CN115084475B - Quick ion conductor coated graphite composite material and preparation method and application thereof - Google Patents
Quick ion conductor coated graphite composite material and preparation method and application thereof Download PDFInfo
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- CN115084475B CN115084475B CN202210783424.4A CN202210783424A CN115084475B CN 115084475 B CN115084475 B CN 115084475B CN 202210783424 A CN202210783424 A CN 202210783424A CN 115084475 B CN115084475 B CN 115084475B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 145
- 239000010439 graphite Substances 0.000 title claims abstract description 145
- 239000010416 ion conductor Substances 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 64
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 47
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000013538 functional additive Substances 0.000 claims abstract description 27
- 239000002184 metal Chemical class 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 30
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- URXQDXAVUYKSCK-UHFFFAOYSA-N hexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH+](C)C URXQDXAVUYKSCK-UHFFFAOYSA-N 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 12
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000013077 target material Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 6
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 54
- 230000008569 process Effects 0.000 abstract description 17
- 238000003763 carbonization Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 10
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- 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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention provides a fast ion conductor coated graphite composite material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing graphite, metal salt and polymer, and sintering to obtain a porous graphite composite; the metal salt comprises any one or a combination of at least two of nickel salt, cobalt salt and ferric salt; (2) Mixing the porous graphite complex, a catalyst, a functional additive and an organic solvent, and carrying out soaking reaction to obtain a graphite precursor; (3) And coating a fast ion conductor on the surface of the graphite precursor by adopting a magnetron sputtering method to obtain the fast ion conductor coated graphite composite material. The porous graphite composite body is prepared, amorphous carbon and a fast ion conductor are grown on the surface of the porous graphite composite body through magnetron sputtering, the traditional carbonization process is omitted, and the deposition is more uniform and compact; the amorphous carbon and the fast ion conductor cooperate to promote the electronic and ion conductivity of the material, and the material has good fast charge and circulation performance.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a fast ion conductor coated graphite composite material, and a preparation method and application thereof.
Background
Along with the improvement of the requirements of the market on the quick charge performance of the lithium ion battery, the quick charge performance of the lithium ion battery anode material is improved while the lithium ion battery anode material has high energy density. The measures for improving the quick charge performance of the anode material at present mainly comprise: the method reduces the aggregate particle size of the material, increases the amorphous carbon coating proportion and improves the lithium ion intercalation and deintercalation channel of the material for material surface modification, and the method achieves the improvement of the quick charge performance by reducing the electron impedance of the material surface coating layer. The fast ion conductor is a compound with high lithium ion conductivity, and can rapidly realize rapid exchange of lithium ions in the charge and discharge process, so that the effective improvement of the fast charge performance is realized.
The fast ion conductor has a problem of poor electron conductivity when used alone, and it is required to be a material having good electron conductivityThe materials are mixed for use to achieve the improvement of the quick charge performance. The patent CN108987687B provides a low-temperature lithium ion battery graphite cathode material and a preparation method thereof, and the particle size of graphite is controlled by ball milling and spray drying, intercalation reaction and surface coating are carried out on graphite powder, a fast ion conductor coating layer is formed on the surface of the graphite, and the diffusion capacity of lithium ions is improved. Patent CN114628659A discloses a graphite negative electrode composite material for a power battery and a preparation method thereof, wherein the inner core of the material is graphite, and the outer shell is Li 5 FeO 4 And the rapid ion conductor is formed by a multi-layer structure, so that the rate capability of the anode material is improved. Patent CN202110798078.2 discloses a high-energy density quick-charging graphite composite negative electrode material, a preparation method thereof and a lithium ion battery, wherein the patent adopts a liquid phase method to prepare the graphite composite negative electrode material with a core-shell structure, the composite negative electrode material comprises a graphite inner core, a quick ion conductor middle layer and a fluorine-containing composite carbon material outer layer which are sequentially arranged from inside to outside, and the quick ion conductor is Li 7 La 3 Zr 2 O 12 And Li (lithium) 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 At least one of the graphite composite anode materials prepared by the patent has the problem of poor consistency of coating layers, and the materials are easily stripped in the charge and discharge process between each coating layer of the shell, so that the circulation and power performance of the materials are affected.
In the prior art, a fast ion conductor is coated on the surface of graphite to improve the fast charging performance of a graphite negative electrode material, but the prepared graphite composite material has poor coating layer consistency, and the power and cycle performance of the material are improved to a limited extent, so that the application of the fast ion conductor coated graphite composite material in the field of lithium ion batteries is affected. Therefore, the preparation of the graphite composite material with excellent quick charge performance has important significance for research and development of lithium ion batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a fast ion conductor coated graphite composite material, and a preparation method and application thereof. The porous graphite composite is prepared firstly, amorphous carbon grows on the surface of the porous graphite composite through soaking reaction and magnetron sputtering, a fast ion conductor is deposited, the deposition density is high, the process is controllable, the deposition layer is thinner, the energy density of the material is improved, the traditional carbonization process is omitted, and the efficiency is improved; meanwhile, the generated amorphous carbon and the fast ion conductor cooperate to improve the electronic and ion conductivity of the material, and the prepared fast ion conductor coated graphite composite material has higher first discharge capacity, first charge and discharge efficiency and good fast charge performance and cycle performance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a fast ion conductor coated graphite composite material, which comprises the following steps:
(1) Mixing graphite, metal salt and polymer, and sintering to obtain a porous graphite composite;
the metal salt comprises any one or a combination of at least two of nickel salt, cobalt salt and ferric salt;
(2) Mixing the porous graphite complex, a catalyst, a functional additive and an organic solvent, and carrying out soaking reaction to obtain a graphite precursor;
(3) And coating a fast ion conductor on the surface of the graphite precursor by adopting a magnetron sputtering method to obtain the fast ion conductor coated graphite composite material.
The preparation method prepares the fast ion conductor coated graphite composite material through the steps of sintering, soaking reaction, magnetron sputtering and the like, and the prepared material has high electronic and ion conductivity, high first discharge capacity, first charge and discharge efficiency, good fast charge performance and good cycle performance, and the technical principle is as follows:
firstly, graphite, specific metal salt and polymer are mixed and sintered in the step (1), most of the polymer is decomposed to generate substances such as carbon monoxide, carbon dioxide and water in the sintering process, and the specific metal salt generates metal oxide to achieve the purpose of pore-forming, so that micron and/or millimeter holes are formed in the material to obtain a porous graphite composite, the liquid absorption and retention capacity of the material is improved, and the lithium ion transmission in the charging and discharging processes is facilitated; meanwhile, the generated metal oxide (such as nickel oxide, cobalt oxide, iron oxide and the like) has a catalytic effect, and can provide a catalytic effect for generating amorphous carbon at a high temperature in the follow-up magnetron sputtering.
Secondly, in the step (2), the obtained porous graphite complex is mixed with a catalyst, a functional additive and an organic solvent for soaking reaction to obtain a graphite precursor containing the catalyst; in the subsequent magnetron sputtering process, part of the organic solvent volatilizes, and the residual part of the organic solvent and the functional additive as well as the residual small part of the polymer in the step (1) are decomposed to generate amorphous carbon, so that the amorphous carbon is coated on the surface of graphite, and the quick charge performance of the material is improved; meanwhile, the functional additive can generate a synergistic effect with a fast ion conductor subjected to subsequent magnetron sputtering at a high temperature of the magnetron sputtering, and the fast ion conductor is promoted to be deposited on the graphite surface more uniformly and compactly.
Thirdly, the invention adopts a magnetron sputtering method to coat a fast ion conductor on the surface of the graphite precursor in the step (3), and in the magnetron sputtering process, residual part of organic solvent, functional additive and small part of polymer are uniformly decomposed to generate amorphous carbon under the action of a catalyst, thereby omitting the traditional carbonization process and improving the efficiency; the generated amorphous carbon and a fast ion conductor sputtered on the surface of graphite can also produce a synergistic effect, so that the electronic and ion conductivity of the material is improved, and the fast charging performance of the material is improved; compared with the traditional liquid phase/solid phase coating material, the magnetron sputtering method has the advantages of high deposition density, high efficiency, controllable process, thinner coating layer and the like, indirectly improves the energy density of the material, simultaneously, the preparation method is adopted for coating the fast ion conductor, the fast ion conductor and the amorphous carbon are uniformly combined, excessive lithium ions are released by the fast ion conductor in the first charge and discharge process, the irreversible capacity of the material can be reduced, the first efficiency is improved, the first efficiency and the amorphous carbon cooperate, and the fast charge performance and the cycle performance of the fast ion conductor coated graphite composite material are improved.
Preferably, the mass ratio of graphite, metal salt and polymer in the step (1) is 100 (1-5): 5-10, wherein the metal salt can be selected from 1-5, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, and the polymer can be selected from 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10, and the like.
In the invention, graphite, metal salt and polymer are mixed and sintered in a certain proportion, so that the pore-forming effect of the polymer and the metal salt and the subsequent catalytic effect of the metal salt can be further improved, in the proportion range, the improvement of the electronic conductivity of the material and the transmission of ions are facilitated, the circulation and the power performance are balanced, when the metal salt is more, the circulation performance is reduced, and when the metal salt is less, the power performance is reduced.
Preferably, the nickel salt in step (1) includes any one or a combination of at least two of nickel carbonate, nickel chloride, nickel sulfate and nickel nitrate, for example, a combination of nickel carbonate and nickel chloride, a combination of nickel sulfate and nickel nitrate, or a combination of nickel carbonate, nickel chloride, nickel sulfate and nickel nitrate.
Preferably, the cobalt salt in step (1) includes any one or a combination of at least two of cobalt chloride, cobalt nitrate and cobalt sulfate, for example, a combination of cobalt chloride and cobalt sulfate, a combination of cobalt nitrate and cobalt sulfate, or a combination of cobalt chloride, cobalt nitrate and cobalt sulfate.
Preferably, the ferric salt in step (1) includes any one or a combination of at least two of ferric chloride, ferric sulfate and ferric nitrate, for example, the ferric chloride and ferric sulfate, the ferric sulfate and ferric nitrate, or the ferric chloride, ferric sulfate and ferric nitrate, etc.
As a preferable technical scheme of the preparation method, the polymer in the step (1) comprises any one or at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethyl cellulose and polyvinylidene fluoride, and can be, for example, a combination of polyvinyl alcohol and polyacrylic acid, a combination of polytetrafluoroethylene and sodium polymethyl cellulose, a combination of sodium polymethyl cellulose and polyvinylidene fluoride, or a combination of polyvinyl alcohol, polyacrylic acid and polytetrafluoroethylene.
The invention preferably adopts a specific polymer which has a certain bonding function, realizes the uniform dispersion of metal salt, graphite and binder, and can leave uniform holes on the porous graphite composite body after sintering, thereby being beneficial to the liquid absorption and retention of the material.
Preferably, the sintering temperature in the step (1) is 300 to 500 ℃, and may be 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, or the like, for example.
Preferably, the sintering time in the step (1) is 1 to 6 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours or the like can be used.
Preferably, the sintering of step (1) is performed under an air atmosphere.
As a preferred technical scheme of the preparation method, the mass ratio of the catalyst, the functional additive, the organic solvent and the porous graphite complex in the step (2) is (1-5): (0.5-2): (100-500): 100, wherein the selection range of the catalyst (1-5) can be, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, the selection range of the functional additive (0.5-2) can be, for example, 0.5, 0.8, 1, 1.2, 1.5, 1.8 or 2, and the selection range of the organic solvent (100-500) can be, for example, 100, 150, 200, 250, 300, 350, 400, 450 or 500, and the like.
The catalyst, the functional additive, the organic solvent and the porous graphite compound which are selected in a proper proportion can promote the reaction process of the material and provide a basis for forming isotropic amorphous carbon later, when the catalyst is too much, the self-discharge of the material is larger, and when the catalyst is too little, the preparation period of the material is longer and the impedance of the amorphous carbon is too large.
Preferably, the catalyst in the step (2) comprises any one or at least two of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and ferric nitrate, for example, the combination of ferric chloride and cobalt chloride, the combination of nickel chloride and ferric nitrate, the combination of cobalt nitrate and ferric nitrate, or the combination of cobalt chloride, nickel chloride and ferric nitrate; by adopting the catalyst, in the subsequent magnetron sputtering process, the decomposition of organic carbon sources such as polymers, functional additives, organic solvents and the like in the material can be promoted to generate amorphous carbon.
As a preferable technical scheme of the preparation method of the invention, the functional additive in the step (2) comprises any one or at least two of hexadecyl dimethyl ammonium chloride, dodecyl dimethyl amine oxide and octadecyl trimethyl ammonium chloride, and can be, for example, a combination of hexadecyl dimethyl ammonium chloride and dodecyl dimethyl amine oxide, a combination of octadecyl trimethyl ammonium chloride and hexadecyl dimethyl ammonium chloride, or a combination of hexadecyl dimethyl ammonium chloride, dodecyl dimethyl amine oxide and octadecyl trimethyl ammonium chloride.
In the invention, a specific nitrogen-containing functional additive with a ring structure is preferably adopted, and the specific carbon-nitrogen ring structure forms nitrogen doped amorphous carbon with a specific structure and orientation after magnetron sputtering, so that the impedance is reduced, and the power performance of the fast ion conductor coated graphite composite material is improved.
Preferably, the organic solvent in the step (2) includes any one or a combination of at least two of carbon tetrachloride, cyclohexane, xylene, N-dimethylpyrrolidone, cyclohexanone and isobutanol, for example, a combination of carbon tetrachloride and cyclohexane, a combination of xylene and N, N-dimethylpyrrolidone, a combination of cyclohexanone and isobutanol, or a combination of carbon tetrachloride, cyclohexane, xylene and N, N-dimethylpyrrolidone, etc.
As a preferable mode of the preparation method of the present invention, the soaking reaction in the step (2) is carried out at a temperature of 50 to 150℃and may be carried out at 50℃60℃70℃80℃90℃100℃110℃120℃130℃140℃150 ℃.
Preferably, the pressure of the soaking reaction in the step (2) is 1-3 MPa, for example, 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 2MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3MPa, etc.
Preferably, the time of the soaking reaction in the step (2) is 1-6 h, for example, 1h, 2h, 3h, 4h, 5h or 6h, etc.
As a preferred technical scheme of the preparation method, the step (3) is carried out according to the following mode:
and (3) taking the fast ion conductor as a target material, taking the graphite precursor as a matrix, and performing magnetron sputtering to coat the fast ion conductor on the surface of the graphite precursor, thereby obtaining the fast ion conductor coated graphite composite material.
Preferably, the distance between the target and the substrate is 10-50 mm, for example, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm or 50mm, etc.
Preferably, the gas in the atmosphere of the magnetron sputtering is any one or a combination of at least two of nitrogen, argon and ammonia, for example, a combination of nitrogen and argon, a combination of argon and ammonia, or a combination of nitrogen, argon and ammonia, etc.
Preferably, the air pressure of the vacuum chamber of the magnetron sputtering is 1×10 -1 ～10×10 -1 Pa may be, for example, 1×10 -1 Pa、2×10 -1 Pa、3×10 -1 Pa、4×10 -1 Pa、5×10 -1 Pa、6×10 -1 Pa、7×10 -1 Pa、8×10 -1 Pa、9×10 -1 Pa or 10×10 -1 Pa, and the like.
Preferably, the deposition rate of the magnetron sputtering is 0.01-10A/min, for example, 0.01A/min, 0.1A/min, 1A/min, 2A/min, 3A/min, 4A/min, 5A/min, 6A/min, 7A/min, 8A/min, 9A/min or 10A/min, etc.
Preferably, the deposition time of the magnetron sputtering is 1 to 30min, for example, 1min, 2min, 4min, 6min, 8min, 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30min, etc.
The invention can adjust the thickness and content of the fast ion conductor deposition by adjusting the deposition rate and deposition time of the magnetron sputtering, thereby further improving the fast charging performance of the fast ion conductor coated graphite composite material.
Preferably, the fast ion conductor of step (3) comprises Li 5 FeO 4 、Li 2 Mn 2 O 4 、Li 3 N, lithium nickelate, lithium sulfide and fluorineAny one or a combination of at least two of lithium compounds, for example, li 5 FeO 4 And Li (lithium) 2 Mn 2 O 4 Is a combination of Li 2 Mn 2 O 4 And Li (lithium) 3 N, lithium nickelate and lithium sulfide, or Li 3 N, lithium nickelate, a combination of lithium sulfide and lithium fluoride, and the like.
According to the invention, the graphite composite material coated by the fast ion conductor is prepared by adopting the appropriate fast ion conductor and matching with magnetron sputtering, so that the function of high fast ion conductivity can be further exerted, and the fast charge performance and the cycle performance of the material are improved.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) Mixing graphite, metal salt and polymer with the mass ratio of (1-5) being (5-10), and sintering for 1-6 hours in the air atmosphere, wherein the sintering temperature is 300-500 ℃, so as to obtain a porous graphite composite body;
the metal salt comprises any one or a combination of at least two of nickel salt, cobalt salt and ferric salt, and the polymer comprises any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethyl cellulose and polyvinylidene fluoride;
(2) Adding a catalyst and a functional additive into an organic solvent, dispersing uniformly, adding the porous graphite composite, mixing, carrying out soaking reaction for 1-6 h at the temperature of 50-150 ℃ and the pressure of 1-3 MPa, filtering and drying to obtain a graphite precursor;
the mass ratio of the catalyst to the functional additive to the organic solvent to the porous graphite complex is (1-5): (0.5-2): (100-500): 100, wherein the catalyst comprises any one or a combination of at least two of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and ferric nitrate, the functional additive comprises any one or a combination of at least two of hexadecyl dimethyl ammonium chloride, dodecyl dimethyl amine oxide and octadecyl trimethyl ammonium chloride, and the organic solvent comprises any one or a combination of at least two of carbon tetrachloride, cyclohexane, dimethylbenzene, N-dimethyl pyrrolidone, cyclohexanone and isobutanol;
(3) Taking a fast ion conductor as a target material, taking the graphite precursor as a matrix, performing magnetron sputtering at a distance of 10-50 mm between the target material and the matrix, and coating the fast ion conductor on the surface of the graphite precursor to obtain the fast ion conductor coated graphite composite material;
the deposition rate of the magnetron sputtering is 0.01-10A/min, the deposition time is 1-30 min, and the air pressure of the vacuum chamber is 1 multiplied by 10 -1 ～10×10 -1 Pa, the gas in the atmosphere is any one or a combination of at least two of nitrogen, argon and ammonia, and the fast ion conductor comprises Li 5 FeO 4 、Li 2 Mn 2 O 4 、Li 3 Any one or a combination of at least two of N, lithium nickelate, lithium sulfide and lithium fluoride.
In a second aspect, the invention provides a fast ion conductor coated graphite composite material prepared by the preparation method in the first aspect, wherein the fast ion conductor coated graphite composite material comprises graphite and a coating layer coated on the surface of the graphite, the coating layer comprises amorphous carbon, a fast ion conductor and a metal oxide, and the metal oxide comprises any one or a combination of at least two of nickel oxide, iron oxide and cobalt oxide.
The fast ion conductor coated graphite composite material comprises a graphite core and a coating layer shell, wherein the graphite and the coating layer have good binding force, the coating layer is uniformly coated and deposited densely, the energy density of the material is improved, the synergistic effect among the graphite and amorphous carbon in the coating layer, the fast ion conductor and metal oxide is improved, and the first discharge capacity, the first charge and discharge efficiency, the fast charge performance and the cycle performance of the material are improved.
The coating layer comprises amorphous carbon, a fast ion conductor and a metal oxide, wherein the amorphous carbon, the fast ion conductor and the metal oxide in the coating layer are all in the same coating layer and are uniformly mixed, so that layering phenomenon is avoided.
Preferably, the coating layer is further doped with nitrogen atoms, so that the impedance of the material is further reduced.
In a third aspect, the invention provides a lithium ion battery, wherein the negative electrode of the lithium ion battery comprises the fast ion conductor coated graphite composite material according to the second aspect.
The lithium ion battery prepared by the method has higher first discharge capacity, first charge and discharge efficiency, and good quick charge performance and cycle performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polymer decomposition and metal salt forming process of the invention can form micron and/or millimeter holes in the material, and the generated metal oxide (such as nickel oxide, cobalt oxide, ferric oxide and the like) has a catalytic effect and can provide a catalytic effect for generating amorphous carbon at a high temperature in the subsequent magnetron sputtering.
(2) According to the graphite precursor containing the catalyst, under the condition of magnetron sputtering, part of organic solvent, functional additives and residual polymers are decomposed to generate amorphous carbon, and the amorphous carbon is coated on the surface of graphite, so that the quick charge performance of the material is improved; meanwhile, the functional additive can generate a synergistic effect with a fast ion conductor subjected to subsequent magnetron sputtering at a high temperature of the magnetron sputtering, and the fast ion conductor is promoted to be deposited on the graphite surface more uniformly and compactly.
(3) The amorphous carbon generated after magnetron sputtering and the fast ion conductor deposited on the graphite surface produce a synergistic effect, so that the electronic and ion conductivity of the material are improved, and the first efficiency and the fast charging performance of the material are improved; meanwhile, compared with the traditional liquid phase/solid phase cladding material, the magnetron sputtering method has the advantages of high deposition density, high efficiency, controllable process, thinner cladding layer and the like, and indirectly improves the energy density of the material.
Drawings
Fig. 1 is an SEM image of a fast ion conductor coated graphite composite material prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a fast ion conductor coated graphite composite material, which comprises the following steps:
(1) Adding 100g of artificial graphite, 3g of nickel carbonate and 7g of polyvinyl alcohol into 500mL of carbon tetrachloride solution, uniformly dispersing, filtering, then sintering at 400 ℃ for 3 hours, and crushing to obtain a porous graphite composite;
(2) Adding 3g of ferric chloride and 1g of hexadecyl dimethyl ammonium chloride into 300g of carbon tetrachloride organic solution, dispersing uniformly, adding 100g of porous graphite complex, transferring into a reaction kettle, carrying out soaking reaction for 3h at the temperature of 100 ℃ and the pressure of 2Mpa, filtering, and carrying out vacuum drying at 80 ℃ for 24h to obtain a graphite precursor containing a catalyst;
(3) By magnetron sputtering method with Li 5 FeO 4 The method is characterized in that a graphite precursor is used as a matrix, and the working air pressure of a vacuum chamber is 5 multiplied by 10 under the condition that the distance between a substrate of the matrix and the target is 30mm and the sputtering atmosphere is nitrogen -1 Pa, the deposition rate is 5A/min, the deposition time is 10min, and a fast ion conductor grows on the surface of the matrix to obtain the fast ion conductor coated graphite composite material.
Example 2
The embodiment provides a preparation method of a fast ion conductor coated graphite composite material, which comprises the following steps:
(1) Adding 100 artificial graphite, 1g nickel carbonate and 5g polyacrylic acid into 500mL carbon tetrachloride solution, uniformly dispersing, filtering, then sintering at 300 ℃ for 6 hours, and crushing to obtain a porous graphite composite;
(2) Adding 1g of cobalt chloride and 0.5g of dodecyl dimethyl amine oxide into 100g of cyclohexane organic solution, uniformly dispersing, adding 100g of porous graphite complex, transferring into a reaction kettle, carrying out soaking reaction for 6h at the temperature of 50 ℃ and the pressure of 3Mpa, filtering, and carrying out vacuum drying at 80 ℃ for 24h to obtain a graphite precursor containing a catalyst;
(3) By magnetron sputtering method with Li 2 Mn 2 O 4 As target material, graphite precursorThe working pressure of the vacuum chamber is 1.0X10 when the distance between the substrate and the target is 10mm -1 Pa, the deposition rate is 0.01A/min, the deposition time is 30min, and a fast ion conductor grows on the surface of the matrix to obtain the fast ion conductor coated graphite composite material.
Example 3
The embodiment provides a preparation method of a fast ion conductor coated graphite composite material, which comprises the following steps:
(1) Adding 100g of artificial graphite, 5g of nickel carbonate and 10g of polyvinylidene fluoride into 500mL of carbon tetrachloride solution, uniformly dispersing, then sintering at 500 ℃ for 1h, and crushing to obtain a porous graphite composite;
(2) Adding 5g of nickel chloride and 2g of octadecyl trimethyl ammonium chloride into 500g of N, N-dimethyl pyrrolidone, dispersing uniformly, adding 100g of porous graphite complex, transferring into a reaction kettle, carrying out soaking reaction for 1h at the temperature of 150 ℃ and the pressure of 1Mpa, filtering, and carrying out vacuum drying at 80 ℃ for 24h to obtain a graphite precursor containing a catalyst;
(3) The magnetron sputtering method is adopted, lithium fluoride is used as a target material, a graphite precursor is used as a matrix, and the working air pressure of a vacuum chamber is 10 multiplied by 10 under the condition that the distance between a substrate of the matrix and the target material is 50mm and the sputtering atmosphere is ammonia -1 Pa, the deposition rate is 10A/min, the deposition time is 1min, and a fast ion conductor grows on the surface of the matrix to obtain the fast ion conductor coated graphite composite material.
Example 4
Except that the mass substitution of the artificial graphite, the nickel carbonate and the polyvinyl alcohol in the step (1) is as follows: 100g of artificial graphite, 6g of nickel carbonate and 4g of polyvinyl alcohol were used as in example 1.
Example 5
Except that the mass substitution of the artificial graphite, the nickel carbonate and the polyvinyl alcohol in the step (1) is as follows: 100g of artificial graphite, 1g of nickel carbonate and 11g of polyvinyl alcohol were used as in example 1.
Example 6
The contents of iron chloride, cetyl dimethyl ammonium chloride and carbon tetrachloride are replaced by: the procedure of example 1 was repeated except that 6g of ferric chloride, 0.4g of cetyldimethyl ammonium chloride and 550mL of carbon tetrachloride were used.
Example 7
The contents of iron chloride, cetyl dimethyl ammonium chloride and carbon tetrachloride are replaced by: the procedure of example 1 was repeated except that 0.8g of ferric chloride, 2.5g of cetyldimethyl ammonium chloride and 90mL of carbon tetrachloride were used.
Example 8
The procedure of example 1 was repeated except that the deposition rate of magnetron sputtering was 12A/min and the deposition time was 32 min.
Example 9
The procedure of example 3 was repeated except that the deposition time of the magnetron sputtering was 0.5 min.
Example 10
The procedure of example 1 was repeated except that the nickel carbonate in step (1) was replaced with cobalt nitrate.
Comparative example 1
The procedure of example 1 was followed except that the operation of step (3) was not performed, the graphite precursor prepared in step (2) was directly transferred to a tube furnace, and carbonized at 850 ℃ for 3 hours under an argon atmosphere, followed by pulverization to obtain a graphite composite material.
Comparative example 2
The procedure of example 1 was followed except that the operation of step (3) was not performed, and the graphite precursor prepared in step (2) was coated with the fast ion conductor in a liquid phase manner;
the liquid phase mode specifically comprises the following steps: li is mixed with 5 FeO 4 Preparing a solution, mixing with the graphite precursor, filtering, drying, carbonizing at 800 ℃ for 3 hours, and crushing to obtain the graphite composite material.
Comparative example 3
The procedure of example 1 was repeated except that the procedure of step (2) was not performed, and the procedure of step (3) was directly performed after the porous graphite composite was prepared in step (1).
Comparative example 4
The procedure of example 1 was followed except that the step (1) was not performed, and artificial graphite was directly used instead of the porous graphite composite in the step (2).
Performance test:
1. button cell and physicochemical test thereof
(1) The fast ion conductor coated graphite composite materials prepared in examples 1 to 10 and the graphite materials of comparative examples 1 to 4 were used as negative electrode materials, and assembled into button cells, respectively, according to the following methods:
adding binder, conductive agent and solvent into the negative electrode material, stirring and mixing uniformly to prepare negative electrode slurry, coating the negative electrode slurry on copper foil, drying, rolling and cutting to prepare the negative electrode plate. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the anode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4:220. The lithium metal sheet is used as a counter electrode, a Polyethylene (PE) film, a polypropylene (PP) film or a polyethylene propylene (PEP) composite film is used as a diaphragm, and LiPF is used 6 /EC+DEC(LiPF 6 The concentration of (2) was 1.3mol/L and the volume ratio of EC and DEC was 1:1) as an electrolyte, and the battery assembly was performed in an argon-filled glove box.
(2) The prepared button cell is respectively arranged on a Wuhan blue electric CT2001A type cell tester, charging and discharging are carried out at a multiplying power of 0.1C, the charging and discharging voltage range is 0.005-2.0V, the first discharge capacity and the first discharge efficiency are measured, and the multiplying power discharge capacity of 3C is tested.
Powder electrical conductivity and specific surface area of the negative electrode material are tested according to national standard GB/T-24533-2019 lithium ion battery graphite negative electrode material, and the test results are shown in Table 1:
TABLE 1
Fig. 1 shows a composite material coated with a fast ion conductor prepared in example 1 of the present invention, and as can be seen from fig. 1, the obtained material is in the form of particles with a particle size of 10-20 μm, and the surface of the material contains bright substances as the fast ion conductor.
As can be seen from Table 1, the discharge capacity of the fast ion conductor coated graphite composite materials prepared in examples 1-10 is significantly higher than that of comparative examples 1-4, and the fast ion conductor, amorphous carbon and metal oxide are coated on the surface of the graphite material prepared by the preparation method of the present application, so that the consumption of lithium ions in the charge and discharge process can be reduced, and the first efficiency and the rate capability can be improved.
2. Soft package battery test
(1) Negative electrodes were prepared with the fast ion conductor coated graphite composite materials prepared in examples 1 to 10 and the graphite materials of comparative examples 1 to 4, respectively, using a ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) Preparation of positive electrode for positive electrode material with LiPF 6 (the solvent is EC+DEC, the volume ratio is 1:1, the concentration is 1.3 mol/L) is electrolyte, and Celebord 2400 is a diaphragm to prepare the 2Ah soft-package battery.
When the negative electrode is prepared, a binder, a conductive agent and a solvent are added into a negative electrode material, the materials are stirred and mixed uniformly to prepare negative electrode slurry, the negative electrode slurry is coated on a copper foil, and the negative electrode plate is prepared by drying, rolling and cutting. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the anode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4:220.
When the positive electrode is prepared, a binder, a conductive agent and a solvent are added into a positive electrode material, the mixture is stirred and mixed uniformly to prepare positive electrode slurry, the positive electrode slurry is coated on an aluminum foil, the aluminum foil is dried, rolled and cut to prepare a positive electrode plate, the binder is PVDF, the conductive agent is SP, and the solvent is N-methylpyrrolidone. The weight ratio of the positive electrode material, the conductive agent, the binder and the solvent is 93:3:4:140.
(2) Rate capability test
The charging and discharging voltage ranges from 2.8V to 4.2V, the testing temperature is 25+/-3.0 ℃, the charging is carried out at 1.0C, 2.0C, 3.0C and 5.0C, the discharging is carried out at 1.0C, the constant current ratio and the temperature of the battery under different charging modes are tested, and the results are shown in Table 2:
TABLE 2
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As can be seen from Table 2, the rate charging performance of the soft-pack battery of the embodiment of the invention is obviously better than that of the comparative example, and the charging time is shorter, so that the fast ion conductor coated graphite composite material of the invention has good fast charging performance. The reason is that the material surface is deposited with a fast ion conductor with high lithium ion conductivity by a magnetron sputtering method to obtain a material with high density and good uniformity, thereby improving the constant current ratio of the battery, namely improving the fast charge performance.
(3) Cycle performance test
The following experiments were conducted on the soft pack battery prepared by using the fast ion conductor coated graphite composite material prepared in 1-10 and the graphite material of comparative examples 1-4 as the negative electrode materials: the capacity retention rate was measured by sequentially performing 100, 300, and 500 charge/discharge cycles at a charge/discharge rate of 2C/2C and a voltage ranging from 2.8 to 4.2V, and the results are shown in Table 3:
TABLE 3 Table 3
As can be seen from table 3, the preparation method of the present invention coats amorphous carbon, fast ion conductor and metal oxide on the graphite surface, and improves the stability of the material surface structure during charge and discharge, thereby improving the cycle performance. Compared with the comparative example, the fast ion conductor coated graphite composite material prepared by the invention has better cycle performance.
As can be seen from comparison of examples 1 and examples 4-5, the adoption of graphite, metal salt and polymer in proper proportions in the invention can further improve the quick charge performance and the cycle performance of the material, and the metal salt content in example 4 is relatively high, and the polymer content is relatively low, so that the cycle performance is affected; in example 5, the metal salt content is smaller, and the polymer content is larger, so that the quick charge performance is affected; thus, the material of example 1 has better fast charge and cycle performance.
As can be seen from the comparison of the examples 1 and the examples 6-7, the power performance of the material can be further improved by adopting the catalyst, the functional additive, the organic solvent and the porous graphite composite in the proper proportion; in the embodiment 6, the catalyst and the organic solvent are more, and the functional additive is less, so that the circulation performance is affected; in the embodiment 7, the catalyst and the organic solvent are less, and the functional additive is more, so that the quick-filling performance is affected; therefore, the quick charge and cycle performance of example 1 are better.
As can be seen from the comparison of the embodiment 1 and the embodiment 8 and the comparison of the embodiment 3 and the embodiment 9, the invention can improve the deposition quality and control the proper deposition thickness by adjusting the deposition rate and the deposition time of the magnetron sputtering, and further improve the quick charge performance; the too high deposition rate in example 8 affects the surface density of the deposited material; the deposition time in example 9 was too short, affecting the coating quality and adversely affecting the impedance reduction, and therefore the materials in examples 1 and 3 had better coating quality, fast charge and cycle performance.
As can be seen from the comparison of the embodiment 1 and the comparative examples 1-2, the invention adopts the magnetron sputtering method to coat the fast ion conductor on the graphite surface, and the amorphous carbon formed by the magnetron sputtering can cooperate to further improve the electronic and ionic conductivity of the material, thereby improving the fast charge performance; in comparative example 1, the magnetron sputtering method is not adopted to coat the fast ion conductor, but the graphite precursor is directly carbonized, no cooperative coordination of the fast ion conductor exists, and the capacity retention rates of 100 times, 300 times and 500 times are lower than those of example 1; in comparative example 2, although the fast ion conductor is coated, the coating is performed in a liquid phase mode, the efficiency is low, the process is uncontrollable, the coating is not uniform, and the fast ion conductor cannot achieve a dense deposition effect, so the cycle performance of comparative example 2 is significantly inferior to that of example 1.
As is clear from the comparison between example 1 and comparative example 3, the present invention does not add catalyst, functional additive and organic solvent to perform soaking reaction, and can not form sufficient amorphous carbon on the graphite surface, which affects the synergistic effect of the fast ion conductor, amorphous carbon and metal oxide, and the fast charge performance and cycle performance of comparative example 3 are significantly inferior to those of example 1.
As is clear from the comparison between the example 1 and the comparative example 4, the present invention does not add metal salts such as nickel salt, cobalt salt and iron salt and polymer, which is difficult to form porous graphite composite with micron/millimeter holes, and affects the liquid retention capacity of the material and thus the cycle performance, so the quick charge performance and the cycle performance of the comparative example 4 are significantly inferior to those of the example 1.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (25)
1. The preparation method of the fast ion conductor coated graphite composite material is characterized by comprising the following steps of:
(1) Mixing graphite, metal salt and polymer, and sintering to obtain a porous graphite composite;
the metal salt comprises any one or a combination of at least two of nickel salt, cobalt salt and ferric salt;
(2) Mixing the porous graphite complex, a catalyst, a functional additive and an organic solvent, and carrying out soaking reaction to obtain a graphite precursor;
the catalyst comprises any one or a combination of at least two of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and ferric nitrate; the functional additive comprises any one or a combination of at least two of hexadecyl dimethyl ammonium chloride, dodecyl dimethyl ammonium oxide and octadecyl trimethyl ammonium chloride;
(3) And coating a fast ion conductor on the surface of the graphite precursor by adopting a magnetron sputtering method to obtain the fast ion conductor coated graphite composite material.
2. The preparation method according to claim 1, wherein the mass ratio of graphite, metal salt and polymer in the step (1) is 100 (1-5): 5-10.
3. The method of claim 1, wherein the nickel salt of step (1) comprises any one or a combination of at least two of nickel carbonate, nickel chloride, nickel sulfate and nickel nitrate.
4. The method of claim 1, wherein the cobalt salt of step (1) comprises any one or a combination of at least two of cobalt chloride, cobalt nitrate, and cobalt sulfate.
5. The method of claim 1, wherein the iron salt of step (1) comprises any one or a combination of at least two of ferric chloride, ferric sulfate, and ferric nitrate.
6. The method of claim 1, wherein the polymer of step (1) comprises any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethyl cellulose, and polyvinylidene fluoride.
7. The method of claim 1 or 2, wherein the sintering temperature in step (1) is 300 to 500 ℃.
8. The method according to claim 1, wherein the sintering time in step (1) is 1 to 6 hours.
9. The method of claim 1, wherein the sintering of step (1) is performed in an air atmosphere.
10. The preparation method according to claim 1, wherein the mass ratio of the catalyst, the functional additive, the organic solvent and the porous graphite composite in the step (2) is (1-5): 0.5-2): 100-500): 100.
11. The method according to claim 1, wherein the organic solvent of step (2) comprises any one or a combination of at least two of carbon tetrachloride, cyclohexane, xylene, N-dimethylpyrrolidone, cyclohexanone and isobutanol.
12. The method according to claim 1, wherein the soaking reaction in step (2) is carried out at a temperature of 50 to 150 ℃.
13. The method according to claim 1, wherein the pressure of the soaking reaction in the step (2) is 1 to 3MPa.
14. The method according to claim 1, wherein the soaking reaction in step (2) takes 1 to 6 hours.
15. The method of claim 1, wherein step (3) is performed in the following manner:
and (3) taking the fast ion conductor as a target material, taking the graphite precursor as a matrix, and performing magnetron sputtering to coat the fast ion conductor on the surface of the graphite precursor, thereby obtaining the fast ion conductor coated graphite composite material.
16. The method of claim 15, wherein the target and substrate are spaced apart by 10 to 50mm.
17. The method according to claim 15, wherein the gas in the atmosphere of the magnetron sputtering is any one or a combination of at least two of nitrogen, argon and ammonia.
18. The method of claim 15, wherein the magnetron sputtering vacuum chamber has a gas pressure of 1 x 10 -1 ～10×10 -1 Pa。
19. The method of claim 15, wherein the magnetron sputtering has a deposition rate of 0.01 to 10A/min.
20. The method of claim 15, wherein the magnetron sputtering is performed for a deposition time of 1 to 30 minutes.
21. The method of claim 1, wherein the fast ionic conductor of step (3) comprises Li 5 FeO 4 、Li 2 Mn 2 O 4 、Li 3 Any one or a combination of at least two of N, lithium nickelate, lithium sulfide and lithium fluoride.
22. The preparation method according to claim 1, characterized in that the preparation method comprises:
(1) Mixing graphite, metal salt and polymer with the mass ratio of (1-5) being (5-10), and sintering for 1-6 hours in the air atmosphere, wherein the sintering temperature is 300-500 ℃, so as to obtain a porous graphite composite body;
the metal salt comprises any one or a combination of at least two of nickel salt, cobalt salt and ferric salt, and the polymer comprises any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethyl cellulose and polyvinylidene fluoride;
(2) Adding a catalyst and a functional additive into an organic solvent, dispersing uniformly, adding the porous graphite composite, mixing, carrying out soaking reaction for 1-6 h at the temperature of 50-150 ℃ and the pressure of 1-3 MPa, filtering and drying to obtain a graphite precursor;
the mass ratio of the catalyst to the functional additive to the organic solvent to the porous graphite complex is (1-5): (0.5-2): (100-500): 100, wherein the catalyst comprises any one or a combination of at least two of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and ferric nitrate, the functional additive comprises any one or a combination of at least two of hexadecyl dimethyl ammonium chloride, dodecyl dimethyl amine oxide and octadecyl trimethyl ammonium chloride, and the organic solvent comprises any one or a combination of at least two of carbon tetrachloride, cyclohexane, dimethylbenzene, N-dimethyl pyrrolidone, cyclohexanone and isobutanol;
(3) Taking a fast ion conductor as a target material, taking the graphite precursor as a matrix, performing magnetron sputtering at a distance of 10-50 mm between the target material and the matrix, and coating the fast ion conductor on the surface of the graphite precursor to obtain the fast ion conductor coated graphite composite material;
the deposition rate of the magnetron sputtering is 0.01-10A/min, the deposition time is 1-30 min, and the air pressure of the vacuum chamber is 1 multiplied by 10 -1 ～10×10 -1 Pa, the gas in the atmosphere is any one or a combination of at least two of nitrogen, argon and ammonia, and the fast ion conductor comprises Li 5 FeO 4 ，Li 2 Mn 2 O 4 、Li 3 Any one or a combination of at least two of N, lithium nickelate, lithium sulfide and lithium fluoride.
23. A rapid ion conductor coated graphite composite material prepared by the preparation method of any one of claims 1 to 22, wherein the rapid ion conductor coated graphite composite material comprises graphite and a coating layer coated on the surface of the graphite, the coating layer comprises amorphous carbon, a rapid ion conductor and a metal oxide, and the metal oxide comprises any one or a combination of at least two of nickel oxide, iron oxide and cobalt oxide.
24. The rapid ion conductor coated graphite composite of claim 23, wherein the coating is further doped with nitrogen atoms.
25. A lithium ion battery, characterized in that the negative electrode of the lithium ion battery comprises the fast ion conductor coated graphite composite material according to claim 23 or 24.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185131A (en) * | 2011-04-13 | 2011-09-14 | 长安大学 | Preparation method of porous current collector/tin-base alloy/carbon nano-tube integrated electrode |
| US11101809B1 (en) * | 2019-08-26 | 2021-08-24 | Hrl Laboratories, Llc | Metal vapor-density control system with composite multiphase electrode |
| CN113690429A (en) * | 2021-08-23 | 2021-11-23 | 武汉立承科技有限公司 | Carbon-coated graphene/metal oxide composite material and preparation method thereof |
| CN114335462A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102185131A (en) * | 2011-04-13 | 2011-09-14 | 长安大学 | Preparation method of porous current collector/tin-base alloy/carbon nano-tube integrated electrode |
| US11101809B1 (en) * | 2019-08-26 | 2021-08-24 | Hrl Laboratories, Llc | Metal vapor-density control system with composite multiphase electrode |
| CN113690429A (en) * | 2021-08-23 | 2021-11-23 | 武汉立承科技有限公司 | Carbon-coated graphene/metal oxide composite material and preparation method thereof |
| CN114335462A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
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