CN117154007A - Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof - Google Patents
Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117154007A CN117154007A CN202311246516.XA CN202311246516A CN117154007A CN 117154007 A CN117154007 A CN 117154007A CN 202311246516 A CN202311246516 A CN 202311246516A CN 117154007 A CN117154007 A CN 117154007A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- phthalocyanine
- phthalocyanine compound
- ion battery
- electrode material
- 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
- -1 phthalocyanine compound modified lithium ion Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011572 manganese Substances 0.000 claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims abstract description 20
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 19
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000007581 slurry coating method Methods 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 description 52
- 238000012360 testing method Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 33
- 230000014759 maintenance of location Effects 0.000 description 30
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000010405 anode material Substances 0.000 description 13
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000004075 alteration Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WVOVLHZWOQJYOB-UHFFFAOYSA-M S(=O)(=O)(OF)[O-].[Li+] Chemical compound S(=O)(=O)(OF)[O-].[Li+] WVOVLHZWOQJYOB-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 238000003760 magnetic stirring Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a phthalocyanine compound modified positive electrode for a lithium ion battery, which comprises a current collector and a positive electrode material deposited on the surface of the current collector, wherein the positive electrode material comprises a positive electrode active component, and the positive electrode active component comprises a layered lithium-rich manganese oxide positive electrode material and a coating layer containing a metal phthalocyanine compound and coated on the surface of the layered lithium-rich manganese oxide positive electrode material; the metal phthalocyanine compound is selected from one or more of iron phthalocyanine, manganese phthalocyanine, copper phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine and zinc phthalocyanine. The phthalocyanine compound modified positive electrode for the lithium ion battery can realize nondestructive modification of a lithium-rich manganese positive electrode material, remarkably improve the cycling stability of the layered lithium-rich manganese positive electrode material, effectively inhibit voltage attenuation and remarkably improve the ion conductivity at room temperature. The preparation method of the positive electrode is simple and efficient, and the positive electrode can be prepared through a traditional slurry coating process.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a positive electrode for a phthalocyanine compound modified lithium ion battery, and a preparation method and application thereof.
Background
Fossil energy is the main energy source in modern society, but its non-renewable nature and the serious environmental problems that it brings force people to find alternatives to it. The lithium ion battery is used as a green energy storage and conversion device, and has been widely applied to the fields of various mobile electronic products, electric automobiles, aviation, medical equipment and the like by virtue of the advantages of high energy density, environmental friendliness, portability and the like.
At present, the traditional anode materials comprise lithium cobaltate, lithium iron phosphate and ternary anode, the capacities of the traditional anode materials are lower than 200 milliampere hours/gram, so that the energy density of the traditional lithium ion battery is lower, and the long endurance requirement of an electric automobile cannot be met. Therefore, development of a positive electrode material having a high capacity, a high energy density, a low cost, and high safety is urgent.
The layered lithium-rich manganese material is a positive electrode material which is widely focused at present and has the advantages of high discharge specific capacity (280 mA/g), moderate average voltage (3.6V), high energy density (more than 1000 Watts/kg), low cost and simple synthesis process. Therefore, if the layered lithium-rich manganese positive electrode material is applied to a power battery, the energy density of the layered lithium-rich manganese positive electrode material is improved greatly. However, the layered lithium-rich manganese positive electrode material has certain disadvantages and shortcomings, and is hindered in commercial application. The layered lithium-rich manganese positive electrode material has high irreversible capacity for the first time, continuous attenuation of capacity and voltage in circulation and poor rate capability, and the intrinsic reasons of the layered lithium-rich manganese positive electrode material are the irreversible oxygen precipitation and the structural degradation and electrode degradation caused by layered-spinel phase change.
At present, the modification mode of the layered lithium-rich manganese anode material is mainly surface modification, for example, surface coating or surface treatment is adopted, so that oxygen release can be inhibited, and side reaction of electrolyte on an electrode is reduced. However, the traditional coating materials such as aluminum oxide, metaboric acid alkali metal compound, aluminum fluoride, lanthanum oxide and the like have complex preparation process and higher cost, and have certain destructive effect on the surface structure of the lithium-rich manganese.
Therefore, development of a modification mode with high efficiency, low cost, simplicity and easiness is needed to be developed, and the electrochemical performance of the layered lithium-rich manganese anode material is comprehensively improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a phthalocyanine compound modified positive electrode for a lithium ion battery, which can realize the nondestructive modification of a lithium-rich manganese positive electrode material, remarkably improve the cycling stability of a layered lithium-rich manganese positive electrode material, effectively inhibit the voltage attenuation of the layered lithium-rich manganese positive electrode material and remarkably improve the ion conductivity at room temperature. The preparation method of the positive electrode is simple and efficient, and the positive electrode can be prepared through a traditional slurry coating process.
The specific technical scheme is as follows:
the positive electrode for the phthalocyanine compound modified lithium ion battery comprises a current collector and a positive electrode material deposited on the surface of the current collector, wherein the positive electrode material comprises a positive electrode active component, and the positive electrode active component comprises a layered lithium-rich manganese oxide positive electrode material and a coating layer containing a metal phthalocyanine compound and coated on the surface of the layered lithium-rich manganese oxide positive electrode material;
the metal phthalocyanine compound is selected from one or more of iron phthalocyanine, manganese phthalocyanine, copper phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine and zinc phthalocyanine.
The invention provides a layered lithium-rich manganese positive electrode material coated by a metal phthalocyanine compound as a positive electrode active material for preparing a positive electrode for a lithium ion battery for the first time, and the cyclic stability of the positive electrode can be obviously improved and voltage attenuation can be effectively inhibited through the coating of the layered lithium-rich manganese positive electrode material by the metal phthalocyanine compound. The metal phthalocyanine compound coating mainly improves the performance of the layered lithium-rich manganese anode by the following aspects:
(1) The metal element and nitrogen element in the metal phthalocyanine compound can serve as redox centers of redox pairs, and the peroxy ions in the layered lithium-rich manganese can be timely reduced into lattice oxygen ions during the charging process by utilizing the electron transfer of the metal element and nitrogen element and oxygen in the lithium-rich manganese, so that irreversible oxygen release is effectively inhibited.
(2) The metal phthalocyanine compound coating effectively protects the surface of the layered lithium-rich manganese anode, reduces direct contact between the layered lithium-rich manganese anode material and electrolyte, thereby reducing interface side reaction, and simultaneously can induce the formation of a stable and uniform anode-electrolyte interface film (CEI) and greatly inhibit the dissolution of transition metal.
(3) The metal phthalocyanine compound inhibits transition metal ion migration in the layered lithium-rich cathode material, and reduces the spinel content generated by phase change in the circulation process.
Through the synergistic effect, the metal phthalocyanine compound coating greatly improves the structural stability of the layered lithium-rich manganese anode material, reduces the capacity and voltage attenuation in the circulation process, and greatly improves the circulation stability and voltage retention rate of the layered lithium-rich manganese anode.
In the test, it is also unexpectedly found that after the metal phthalocyanine compound is coated, the room-temperature ion conductivity of the layered lithium-rich manganese anode material is obviously improved.
In the invention, the structural general formula of the layered lithium-rich manganese oxide positive electrode material is xLi 2 MnO 3 -(1-x)LiMO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is selected from one or more of Ni, co, mn, cr, fe, al, nb, mo, ru, and x is more than or equal to 0 and less than or equal to 1.
Preferably, x is more than or equal to 0.5 and less than or equal to 0.7; further preferably, x=0.5.
In the present invention, the thickness of the coating layer containing the metal phthalocyanine compound is 1 to 50nm; preferably 2 to 20nm.
Preferably, the metal phthalocyanine compound is selected from one or more of copper phthalocyanine, iron phthalocyanine, manganese phthalocyanine and cobalt phthalocyanine.
Further preferably, the metal phthalocyanine compound is selected from copper phthalocyanine and/or iron phthalocyanine.
More preferably, the metal phthalocyanine compound is selected from copper phthalocyanines.
Experiments show that the cyclic stability and the voltage retention rate of the layered lithium-rich manganese anode material can be effectively improved after the metal phthalocyanine compound of the type is coated; however, with the continuous preference of the metal phthalocyanine compound, the room-temperature ionic conductivity of the prepared coated layered positive plate is continuously improved.
The invention also discloses a preparation method of the phthalocyanine compound modified positive electrode for the lithium ion battery, which comprises the following steps:
and uniformly mixing the layered lithium-rich manganese oxide positive electrode material, the metal phthalocyanine compound, the conductive agent, the binder and the solvent to form slurry, and coating the slurry on a current collector to obtain the positive electrode for the lithium ion battery.
Preferably, the mass ratio of the metal phthalocyanine compound is 0.5-10%, the mass ratio of the conductive agent is 1-20%, the mass ratio of the binder is 1-15% and the balance is the layered lithium-rich manganese oxide positive electrode material, based on the total mass of all raw materials except the solvent.
More preferably, the mass ratio of the metal phthalocyanine compound is 7 to 9%.
In the present invention, there is no particular requirement for the kind of current collector, and it is sufficient to select from the kinds commonly used in the art, such as aluminum foil, carbon-coated aluminum foil, nickel foil, and the like.
In the invention, the type of the conductive agent is not particularly required, and the conductive agent is selected from one or more of Super P, graphite, ketjen black, acetylene black, carbon nano tubes and graphene which are commonly used in the field.
In the invention, the binder is selected from one or more of common types in the field, such as polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyvinyl alcohol, polyacrylonitrile, styrene-butadiene rubber, sodium alginate and sodium carboxymethyl cellulose.
In the invention, the solvent is selected from water or a mixed solvent consisting of water and an organic solvent; the organic solvent is selected from the conventional classes in the art, such as ethanol, N-methylpyrrolidone, p-xylene, etc.
Preferably, the solvent is selected from water and the binder is selected from water-soluble binders such as sodium carboxymethyl cellulose.
In the slurry, the mass ratio of all raw materials except the solvent to the solvent is 1:2 to 10. Either too thin or too thick a slurry is detrimental to coating, further preferably 1:5.
the mixing may be by mixing means common in the art, such as mechanical ball milling, mechanical stirring, or magnetic stirring, among others.
Post-treatment, including drying, cold pressing or rolling treatment, is also required after coating, and the pressure adopted is 5-40 MPa.
The invention also discloses a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode adopts the metal phthalocyanine compound modified positive electrode for the lithium ion battery.
The negative electrode adopts raw material types common in the field, such as graphite carbon negative electrode, silicon-based negative electrode, metal oxide negative electrode, lithium metal negative electrode and the like.
The electrolyte also adopts non-aqueous electrolyte commonly used in the field, and comprises lithium salt and a non-aqueous solvent, wherein the lithium salt can be one or more of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate and lithium fluorohydroxysulfonate; the nonaqueous solvent can be one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and vinylene carbonate.
Experiments show that the lithium ion battery assembled by the positive electrode disclosed by the invention has excellent cycling stability and voltage retention rate, and the room-temperature ion conductivity of the lithium ion battery is obviously improved.
Compared with the prior art, the invention has the following advantages:
the invention discloses a positive electrode for a lithium ion battery, which takes a layered lithium-rich manganese positive electrode material coated by a metal phthalocyanine compound as a positive electrode active material, and experiments show that the cyclic stability and the voltage retention rate of the positive electrode can be effectively improved and the room-temperature ionic conductivity of the positive electrode can be obviously improved through coating the layered lithium-rich manganese positive electrode material by the metal phthalocyanine compound. The lithium ion battery assembled by the positive electrode circulates 500 times under the current density of 1C (1 C=200 milliamperes/gram), the capacity retention rate can reach 97% at most, the cycle is continued to be prolonged 1000 times, and the capacity retention rate still reaches at least 90%, and can reach 94.2% at most; the ionic conductivity at room temperature is improved by at least 6 orders of magnitude, and the maximum ionic conductivity is 8.
The preparation method of the positive electrode for the lithium ion battery disclosed by the invention is a conventional coating process in the field, wherein the metal phthalocyanine compound is formed in one step in the process of preparing an electrode, is uniformly distributed in slurry, has good dispersibility, becomes a uniform coating layer after the electrode is dried, and is coated on the surface of a lithium-manganese-rich positive electrode material; the preparation process does not increase electrode preparation steps, does not increase extra preparation cost, is simple to operate, has strong material preparation controllability, and is completely suitable for industrial production requirements.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the positive electrode material of the positive electrode sheet surface prepared in example 1;
FIG. 2 is an energy spectrum of a positive electrode material on the surface of a positive electrode sheet prepared in example 1;
FIG. 3 is an X-ray photoelectron spectrum (XPS) of O during the first charge and discharge of the positive electrode material on the surface of the positive electrode sheet prepared in example 1;
FIG. 4 is X-ray photoelectron Spectrometry (XPS) of N in the first charge-discharge process of (a) the positive electrode material of the positive electrode sheet surface prepared in example 1; (b) In-situ differential electrochemical mass spectrometry in the first cycle process;
fig. 5 is (a) a first charge-discharge curve of the assembled battery of example 1; (b) a 0.1C cycle performance curve; (C) a 1C cycle performance curve;
FIG. 6 is a plot of the median voltage decay for the assembled battery of example 1;
FIG. 7 is a spherical aberration correcting transmission electron microscope morphology of positive electrode material on the surface of a positive electrode sheet after 500 cycles at 200 mA/g for the assembled battery of example 1;
fig. 8 is (a) a first charge-discharge curve of the assembled battery of example 4; (b) a 1C cycle performance curve;
FIG. 9 is an X-ray photoelectron spectrum (XPS) of O during the first charge and discharge of the positive electrode material on the surface of the positive electrode sheet prepared in comparative example 1;
FIG. 10 is an in-situ differential electrochemical mass spectrum of the positive electrode material on the surface of the positive electrode sheet prepared in comparative example 1 during the first cycle;
fig. 11 is (a) a first charge-discharge curve of the assembled battery of comparative example 1; (b) a 0.1C cycle performance curve; (C) a 1C cycle performance curve;
FIG. 12 is a plot of the median voltage decay for the assembled battery of comparative example 1;
fig. 13 is a spherical aberration correcting transmission electron microscope morphology of positive electrode material on the surface of a positive electrode sheet after 500 cycles at 200 milliamp/g for the assembled battery of comparative example 1.
Detailed Description
The following examples are provided to further illustrate the present invention and should not be construed as limiting the scope of the invention.
Example 1
The component is 0.5Li 2 MnO 3 -0.5LiNi 0.33 Co 0.33 Mn 0.33 O 2 The particle size of the layered lithium-rich manganese anode material is 200-400 nm. Mixing a layered lithium-rich manganese anode material, a conductive agent Super P, a binder sodium carboxymethylcellulose (CMC) and copper phthalocyanine (CuPc) according to the mass ratio of 78:10:5:7, adding deionized water as a solvent (the mass ratio of the total mass of the raw materials to the deionized water is 1:5), magnetically stirring for 2 hours, ultrasonically dispersing for 2 hours, magnetically stirring for 2 hours to obtain a slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 80 ℃, and pressing at 10MPa to obtain a positive plate, wherein the positive plate is marked as a 7wt% CuPc coated positive plate.
The morphology of the positive electrode material in the positive electrode plate prepared in the embodiment is characterized, a picture of a spherical aberration correction transmission electron microscope is shown in fig. 1, and it can be seen from the picture that a coating layer with the thickness of about 2nm is arranged on the surface of the layered lithium-manganese-rich positive electrode particle. Energy Dispersive Spectroscopy (EDS) analysis was performed on the cathode material, and fig. 2 shows that copper element and nitrogen element are uniformly distributed on the surface of the lithium-rich manganese particles.
The electron microscope photo and the energy spectrum data are combined to show that in the positive electrode material prepared by the embodiment, copper phthalocyanine is uniformly coated on the surface of the layered lithium-manganese-rich positive electrode material particles, and the crystal structure of the lithium-manganese-rich positive electrode material is not damaged.
The electrochemical performance of the positive plate prepared in the embodiment is characterized by adopting 2025 button cells, and the positive plate is assembled in a glove box filled with Ar, wherein the water content and the oxygen content of the glove box are both less than 0.1 ppm. The anode is an electrode slice prepared by adopting a metal Li slice as a reference electrode and a counter electrode, the diaphragm adopts Celgard-2400, and the electrolyte is LiPF 6 (1 mol/L)/EC+DEC+EMC (1:1:1). The test voltage window is 2.0-4.8V, and the electrochemical performance of the battery is tested by adopting a constant current charging and discharging mode.
Fig. 3 is an X-ray photoelectron spectrum of oxygen during the first charge and discharge process of the positive electrode material on the surface of the positive electrode sheet prepared in this example. Peroxide ion O when charged to 4.8V (middle graph) 2 2- The content of (a) is less than that of the positive electrode of uncoated copper phthalocyanine (comparative example 1, fig. 9), indicating that the oxidation behavior at the surface is suppressed; when discharged to 2.0V (lower graph), peroxy ion O 2 2- The disappearance shows that the oxidation-reduction reaction of oxygen in the layered lithium-rich manganese positive electrode material coated by copper phthalocyanine has high reversibility.
Fig. 4 (a) is an X-ray photoelectron spectrum of nitrogen during the first charge and discharge of the positive electrode material on the surface of the positive electrode sheet prepared in this example. In the charging process, the N element can timely reduce the peroxy ion into oxygen ion O 2- The oxidation of the N element to oxygen is prevented, and the oxidized N element can be gradually reduced in the discharging process and continuously plays a role in the subsequent circulation. FIG. 4 (b) is an in-situ differential electrochemical mass spectrum of the positive electrode material on the surface of the positive electrode sheet prepared in the present example in the first charge/discharge processThe gas generation during charge and discharge is shown. Compared with the uncoated layered lithium-rich manganese positive electrode material (comparative example 1, fig. 10), the content of oxygen and carbon dioxide released by the positive electrode in the embodiment is greatly reduced, which indicates that the introduction of the copper phthalocyanine redox couple can effectively inhibit the oxygen release and the electrolyte side reaction of the layered lithium-rich manganese positive electrode material.
Fig. 5 (a) is a graph showing the first charge and discharge curves of the assembled battery of this example at a current density of 20 ma/g, with a first discharge capacity of up to 278.5 ma/g and a first coulombic efficiency of 78.10%. (b) The assembled battery of this example has a capacity of 264.6 milliamp/gram after 50 cycles with a capacity retention of 95.0% for a cycle performance curve at a current density of 20 milliamp/gram (0.1C). (c) The assembled battery for this example has a cycling performance profile of (1C) at a current density of 200 milliamp/gram. The first discharge capacity reaches 224.2 milliampere hour/gram. After the positive electrode is subjected to an activation process in the previous 100 weeks, the capacity of the positive electrode is slowly increased and kept stable in the subsequent cycles, after 500 cycles, the capacity still has 213.5 milliampere hours/gram, the capacity retention rate reaches 95.0%, after 1000 cycles, the capacity still has 207.5 milliampere hours/gram, the capacity retention rate reaches 92.6%, and the positive electrode has excellent cycle stability.
Fig. 6 is a graph of the median discharge voltage of the assembled battery of this example at a current density of 200 milliamp/gram, after 500 cycles, at a median voltage of 2.81V and a retention of 80.3%.
Fig. 7 is a spherical aberration correction transmission electron microscope image of the positive electrode material on the surface of the positive electrode sheet prepared in this example after 500 cycles. After 500 cycles, the structure of the layered lithium-rich manganese anode material particles still remains complete and ordered, and the inside of the layered lithium-rich manganese anode material particles still remains a layered structure. Compared with a spherical aberration correction transmission electron microscope picture (figure 13) of an uncoated layered lithium-rich manganese positive electrode material after 500 cycles, the copper phthalocyanine coating can inhibit spinel phase change of the lithium-rich manganese positive electrode in the cycle and inhibit metal ion dissolution, so that the complete and ordered crystal structure is maintained.
Through tests, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment reaches 3.95 multiplied by 10 -6 S/cm。
Example 2
The preparation process of the positive plate is basically the same as that of example 1, except that the mass ratio of the layered lithium-rich manganese positive electrode material, super P, CMC and copper phthalocyanine is replaced by 80:10:5:5, and the obtained positive plate is marked as a 5wt% CuPc coated positive plate. The battery assembly and test conditions were the same as in example 1.
By characterization, the XPS spectrum of O in the first charge and discharge process and the XPS spectrum of N in the first charge and discharge process of the positive electrode material on the surface of the positive electrode plate prepared by the embodiment. The results showed a similar law as in example 1.
The battery assembled in this example was tested to have a first discharge capacity of 273.4 milliamp hours per gram at a current density of 20 milliamp/gram; the first discharge capacity of the lithium ion battery is 219.5 milliampere hours/gram at the current density of 200 milliampere/gram, the capacity is 211.4 milliampere hours/gram after 500 times of circulation, the capacity retention rate is 96.3%, the capacity still has 203.6 milliampere hours/gram after 1000 times of circulation, the capacity retention rate reaches 92.8%, and the lithium ion battery shows excellent circulation stability.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 1.27 multiplied by 10 -6 S/cm。
Example 3
The preparation process of the positive plate is basically the same as that of example 1, except that the mass ratio of the layered lithium-rich manganese positive electrode material, super P, CMC and CuPc is replaced by 76:10:5:9, and the obtained positive plate is marked as a 9wt% CuPc coated positive plate. The battery assembly and test conditions were the same as in example 1.
The positive electrode material on the surface of the positive electrode plate prepared in the embodiment is characterized by a transmission electron microscope, and a layer of uniform coating layer with the thickness of about 4nm is arranged on the surface of the layered lithium-rich manganese positive electrode material particles.
Further characterizes XPS spectrum of O in the first charge and discharge process and XPS spectrum of N in the first charge and discharge process of the positive electrode material on the surface of the positive electrode plate prepared by the embodiment. The results showed a similar law as in example 1.
The test shows that the first discharge capacity of the battery assembled by the embodiment is 267.6 milliampere hours/gram at the current density of 20 milliampere/gram, the first discharge capacity of the battery reaches 223.5 milliampere hours/gram at the current density of 200 milliampere/gram, the capacity of the battery is 215.5 milliampere hours/gram after 500 times of circulation, the capacity retention rate is 96.4%, the capacity of the battery still reaches 210.6 milliampere hours/gram after 1000 times of circulation, and the capacity retention rate reaches 94.2%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 1.14x10 -6 S/cm。
Example 4
The preparation process of the positive plate is basically the same as that of example 1, except that:
the copper phthalocyanine is replaced by iron phthalocyanine (FePc), the mass ratio of the layered lithium-rich manganese anode material, super P, CMC and iron phthalocyanine is replaced by 84.5:10:5:0.5, and the obtained anode sheet is marked as an anode sheet coated with 0.5wt% FePc. The battery assembly and test conditions were the same as in example 1.
Fig. 8 (a) is a first charge-discharge curve of the assembled battery of this example at a current density of 20 milliamp/gram, with a first discharge capacity of up to 282.4 milliamp/gram and a first coulomb efficiency of 76.3%. (b) The assembled battery for this example has a cycling performance profile of (1C) at a current density of 200 milliamp/gram. The first discharge capacity of the material reaches 217.5 milliampere hours/gram, after 500 times of circulation, the capacity still has 209.7 milliampere hours/gram, the capacity retention rate is 96.4 percent, after 1000 times of circulation, the capacity still has 196.3 milliampere hours/gram, the capacity retention rate reaches 90.3 percent, and the material shows excellent circulation stability.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 5.82 multiplied by 10 -7 S/cm。
Example 5
The preparation process of the positive plate is basically the same as that of example 4, except that the mass ratio of the layered lithium-rich manganese positive electrode material, super P, CMC and iron phthalocyanine is replaced by 78:10:5:7, and the obtained positive plate is marked as a 7wt% FePc coated positive plate. The battery assembly and test conditions were the same as in example 1.
The assembled battery of this example had a first discharge capacity of up to 278.3 milliamp/gram and a first coulomb efficiency of 777.4% at a current density of 20 milliamp/gram. The initial discharge capacity of (1C) reaches 218.2 milliampere hours/g at a current density of 200 milliampere/g, the capacity still remains 208.1 milliampere hours/g after 500 cycles, the capacity retention rate is 95.4%, the capacity is 196.7 milliampere hours/g after 1000 cycles, and the capacity retention rate is 90.1%. Exhibits excellent cycle stability.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 4.26 multiplied by 10 -7 S/cm。
Example 6
The preparation process of the positive plate is basically the same as that of example 4, except that iron phthalocyanine is replaced with manganese phthalocyanine (MnPc) of equal mass, and the obtained positive plate is marked as a positive plate coated with 0.5wt% MnPc. The battery assembly and test conditions were the same as in example 1.
The battery assembled in this example has a first discharge capacity of 283.6 milliamp/gram and a coulomb efficiency of 81.9% at a current density of 20 milliamp/gram. The first discharge capacity of the lithium ion battery is 210.0 milliampere hour/gram under the current density of 200 milliampere/gram, the capacity is kept at 201.6 milliampere hour/gram after 500 times of circulation, the capacity retention rate is 96.0%, and the capacity still has 195.7 milliampere hour/gram after 1000 times of circulation, and the capacity retention rate reaches 93.2%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 8.31 multiplied by 10 -8 S/cm。
Example 7
The preparation process of the positive plate is basically the same as that of example 1, except that:
the copper phthalocyanine is replaced by cobalt phthalocyanine (CoPc), and the mass ratio of the layered lithium-rich manganese positive electrode material, super P, CMC and CoPc is replaced by 82:10:5:3, and the obtained positive electrode sheet is marked as a 3wt% CoPc coated positive electrode sheet. The battery assembly and test conditions were the same as in example 1.
The battery assembled in this example has a first discharge capacity of 280.7 milliamp/gram and a coulomb efficiency of 75.6% at a current density of 20 milliamp/gram. The first discharge capacity of the lithium ion battery is 212.5 milliampere-hour/gram under the current density of 200 milliampere/gram, the capacity is kept at 206.5 milliampere-hour/gram after 500 times of circulation, the capacity keeping rate is 97.2%, and the capacity still has 193.4 milliampere-hour/gram after 1000 times of circulation, and the capacity keeping rate reaches 91.0%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 6.37 multiplied by 10 -8 S/cm。
Example 8
The preparation process of the positive electrode sheet was substantially the same as in example 1, except that a composition of 0.7Li was used 2 MnO 3 -0.3LiNi 0.33 Co 0.33 Mn 0.33 O 2 Layered lithium-rich manganese oxide positive electrode materials. The battery assembly and test conditions were the same as in example 1.
The assembled battery of this example had a first discharge capacity of 272.4 milliamp/gram and a first coulomb efficiency of 71.9% at a current density of 20 milliamp/gram. The primary discharge capacity of the lithium ion battery is 201.4 milliampere-hour/gram under the current density of 200 milliampere/gram, the capacity reaches 191.6 milliampere-hour/gram after 500 times of circulation, the capacity retention rate reaches 95.1 percent, and the capacity still reaches 183.7 milliampere-hour/gram after 1000 times of circulation, and the capacity retention rate reaches 91.2 percent.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the embodiment is 1.95 multiplied by 10 -6 S/cm。
Comparative example 1
The preparation process of the positive plate is basically the same as that of the example 1, except that copper phthalocyanine is not added, and the layered lithium-rich manganese oxide, super P and CMC are mixed according to the mass ratio of 85:10:5. The battery assembly and test conditions were the same as in example 1.
FIG. 9 is an X-ray photoelectron spectrum of oxygen during the first charge and discharge of the positive electrode material prepared in this comparative example, the peak at 530.5eV corresponding to the peroxy ion O 2 2- Is a combination of the binding energy of the above-mentioned materials. When charged to 4.8V, obvious peroxide is generated, the content of the peroxide is larger, the oxygen reaction on the surface is more intense, and meanwhile, the electrolyte is partially oxidized, so that the interface reaction is serious. And the peroxide ions remain residual when discharged to 2.0V (lower panel), indicating poor reversibility of oxygen reaction.
Fig. 10 is an in-situ differential electrochemical mass spectrum of the positive electrode material on the surface of the positive electrode sheet prepared in this comparative example in the first charge and discharge process, and shows the gas generation condition in the charge and discharge process. The positive electrode in the comparative example releases a large amount of oxygen and carbon dioxide content, which indicates that the untreated layered lithium-rich manganese positive electrode has serious oxygen evolution reaction and electrode liquid side reaction.
Fig. 11 (a) is a first charge-discharge curve of the assembled battery of this comparative example at a current density of 20 milliamp/gram, with a first discharge capacity of 272.8 milliamp/gram and a first coulombic efficiency of 79.5%.
(b) The cell assembled for this comparative example had a cycle performance curve at a current density of 20 milliamp/gram (0.1C), a capacity cycle decay over a 50 week test range, a capacity of only 233.4 milliamp/gram after 50 cycles, and a retention of 86.1%. (c) The cycling performance curve of the cell assembled for this comparative example at a current density of 200 milliamp/gram (1C). The first discharge capacity is 214.2 milliampere hours/gram, the capacity is rapidly attenuated in the circulation process, after 500 times of circulation, the capacity is only 119.6 milliampere hours/gram, and the capacity retention rate is only 55.8%.
Fig. 12 is a plot of the median discharge voltage of the assembled battery of this comparative example at a current density of 200 milliamp/gram, with a rapid voltage decay after 500 cycles, a median voltage of 2.61V and a retention of 73.9%.
Fig. 13 is a spherical aberration correction transmission electron microscope image of the positive electrode material in this comparative example after 500 cycles. After 500 cycles, a large amount of spinel phases are generated, and a large amount of oxygen defects and voids exist on the surface and in the bulk phase, which indicates that the lithium-rich manganese oxide material of the comparative example undergoes serious structural damage and phase transformation, and is obviously inferior to the structure stability of the embodiment 1 of the invention.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the comparative example is 6.29 multiplied by 10 -14 S/cm。
Comparative example 2
The preparation process of the positive plate is basically the same as that of example 7, except that CuPc is not added, and layered lithium-rich manganese oxide, super P and CMC are mixed according to the mass ratio of 85:10:5. The battery assembly and test conditions were the same as in example 1.
The positive electrode sheet-assembled battery prepared in this comparative example had a first discharge capacity of 252.1 milliamp hour/gram and a first coulombic efficiency of 75.0% at a current density of 20 milliamp/gram. The first discharge capacity and coulombic efficiency were not as good as those of the examples of the present invention. At a current density of 200 milliamp/gram (1C) its first discharge capacity was 197.6 milliamp hours/gram, after 500 cycles the capacity decayed rapidly, only 144.8 milliamp hours/gram and the capacity retention was only 73.3%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the comparative example is 5.82 multiplied by 10 -14 S/cm, is clearly inferior to the examples of the present invention.
Comparative example 3
The preparation process of the positive electrode sheet was substantially the same as in example 1, except that copper phthalocyanine was replaced with phthalocyanine of equal quality. The battery assembly and test conditions were the same as in example 1.
The test shows that the first discharge capacity of the battery assembled by the positive plate prepared in the comparative example is 115.2 milliampere hours/gram at the current density of 20 milliampere/gram, and the first coulomb efficiency is 60.3%. The initial discharge capacity of (1C) was 73.7 milliamp hours/gram at a current density of 200 milliamp/gram, and after 500 cycles, the capacity reached 38.9 milliamp hours/gram, with a capacity retention of 52.8%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the comparative example is 3.62 multiplied by 10 -14 S/cm。
Comparative example 4
The preparation process of the positive electrode sheet was substantially the same as in example 1, except that copper phthalocyanine was replaced with benzonitrile of equal mass. The battery assembly and test conditions were the same as in example 1.
The test shows that the first discharge capacity of the battery assembled by the positive plate prepared in the comparative example is 103.5 milliampere hours/gram at the current density of 20 milliampere/gram, and the first coulomb efficiency is 52.3%. The initial discharge capacity of (1C) was 57.1 milliamp hours/gram at a current density of 200 milliamp/gram, and after 500 cycles, the capacity reached 23.9 milliamp hours/gram, and the capacity retention was 41.9%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the comparative example is 6.22 multiplied by 10 -14 S/cm。
Comparative example 5
The preparation process of the positive electrode sheet was basically the same as in example 1, except that copper phthalocyanine was replaced with copper chloride of equal quality. The battery assembly and test conditions were the same as in example 1.
The positive electrode sheet assembled battery prepared in this comparative example was tested to have a first discharge capacity of 165.3 milliamp/gram and a first coulomb efficiency of 73.9% at a current density of 20 milliamp/gram. The initial discharge capacity of (1C) at a current density of 200 mA/g was 112.6 mA/g, and after 500 cycles, the capacity reached 78.1 mA/g, and the capacity retention was 69.4%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the comparative example is 8.69 multiplied by 10 -11 S/cm。
Comparative example 6
The preparation process of the positive plate is basically the same as that of example 4, except that iron phthalocyanine is replaced with equal mass of ferric chloride. The battery assembly and test conditions were the same as in example 1.
The test shows that the first discharge capacity of the battery assembled by the positive plate prepared in the comparative example is 185.6 milliampere hours/gram at the current density of 20 milliampere/gram, and the first coulomb efficiency is 65.7%. The initial discharge capacity of (1C) was 128.3 mA/g at a current density of 200 mA/g, and after 500 cycles, the capacity reached 56.9 mA/g, and the capacity retention was 44.3%.
Through testing, the room-temperature ionic conductivity of the positive electrode material on the surface of the positive electrode sheet prepared in the comparative example is 2.91 multiplied by 10 -11 S/cm。
The foregoing is merely a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and the present invention is described by using the specific examples, which are only for aiding in understanding the present invention, and are not limited thereto. Several simple deductions, variations, substitutions or combinations may also be made by those skilled in the art to which the invention pertains based on the inventive concept. Such deductions, modifications, substitutions or combinations are also within the scope of the claims of the present invention.
Claims (10)
1. The positive electrode for the phthalocyanine compound modified lithium ion battery comprises a current collector and a positive electrode material deposited on the surface of the current collector, wherein the positive electrode material comprises a positive electrode active component and is characterized in that:
the positive electrode active component comprises a layered lithium-rich manganese oxide positive electrode material and a coating layer which is coated on the surface of the layered lithium-rich manganese oxide positive electrode material and contains a metal phthalocyanine compound;
the metal phthalocyanine compound is selected from one or more of iron phthalocyanine, manganese phthalocyanine, copper phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine and zinc phthalocyanine.
2. The positive electrode for a lithium ion battery modified with a phthalocyanine compound according to claim 1, wherein:
the structural general formula of the layered lithium-rich manganese oxide positive electrode material is xLi 2 MnO 3 -(1-x)LiMO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is selected from one or more of Ni, co, mn, cr, fe, al, nb, mo, ru, and x is more than or equal to 0 and less than or equal to 1.
3. The positive electrode for a lithium ion battery modified with a phthalocyanine compound according to claim 1, wherein:
the thickness of the coating layer containing the metal phthalocyanine compound is 1-50 nm.
4. The positive electrode for a lithium ion battery modified with a phthalocyanine compound according to claim 1, wherein the metal phthalocyanine compound is one or more selected from copper phthalocyanine, iron phthalocyanine, manganese phthalocyanine and cobalt phthalocyanine.
5. The positive electrode for a lithium ion battery modified with a phthalocyanine compound according to claim 1, wherein the metal phthalocyanine compound is selected from copper phthalocyanine and/or iron phthalocyanine.
6. The positive electrode for a lithium ion battery modified with a phthalocyanine compound according to claim 1, wherein the metal phthalocyanine compound is selected from copper phthalocyanines.
7. A method for producing a positive electrode for a lithium ion battery modified with a phthalocyanine compound according to any one of claims 1 to 6, comprising:
and uniformly mixing the layered lithium-rich manganese oxide positive electrode material, the metal phthalocyanine compound, the conductive agent, the binder and the solvent to form slurry, and coating the slurry on a current collector to obtain the positive electrode for the lithium ion battery.
8. The method for producing a positive electrode for a phthalocyanine compound-modified lithium ion battery according to claim 7, wherein:
the mass ratio of the metal phthalocyanine compound is 0.5 to 10% based on the total mass of all the raw materials except the solvent.
9. The method for producing a positive electrode for a phthalocyanine compound-modified lithium ion battery according to claim 7, wherein:
the mass ratio of the conductive agent is 1-20%, the mass ratio of the binder is 1-15% by the total mass of all raw materials except the solvent, and the balance is the layered lithium-rich manganese oxide positive electrode material.
10. A lithium ion battery comprising a positive electrode and a negative electrode, wherein the positive electrode is a positive electrode for a lithium ion battery modified with the phthalocyanine compound according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311246516.XA CN117154007A (en) | 2023-09-26 | 2023-09-26 | Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311246516.XA CN117154007A (en) | 2023-09-26 | 2023-09-26 | Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117154007A true CN117154007A (en) | 2023-12-01 |
Family
ID=88900826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311246516.XA Pending CN117154007A (en) | 2023-09-26 | 2023-09-26 | Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117154007A (en) |
-
2023
- 2023-09-26 CN CN202311246516.XA patent/CN117154007A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110024188B (en) | Negative electrode material and nonaqueous electrolyte secondary battery | |
| EP2924785B1 (en) | Binder for use in positive electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery containing said binder, lithium ion secondary battery using said positive electrode, and electrical machinery and apparatus | |
| KR101342601B1 (en) | Negative active material, manufacturing method thereof, and lithium battery containing the material | |
| KR101587293B1 (en) | Li-Ni-BASED COMPOSITE OXIDE PARTICLE POWDER FOR RECHARGEABLE BATTERY WITH NONAQUEOUS ELECTROLYTE, PROCESS FOR PRODUCING THE POWDER, AND RECHARGEABLE BATTERY WITH NONAQUEOUS ELECTROLYTE | |
| JP4945906B2 (en) | Secondary battery negative electrode and secondary battery using the same | |
| WO2014022986A1 (en) | Composite cathode materials with controlled irreversible capacity loss for lithium ion batteries | |
| US8722244B2 (en) | Lithium secondary battery and method of manufacturing same | |
| JP2009295465A (en) | Positive electrode active material for lithium secondary battery and manufacturing method | |
| KR101166281B1 (en) | Surface-coated lithium titanate powder, electrode, and secondary battery comprising the same | |
| CN113424340A (en) | Anode active material, method of preparing the same, and lithium secondary battery including anode of the anode active material | |
| JP2010080407A (en) | Positive electrode active material, positive electrode, and non-aqueous electrolyte secondary battery | |
| CN113113586B (en) | Positive electrode for lithium ion battery and preparation method and application thereof | |
| JP7258372B2 (en) | Positive electrode active material, manufacturing method thereof, and lithium secondary battery including positive electrode containing the same | |
| CN110495026B (en) | Negative electrode material and nonaqueous electrolyte secondary battery | |
| CN112292350B (en) | Fluorinated oxides based on Li and Mn | |
| JP7165913B2 (en) | Non-aqueous electrolyte secondary battery | |
| US20180062165A1 (en) | Electrode material, method for manufacturing electrode material, electrode, and lithium ion battery | |
| CN114846652A (en) | Positive electrode active material, method for preparing same, and lithium secondary battery including positive electrode including same | |
| JP6802111B2 (en) | Method for manufacturing negative electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and negative electrode material for non-aqueous electrolyte secondary battery | |
| KR101278832B1 (en) | Surface-coated lithium titanate powder, electrode, and secondary battery comprising the same | |
| CN117936787A (en) | Positive electrode lithium supplementing agent, preparation method and application thereof | |
| CN109216692B (en) | Modified ternary cathode material, preparation method thereof and lithium ion battery | |
| CN117154007A (en) | Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof | |
| US11171321B2 (en) | Electrode material and method for manufacturing the same | |
| CN117293273A (en) | Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof |
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 |