属锂或基于碳的颗粒，如石墨碳或能嵌入锂的非石墨碳材料。此外，负极还可以含有可与锂合金化的金属和半金属材料。因此，例如，元素锡、锑和硅能够与锂形成金属间相。
此外，包含如上所述的电极的各个超级电容器或含有根据上述通式(I)和(II)的亚单元或由其组成的聚合电极材料被要求作为本发明的一部分。
众所周知，超级电容器既显示双电层电容又显示赝电容。双电层电容意味着通过在导电电极表面和电解质之间的界面处的亥姆霍兹双电层中分隔电荷来实现静电储存，且赝电容是指通过氧化还原反应、嵌入或电吸附实现的具有电子电荷转移的法拉第电化学储存。
优选地，根据本发明的超级电容器包括作为负极的碳电极，特别是包含活性炭或由其组成的电极。优选地，负极含有10重量%至100重量%，更优选25重量%至99重量%，特别是50重量%至99重量%之间的量的碳或活性炭。甚至更优选的是75重量%至99重量%的量。
根据本发明的超级电容器的正极优选包含上述聚合化合物，优选与碳组合，特别是与活性炭组合。
根据本发明的超级电容器的正极优选包含1重量%至99重量%，更优选15重量%至95重量%，更优选50重量%至85重量%，特别是60重量%至80重量%的碳。
聚合电极材料优选包含在根据本发明的超级电极的正极中，其量为5重量%至75重量%，更优选10重量%至50重量%，特别是15重量%至40重量%。
如果聚合化合物与碳组合存在，则碳优选以40重量%至99重量%，更优选50重量%至80重量%的量包含在电极中，并且聚合化合物优选以1重量%至60重量%，更优选20重量%至50重量%的量包含在电极中。
在优选的实施方案中，根据本发明的用于超级电容器的正极和/或负极中或电极中的活性碳具有至少900m2/g的BET表面积(根据德国标准DIN ISO 9277确定)和/或至少60F/g的容量(根据德国标准DIN IEC 62391确定)。
根据本发明的超级电容器的正极和负极可以包含电极粘结剂和/或电导率改进添加剂，特别是用于锂离子电池的已知粘结剂之一和/或上述电导率改进添加剂之一，优选量为0.1重量%至20重量%，更优选0.1重量%至10重量%，特别是1重量%至10重量%。
上述百分比在各种情况下都涉及干燥条件下电极的总重量，即在电极浸渍电解质之前，而不考虑集电器的重量(如果有的话)。此外，上述百分比优选总计高达100重量%。
本发明还包括根据式(I)和(II)的化合物的用途或上述优选实施方案之一作为电池的电极中，特别是锂离子电池中，或超级电容器的电极中的电极活性材料的用途。
此外，本发明包括根据式(I)和(II)的化合物作为电池的电极中，特别是锂离子电池中的电极粘结剂的用途。
作为有机电解质，根据本发明的电化学元件和电极可特别包含已知适合用作锂离子电池或超级电容器的电解质的任何有机电解质。优选地，电解质是溶剂和其中含有的导电盐的混合物。溶剂优选包含碳酸亚乙酯(EC)和至少一种选自碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)和碳酸亚丙酯(PC)的其它碳酸酯。
导电盐优选为氟磷酸锂、硼酸锂和/或烷基磺酰亚胺锂。
然而，本发明通过以下附图和实施例进一步说明，但不限于此。
实施例
实施例1：根据本发明根据以下方案，合成N,N'-双(4-氨基苯基)-N,N'-二苯基-1,4-苯二胺和间苯二甲酰氯的共聚物(化合物1)作为聚合电极材料的第一实施例：
步骤A：N,N'-双(4-硝基苯基)-N,N'-二苯基-1,4-苯二胺
如Davis, M. C.; Chafin, A. C.; Sathrum, A. J. Synthetic Communications2005, 35, 2085-2090所述制备。
将纯化的N,N'-二苯基对苯二胺(2.03g，7.8mmol)溶于无水DMSO(13.4mL)中，加入叔丁醇钾(2.20g，2.5当量)和1-氟-4-硝基苯(2.15 mL，2.6当量)，将反应混合物在90℃下搅拌17小时。将混合物冷却至室温，并逐滴加入到200mL经搅拌的饱和NaCl水溶液。将所得的橙棕色沉淀过滤，用100mL水洗涤并溶解于100mL二氯甲烷中。将有机相用约50mL水洗涤2次，经Na2SO4干燥并减压浓缩。将粗产物分散在100mL回流的乙腈中1小时，冷却，过滤并真空干燥，得到标题化合物，为橙红色固体(3.57g，91%)。
1H NMR (300.36 MHz, DMSO-d6, δ, ppm): 8.14-8.04 (m, 4H), 7.54-7.43(m, 4H), 7.35-7.25 (m, 10H), 6.92-6.83 (m, 4H); 13C NMR (APT, 75.53 MHz, DMSO-d6, δ , ppm): 153.18, 144.82, 142.38, 139.28, 130.37, 127.93, 127.00, 126.44,125.65, 117.34; EI-MS: M+, m/z 测量：502.1635 Da, 对C30H22N4O4计算：502.1641 Da;IR: 1581, 1486, 1310, 1298, 1279, 1255, 1185, 1107, 997, 832, 749, 710, 691,649, 553, 519, 502, 414 cm-1。
步骤B：N,N'-双(4-氨基苯基)-N,N'-二苯基-1,4-苯二胺
如Liou, G.-S.; Hsiao, S.-H.; Ishida, M.; Kakimoto, M.; Imai, Y. Journalof Polymer Science Part A: Polymer Chemistry 2002, 40, 2810-2818中所述制备。
将N,N'-二(4-硝基苯基)-N,N'-二苯基-1,4-苯二胺(1.52g，3mmol)和Pd/C(80mg，5.3重量%)分散在乙醇(10mL)中，逐滴加入水合肼(1.5mL，10.2当量)，将反应混合物在80℃下搅拌17小时。冷却后，加入20mL DMF，过滤混合物以除去催化剂，并用约30mL的DMF充分洗涤。将滤液减压浓缩，逐滴加入到100ml经搅拌的饱和NaCl水溶液中，过滤所得沉淀。将粗产物在50ml沸腾的甲苯中浆化3小时，冷却并过滤。重复该纯化程序，所得固体在真空下干燥，得到标题化合物，为米色固体(0.62g，46%)。
1H NMR (300.36 MHz, DMSO-d6, δ, ppm)：7.20-7.10 (m, 4H), 6.90-7.73 (m,14H), 6.60-6.52 (m, 4H), 5.05 (s, 4H, -NH2); 13C NMR (APT, 75.53 MHz, DMSO-d6,δ, ppm): 148.45, 146.11, 142.06, 135.27, 128.95, 127.91, 123.80, 119.95,119.78, 115.0; EI-MS: M+, m/z测量: 442.2146 Da, 对C30H26N4计算：442.2158 Da; IR:3469, 3377, 3032, 1620, 1590, 1501, 1482, 1306, 1263, 1175, 1121, 1079, 1026,834, 754, 723, 697, 665, 586, 534, 518, 507, 442, 409cm-1。
步骤C：聚合
将N,N'-双(4-氨基苯基)-N,N'-二苯基-1,4-苯二胺(306mg，0.69mmol)溶于无水NMP(1.85mL)中，冷却至0℃，分部分加入间苯二甲酰氯(140mg，1当量，在使用前从正己烷中重结晶)。在搅拌下将反应混合物逐渐温热至室温。3小时后，将现在高度粘稠的溶液逐滴加入到20mL经搅拌的甲醇中。将沉淀在20mL沸腾甲醇中搅拌3小时，过滤并真空干燥，得到化合物1，为绿色固体(389mg，98%)。
1H NMR (300.36 MHz, DMSO-d6, δ, ppm): 10.35 (s, 2H, -NH-CO-), 8.44(s, 1H), 8.12-7.98 (m, 2H), 7.75-7.55 (m, 5H), 7.20 (br, 4H), 7.05-6.81 (m,14H); 13C NMR (APT, 75.53 MHz, DMSO-d6, δ, ppm): 164.78, 147.47, 142.97,142.24, 135.19, 134.47, 129.40, 124.84, 124.49, 122.52, 121.72; IR: 3273,3035, 1665, 1593, 1498, 1308, 1263, 1111, 827, 753, 718, 695, 522, 470,411cm-1。
实施例2：根据本发明根据以下方案，合成N,N-双(4-氨基苯基)-N',N'-二(4-甲氧基苯基)-1,4-苯二胺和对苯二甲酸的共聚物 (化合物3)作为聚合电极材料的第二实施例：
步骤A：4-硝基-4',4''-二甲氧基三苯胺
将碘代茴香醚(2g，8.54mmol，4当量)和硝基苯胺(295mg，2.14mmol，1当量)溶于8mLDMF中，逐滴加入到2-哌啶酸(221mg，1.71mmol，0.8当量)、碘化铜(I) (163mg，0.86mmol，0.4当量)和碳酸钾(2.4g，0.22mol，8当量)。将反应混合物在120℃下搅拌48小时。冷却后，用乙酸乙酯和NaOH萃取混合物。将有机相经Na2SO4干燥并减压浓缩。在硅胶上柱层析(洗脱液：环己烷/乙酸乙酯= 1:1)后，得到标题化合物(487mg，65%)。
1H-NMR (300 MHz, CDCl3, δ): 8.00 (d, 2H) 7.13 (d, 4H), 6.91 (d, 4H),6.75 (d, 2H), 3.82 (s, 6H, OCH3); 13C-NMR (75 MHz, CDCl3, δ): 157.7, 154.1,139.0, 138.3, 128.1, 125.6, 115.7, 115.2, 55.5。
步骤B：4-氨基-4',4''-二甲氧基三苯胺
将4-硝基-4',4''-二甲氧基三苯胺(0.3g，0.86mmol，1当量)溶于14mL乙腈和12mL乙醇中。加入氯化锡(II)(1.8g，9.64mmol，11当量)，将混合物在80℃下搅拌过夜。冷却后，加入乙酸乙酯，混合物用NaHCO3和盐水洗涤。再用乙酸乙酯萃取10次。将有机相经Na2SO4干燥并减压浓缩(240mg，88%)。
1H-NMR (300 MHz, CDCl3, δ): 6.81 (d, 4H), 6.77 (d, 4H), 6.72 (d, 2H),6.53 (d, 2H), 4.90 (s, 2H, NH2), 3.67 (s, 6H, OCH3); 13C-NMR (75 MHz, CDCl3,δ): 154.1, 145.1, 142.2, 137.1, 126.6, 123.4, 115.1, 114.7, 55.3; IR: 3455,3371 cm-1 (N-H伸缩), 2966, 2920, 2845 cm-1 (OCH3, C-H伸缩)。
步骤C：N,N-双(4-硝基苯基)-N',N'-二(4-甲氧基苯基)-1,4-苯二胺
如Liou, G.; Chang, C. Macromolecules 2008, 41, 1667–1674中所述制备。
在室温下搅拌4mL DMSO中的氟化铯(247mg，1.62mmol，2.2当量)。依次加入4-氨基-4',4''-二甲氧基三苯胺(240mg，0.75mmol，1.1当量)和4-氟硝基苯(165μL= 220mg，1.56mmol，2当量)，将反应混合物在120℃下搅拌。24小时后，将混合物缓慢倒入50mL经搅拌的H2O中，过滤沉淀。将粗产物从DMF/MeOH(315mg，75%)中重结晶。
1H-NMR (300 MHz, DMSO-d6, δ): 8.16 (d, 4H), 7.19 (d, 4H), 7.11 (d,4H), 7.04 (d, 2H), 6.93 (d, 4H), 6.77 (d, 2H), 3.73 (s, 6H, OCH3); 13C-NMR (75MHz, DMSO-d6, δ): 156.5, 151.9, 147.8, 141.8, 139.6, 135.5, 128.8, 127.7,125.8, 122.0, 119.4, 115.3, 55.5; IR: 2934, 2834 (OCH3, C-H伸缩), 1581, 1311(NO2伸缩)。
步骤D：N,N-双(4-氨基苯基)-N',N'-二(4-甲氧基苯基)-1,4-苯二胺
将N,N-双(4-硝基苯基)-N',N'-二(4-甲氧基苯基)-1,4-苯二胺(1.6g，2.84mmol，1当量)溶于45mL乙腈和50mL乙醇中，加入二氯化锡(II)(14.1g，62.6mmol，22当量)。将反应混合物在80℃下搅拌过夜。冷却后，加入乙酸乙酯，混合物用盐水和NaHCO3洗涤。将有机相经Na2SO4干燥并减压浓缩。在硅胶上柱层析之后，得到标题化合物(1.4g，70%)。
1H-NMR (300 MHz, DMSO-d6, δ): 6.85 (d, 4H), 6.80 (d, 4H), 6.77 (d,4H), 6.70 (d, 2H), 6.56 (d, 2H), 6.50 (d, 4H), 4.50 (bs, 4H, NH2), 3.73 (s,6H, OCH3); 13C-NMR (75 MHz, DMSO-d6, δ): 154.6, 145.3, 144.9, 141.8, 139.6,136.6, 127.7, 124.6, 124.4, 118.9, 115.0, 114.9, 55.4; IR: 3434, 3360 cm-1 (N-H伸缩), 2947, 2832 cm-1 (OCH3, C-H伸缩)。
步骤E：聚合
如Liou, G.; Chang, C. Macromolecules 2008, 41, 1667-1674中所述制备。
N,N-双(4-氨基苯基)-N',N'-二(4-甲氧基苯基)-1,4-苯二胺(0.1g，0.2mmol，1当量)、对苯二甲酸(33mg，0.2mmol，1当量)、氯化钙(24mg，0.21mmol，1当量)溶解在0.19mLNMP中并在搅拌下抽真空。加入吡啶(0.1mL，1.24mmol，6当量)，将混合物加热至100℃。在该温度下，加入亚磷酸三苯酯(0.17g，0.77mmol，3.6当量)，将反应混合物搅拌4小时，然后逐滴加入到冷甲醇(129mg，97%)中。
1H-NMR (300 MHz, DMSO-d6, δ): 10.40 (s, 2H, -NH-CO-), 8.11 (s, 4H),7.70 (d, 4H), 7.00 (d, 8H), 6.88 (d, 6H), 6.77 (d, 2H), 3.72 (s, 6H, OCH3);13C-NMR (75 MHz, DMSO-d6, δ): 164.7, 155.5, 144.0, 143.7, 140.8, 137.6, 133.8,127.8, 126.1, 125.3, 123.3, 122.0, 115.1, 55.4; IR: 3312 cm-1 (N-H伸缩), 3037cm-1 (芳族C-H伸缩), 2932, 2833 cm-1 (OCH3, C-H伸缩), 1654 cm-1 (酰胺羰基), 1239cm-1 (不对称伸缩 C-O-C), 1034 cm-1 (对称伸缩 C-O-C)。
电极实施例1-锂离子电池
将在NMP中含有25重量%化合物1、55重量%的Super P和20重量%的PVdF(聚偏二氟乙烯)粘结剂的浆料通过刮刀流延到碳涂覆的铝箔(集电器)上(百分数在各种情况下与浆料中固体的总重量有关，而不考虑NMP的重量)。
将电极模切、干燥并组装在Swagelok单电池中，其包含作为阳极和参比电极的锂、Freudenberg 2190隔膜、含有1M LiPF6作为电解质的碳酸亚乙酯/碳酸二乙酯(3/7，v/v)。
图1显示电极实施例1的复合电极的循环伏安图(扫描速率：0.1mV/s)
图2显示电极实施例1的复合电极的倍率容量试验。
图3显示电极实施例1的复合电极在10C下充电/放电的恒定电流。
图4显示电极实施例1的复合电极的IU充电试验，其中半电池以1C的恒定电流充电，直到达到4V(相对于Li/Li+)的截止电压。半电池保持4 V(相对于Li/Li+)2 h，然后以1 C的恒定电流放电。
比较电极实施例1
将在NMP中含有10重量%比较化合物(见下文结构)、80重量%的Super P和10重量%的PVdF(聚偏二氟乙烯)粘结剂的浆料通过刮刀流延到铝箔(集电器)上(百分数在各种情况下与浆料中固体的总重量有关，而不考虑NMP的重量)。
将电极模切，干燥并组装在Swagelok单电池中，其包含作为阳极和参比电极的锂、Freudenberg 2190隔膜、含有1M LiPF6作为电解质的碳酸亚乙酯/碳酸二乙酯(3/7，v/v)。
(比较化合物)
(109 Ah/kg)
图5显示比较电极实施例1的复合电极的IU充电试验，其中半电池用1C的恒定电流充电，直到达到4V(相对于Li/Li+)的截止电压。半电池保持在4V(相对于Li/Li+)1小时，然后以1C的恒定电流放电。
电极实施例2-超级电容器
将在NMP中含有22重量%的化合物1、5重量%的Super P(炭黑，电导率改进添加剂)、5重量%的PVdF(聚偏二氟乙烯)粘结剂和68重量%活性炭的浆料通过刮刀流延到碳涂覆的铝箔(集流体)上(百分比在各种情况下与浆料中固体的总重量有关，而不考虑NMP的重量)。将电极模切并干燥。
为了制备超级电容器，将一些得到的正极与碳负极结合。正极和负极通过聚烯烃隔膜分离。使用在NMP中含有6重量%的Super P(电导率增强剂)、6重量%的PVdF粘结剂和88重量%活性炭的浆料制备碳电极。
所获得的正极已经与常规的碳超级电容器电极进行比较。为了表征，使用含有1MLiPF6的有机电解质碳酸亚乙酯/碳酸二乙酯(3/7，v/v)。
图6中的电压曲线对应于充电/放电过程，其中一个用包含化合物1的所获得的正极进行(2)，另一个用常规的碳超级电容器电极进行(1)。
电极实施例3-锂离子电池
将在NMP中含有5重量%的化合物1、5重量%的Super P、85重量%的磷酸锂铁和5重量%的PVdF(聚偏二氟乙烯)粘结剂的浆料通过刮刀流延到碳涂覆的铝箔(集电器)上(百分比在各种情况下与浆料中固体的总重量有关，而不考虑NMP的重量)。
将电极模切，干燥并组装在Swagelok单电池中，其包含作为阳极和参比电极的锂、Freudenberg 2190隔膜、含有1M LiPF6作为电解质的碳酸亚乙酯/碳酸二乙酯(3/7，v/v)。电池显示良好的可循环性。
电极实施例4-锂离子电池
将在NMP中含有7.5重量%化合物1、5重量%的Super P和87.5重量%的磷酸锂铁的浆料通过刮刀流延到碳涂覆的铝箔(集电器)上(百分比在各种情况下与浆料中固体的总重量有关，而不考虑NMP的重量)。
将电极模切、干燥并组装在Swagelok单电池中，其包含作为阳极和参比电极的锂、Freudenberg 2190隔膜、含有1M LiPF6作为电解质的碳酸亚乙酯/碳酸二乙酯(3/7，v/v)。单电池显示良好的可循环性。
Claims (8)
1. 用于具有有机电解质的电化学元件的电极，包括含有根据通式(I)和/或(II)的亚单元或由其组成的聚合材料，
(I) (II)
其中在这些结构(I)和(II)中
n为整数≥2，优选≥20，
Y表示酰胺基团(-NH-CO-或-CO-NH-)、酯基(-O-CO-或-CO-O-)或氨基甲酸酯基(-NH-CO-O-或-O-CO-NH-)，
R1、R2、R3和R4各自独立地表示H、烷基(优选-CH3、-C2H5)、烷氧基-(优选-OCH3、-OC2H5)、-卤素或-CN，
Ar1和Ar4独立地表示桥连芳基，
Ar2和Ar3独立地表示非桥连芳基，和
R5是桥连烷基、烯烃或芳基，
其中结构(I)和(II)中的Ar1和Ar4独立地表示式(IIIa)、(IIIb)或(IIIc)的桥连芳基，
(IIIa), (IIIb), (IIIc)
其中，在这些结构(IIIa)至(IIIc)中
*标记连接点
R6、R7、R8和R9各自独立地表示H、烷基(优选-CH3、-C2H5)、烷氧基-(优选-OCH3、-OC2H5)、-卤素或-CN
且其中R5表示式(IVa)至(IVn)基团中的一个，
(IVa), (IVb), (IVc),
(IVd), (IVe), (IVf),
(IVg), (IVh), (IVi),
(IVj), (IVk),
(IVl), (IVm), (IVn)
其中，
*标记连接点，
m = 1-20，
R1、R2、R3、R4、R6、R7、R8、R9、Ar1、Ar2、Ar3和Ar4具有与前文相同的含义。
2. 根据权利要求1的电极，其中结构(I)和(II)中的Ar2和Ar3独立地表示式(V)的非桥连芳基，
(V)
其中
R10、R11、R12、R13和R14各自独立地表示H、烷基(优选-CH3、-C2H5)、烷氧基-(优选-OCH3、-OC2H5)、卤素、CN或式(VIa)和(VIb)的基团之一
(VIa), (VIb)
其中，
*标记连接点
X表示O或NH。
3.根据权利要求1或2的电极，其还包括至少一种选自炭黑、石墨、碳纳米管和石墨烯的碳材料。
4.根据前述权利要求中任一项的电极，其还包括至少一种电极粘结剂，优选选自基于纤维素的粘结剂、基于聚丙烯酸酯的粘结剂和基于聚乙烯的粘结剂。
5.锂离子电池，特别是二次锂离子电池，其含有根据前述权利要求中任一项的电极或包含根据通式(I)和(II)的亚单元或由其组成的聚合材料。
6.超级电容器，其包含根据前述权利要求中任一项的电极或含有根据通式(I)和(II)的亚单元或由其组成的聚合材料。
7.根据式(I)和(II)的化合物在电池电极中，特别是在锂离子电池中或超级电容器电极中作为电极活性材料的用途。
8.根据式(I)和(II)的化合物在电池电极中，特别是在锂离子电池中作为电极粘结剂的用途。
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| EP14197166.3A EP3032621A1 (en) | 2014-12-10 | 2014-12-10 | Electrode for an electrochemical element with an organic electrolyte, electrochemical elements comprising the electrode and polymeric material and its use as electrode active material or as electrode binder |
| EP14197166.3 | 2014-12-10 | ||
| PCT/EP2015/077346 WO2016091569A1 (en) | 2014-12-10 | 2015-11-23 | Electrode for an electrochemical element with an organic electrolyte, electrochemical elements comprising the electrode and polymeric material and its use as electrode active material or as electrode binder |
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| EP3154111B1 (en) * | 2015-10-07 | 2019-06-12 | VARTA Microbattery GmbH | Composite material, electrode, method to produce the material and the electrode and electrochemical cell comprising the electrode |
| WO2018079262A1 (ja) * | 2016-10-24 | 2018-05-03 | Jsr株式会社 | 重合体、電極、蓄電デバイス及び重合体の製造方法 |
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| WO2010051259A1 (en) * | 2008-10-27 | 2010-05-06 | Plextronics, Inc. | Polyarylamine ketones |
| TWI412545B (zh) | 2010-07-21 | 2013-10-21 | Univ Nat Taiwan Science Tech | 共軛高分子、其製造方法及包含其之光電裝置 |
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| GUEY-SHENG LIOU等: "Electrochemical behavior of N,N,N’,N’-tetraphenyl-1,4-phenylenediamine moiety on novel aromatic polyamides and their electrochromic properties", 《DYES AND PIGMENTS》 * |
| GUEY-SHENG LIOU等: "Highly Stable Anodic Electrochromic Aromatic Polyamides Containing N,N,N’,N’-Tetraphenyl-p-Phenylenediamine Moieties：Synthesis，Electrochemical，and Electrochromic Properties", 《MACROMOLECULES》 * |
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| CN111574402A (zh) * | 2020-05-29 | 2020-08-25 | 江苏畅鸿新材料科技有限公司 | 一种荧光材料制备方法 |
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