CN115084475A - Fast ion conductor coated graphite composite material and preparation method and application thereof - Google Patents
Fast ion conductor coated graphite composite material and preparation method and application thereof Download PDFInfo
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- CN115084475A CN115084475A CN202210783424.4A CN202210783424A CN115084475A CN 115084475 A CN115084475 A CN 115084475A CN 202210783424 A CN202210783424 A CN 202210783424A CN 115084475 A CN115084475 A CN 115084475A
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- ion conductor
- graphite
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- nickel
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 146
- 239000010439 graphite Substances 0.000 title claims abstract description 146
- 239000010416 ion conductor Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 28
- 150000003839 salts Chemical class 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 22
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 150000002505 iron Chemical class 0.000 claims abstract description 7
- 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 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000011247 coating layer Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 13
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- 229910021586 Nickel(II) 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
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 239000012298 atmosphere 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 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
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 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
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052744 lithium 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 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
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000008096 xylene Substances 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
- 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
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 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 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 55
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 238000007599 discharging Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 11
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000010406 cathode material 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
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000003756 stirring 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
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007790 solid phase Substances 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
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
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- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 229910001868 water Inorganic materials 0.000 description 1
Images
Classifications
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- 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 complex; the metal salt comprises any one or the combination of at least two of nickel salt, cobalt salt and iron 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 the surface of the graphite precursor with the fast ion conductor by adopting a magnetron sputtering method to obtain the fast ion conductor coated graphite composite material. According to the invention, the porous graphite complex is prepared, and then amorphous carbon and a fast ion conductor are grown on the surface of the porous graphite complex through magnetron sputtering, so that the traditional carbonization procedure is omitted, and the deposition is more uniform and compact; the amorphous carbon and the fast ion conductor have synergistic effect, so that the electronic and ionic conductivity of the material is improved, and the material has good fast charge and cycle 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 market on the quick charge performance requirement of the lithium ion battery, the quick charge performance of the lithium ion battery cathode material is also improved while the lithium ion battery cathode material has high energy density. At present, measures for improving the quick charging performance of the cathode material mainly comprise: the method reduces the particle size of the aggregate of the material, increases the coating proportion of amorphous carbon, and improves the lithium ion intercalation and deintercalation channel of the material by modifying the surface of the material. The fast ion conductor is a compound with high lithium ion conductivity, and can quickly realize the quick exchange of lithium ions in the charging and discharging process, thereby effectively improving the fast charging performance.
The fast ion conductor has the problem of poor electronic conductivity when used alone, and needs to be mixed with a material with good electronic conductivity to achieve the improvement of the fast charge performance. Patent CN108987687B provides a low-temperature lithium ion battery graphite negative electrode material and a preparation method thereof, the patent controls the particle size of graphite by ball milling and spray drying, and performs intercalation reaction and surface coating on graphite powder to form a fast ion conductor coating layer on the graphite surface, thereby improving the diffusion capacity of lithium ions. Patent CN114628659A discloses a graphite cathode composite material for power batteries and a preparation method thereof, wherein the core of the material is graphite, and the shell is made of Li 5 FeO 4 And the fast ion conductor is composed of a multilayer structure, so that the rate capability of the cathode material is improved. The 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 graphite composite negative electrode material with a core-shell structure is prepared by adopting a liquid phase method, the composite negative electrode material comprises a graphite core, a quick ion conductor intermediate 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 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 In order to improve the quick charge and cycle performance of the material, but the graphite composite anode material prepared by the patent has the consistency of a coating layerPoor performance, and material peeling easily occurs between each coating layer of the shell during charging and discharging, thereby affecting the cycle and power performance of the material.
In the prior art, the quick ion conductor is coated on the surface of graphite to improve the quick charging performance of a graphite cathode material, but the coating layer of the graphite composite material prepared by the method is poor in consistency, the improvement of the power and the cycle performance of the material is limited, and the application of the graphite composite material coated by the quick ion conductor in the field of lithium ion batteries is influenced. Therefore, the preparation of the graphite composite material with excellent quick charge performance has important significance for the research and development of the lithium ion battery.
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. According to the invention, the porous graphite complex is prepared, then amorphous carbon is grown on the surface of the porous graphite complex through soaking reaction and magnetron sputtering, and the fast ion conductor is deposited, so that the deposition density is high, the process is controllable, the deposition layer is thin, the energy density of the material is improved, the traditional carbonization procedure is also omitted, and the efficiency is improved; meanwhile, the generated amorphous carbon and the fast ion conductor have synergistic effect, so that the electronic and ionic conductivity of the material is improved, and the prepared fast ion conductor coated graphite composite material has high first discharge capacity, first charge and discharge efficiency, and good fast charge performance and cycle performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a fast ion conductor coated graphite composite material, comprising the following steps:
(1) mixing graphite, metal salt and polymer, and sintering to obtain a porous graphite complex;
the metal salt comprises any one or the combination of at least two of nickel salt, cobalt salt and iron 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 the surface of the graphite precursor with the fast ion conductor by adopting a magnetron sputtering method to obtain the fast ion conductor coated graphite composite material.
The fast ion conductor coated graphite composite material is prepared by the steps of sintering, soaking reaction, magnetron sputtering and the like, the prepared material has high electronic and ionic conductivity, and simultaneously has higher 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 can be decomposed to generate substances such as carbon monoxide, carbon dioxide, water and the like in the sintering process, and the specific metal salt can generate metal oxide to achieve the aim 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 process is facilitated; meanwhile, the generated metal oxide (such as nickel oxide, cobalt oxide, iron oxide and the like) has a catalytic effect, and the catalytic effect can be provided for the subsequent magnetron sputtering high-temperature generation of amorphous carbon.
Secondly, mixing the obtained porous graphite complex with a catalyst, a functional additive and an organic solvent in the step (2) for soaking reaction to obtain a graphite precursor containing the catalyst; in the subsequent magnetron sputtering process, the organic solvent is partially volatilized, the residual organic solvent, the functional additive and the residual small part of polymer in the step (1) are decomposed to generate amorphous carbon which is coated on the surface of graphite, and the quick filling performance of the material is improved; meanwhile, the functional additive can generate a synergistic effect with a subsequent fast ion conductor subjected to magnetron sputtering at a high temperature, so that the fast ion conductor is promoted to be deposited on the surface of the graphite more uniformly and compactly.
Thirdly, in the step (3), a magnetron sputtering method is adopted to coat the surface of the graphite precursor with the fast ion conductor, and in the magnetron sputtering process, under the action of the catalyst, residual part of the organic solvent, functional additive and small part of polymer are decomposed to generate amorphous carbon, so that the traditional carbonization process is omitted, and the efficiency is improved; the generated amorphous carbon and a fast ion conductor which is magnetron sputtered on the surface of the graphite can generate a synergistic effect, so that the electronic and ionic 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 material has the advantages of high deposition density, high efficiency, controllable process, thinner coating layer and the like, the energy density of the material is indirectly improved, meanwhile, the preparation method disclosed by the invention is adopted for coating the fast ion conductor, the fast ion conductor and the amorphous carbon are uniformly combined, the fast ion conductor releases excessive lithium ions in the first charging and discharging process, the irreversible capacity of the material can be reduced, the first efficiency is improved, and the fast charging performance and the cycle performance of the graphite composite material coated by the fast ion conductor are improved under the synergistic effect of the fast ion conductor and the amorphous carbon.
Preferably, the mass ratio of the graphite, the metal salt and the polymer in the step (1) is 100 (1-5): (5-10), wherein the selection range of the metal salt (1-5) can be, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, etc., and the selection range of the polymer (5-10) can be, for example, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10, etc.
In the invention, the graphite, the metal salt and the polymer are mixed and sintered according to 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, the improvement of the electronic conductivity and the ion transmission of the material are facilitated within the proportion range, the cycle performance and the power performance of the material are balanced, when the metal salt is more, the cycle 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, and may be, 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, and may be, for example, a combination of cobalt chloride and cobalt sulfate, a combination of cobalt nitrate and cobalt sulfate, a combination of cobalt chloride, cobalt nitrate and cobalt sulfate, or the like.
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, and may be, for example, a combination of ferric chloride and ferric sulfate, a combination of ferric sulfate and ferric nitrate, a combination of ferric chloride, ferric sulfate and ferric nitrate, or the like.
As a preferable embodiment of the preparation method of the present invention, the polymer in step (1) includes any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethylcellulose and polyvinylidene fluoride, and may be, for example, a combination of polyvinyl alcohol and polyacrylic acid, a combination of polytetrafluoroethylene and sodium polymethylcellulose, a combination of sodium polymethylcellulose and polyvinylidene fluoride, or a combination of polyvinyl alcohol, polyacrylic acid and polytetrafluoroethylene.
In the invention, a specific polymer is preferably adopted, has a certain binding function, realizes the uniform dispersion of the metal salt, the graphite and the binding agent, leaves uniform holes on the porous graphite complex after sintering, and is beneficial to the liquid absorption and retention of the material.
Preferably, the sintering temperature in step (1) is 300 to 500 ℃, for example, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ or 500 ℃ and the like.
Preferably, the sintering time in the step (1) is 1-6 h, for example, 1h, 2h, 3h, 4h, 5h or 6h, etc.
Preferably, the sintering of step (1) is performed under an air atmosphere.
In a preferred embodiment of the preparation method of the present invention, in the step (2), the mass ratio of the catalyst, the functional additive, the organic solvent, and the porous graphite composite is (1-5): (0.5-2): (100-500): 100, wherein the selection range (1-5) of the catalyst may be, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5, the selection range (0.5-2) of the functional additive may be, for example, 0.5, 0.8, 1, 1.2, 1.5, 1.8, or 2, and the selection range (100-500) of the organic solvent may be, for example, 100, 150, 200, 250, 300, 350, 400, 450, or 500.
The invention selects the catalyst, the functional additive, the organic solvent and the porous graphite complex with proper proportion to promote the material reaction process and provide a basis for forming isotropic amorphous carbon later, when the catalyst is more, the self-discharge of the material is larger, and when the catalyst is less, the material preparation period is longer and the resistance of the amorphous carbon is larger.
Preferably, the catalyst in step (2) comprises any one or a combination of at least two of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and ferric nitrate, for example, the catalyst can be a combination of ferric chloride and cobalt chloride, a combination of nickel chloride and ferric nitrate, a combination of cobalt nitrate and ferric nitrate, a combination of cobalt chloride, nickel chloride and ferric nitrate, or the like; 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 embodiment of the preparation method of the present invention, the functional additive in step (2) includes any one or a combination of at least two of cetyldimethyl ammonium chloride, dodecyldimethyl amine oxide and octadecyltrimethyl ammonium chloride, and may be, for example, a combination of cetyldimethyl ammonium chloride and dodecyldimethyl amine oxide, a combination of octadecyltrimethyl ammonium chloride and hexadecyldimethyl ammonium chloride, or a combination of cetyldimethyl ammonium chloride, dodecyldimethyl amine oxide and octadecyltrimethyl ammonium chloride.
According to the invention, a specific nitrogen-containing functional additive with a ring structure is preferably adopted, and a specific carbon nitrogen ring structure forms nitrogen-doped amorphous carbon with a specific structure and orientation after magnetron sputtering, so that the impedance is favorably reduced, and the power performance of the fast ion conductor coated graphite composite material is improved.
Preferably, the organic solvent in step (2) includes any one or a combination of at least two of carbon tetrachloride, cyclohexane, xylene, N-dimethylpyrrolidone, cyclohexanone and isobutanol, and may be, 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 preferred embodiment of the preparation method of the present invention, the temperature of the soaking reaction in the step (2) is 50 to 150 ℃, and may be, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the pressure of the soaking reaction in the step (2) is 1 to 3MPa, and may be 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 2MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3MPa, for example.
Preferably, the soaking reaction in the step (2) is carried out for 1-6 h, for example, 1h, 2h, 3h, 4h, 5h or 6 h.
As a preferred technical scheme of the preparation method, the step (3) is carried out according to the following mode:
and performing magnetron sputtering by taking the fast ion conductor as a target material and the graphite precursor as a matrix, and coating the fast ion conductor on the surface of the graphite precursor to obtain 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 50 mm.
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, and for example, the gas may be a combination of nitrogen and argon, a combination of argon and ammonia, a combination of nitrogen, argon and ammonia, or the like.
Preferably, the pressure of the vacuum chamber of the magnetron sputtering is 1 × 10 -1 ～10×10 -1 Pa, for example, may be 1X 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 10X 10 -1 Pa, and the like.
Preferably, the deposition rate of the magnetron sputtering is 0.01-10A/min, such as 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.
Preferably, the deposition time of the magnetron sputtering is 1-30 min, for example, 1min, 2min, 4min, 6min, 8min, 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30 min.
According to the invention, the deposition rate and deposition time of magnetron sputtering are adjusted, so that the deposition thickness and content of the fast ion conductor can be adjusted, and the fast charging performance of the fast ion conductor coated graphite composite material is further improved.
Preferably, the fast ion 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, for example, Li 5 FeO 4 And Li 2 Mn 2 O 4 Combination of (1), Li 2 Mn 2 O 4 And Li 3 A combination of N, a combination of 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 with the fast ion conductor is prepared by matching the appropriate fast ion conductor with magnetron sputtering, so that the function of high fast ion conductivity can be further exerted, and the fast charging performance and the cycle performance of the material are improved.
As a preferable technical scheme of the preparation method of the invention, the preparation method comprises the following steps:
(1) mixing graphite, metal salt and polymer in a mass ratio of (1-5) to (5-10) of 100, and sintering for 1-6 hours in an air atmosphere at the sintering temperature of 300-500 ℃ to obtain a porous graphite composite;
the metal salt comprises any one or the combination of at least two of nickel salt, cobalt salt and iron salt, and the polymer comprises any one or the combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethylcellulose and polyvinylidene fluoride;
(2) adding a catalyst and a functional additive into an organic solvent, uniformly dispersing, adding the porous graphite complex, mixing, performing a soaking reaction at a temperature of 50-150 ℃ and a pressure of 1-3 MPa for 1-6 h, 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, the catalyst comprises any one or 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 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 combination of at least two of carbon tetrachloride, cyclohexane, xylene, N-dimethyl pyrrolidone, cyclohexanone and isobutanol;
(3) taking a fast ion conductor as a target material, taking the graphite precursor as a matrix, and carrying out magnetron sputtering with the distance between the target material and the matrix being 10-50 mm, 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 the 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 present invention provides a fast ion conductor coated graphite composite material prepared by the preparation method of the first aspect, where the fast ion conductor coated graphite composite material includes graphite and a coating layer coated on the surface of the graphite, the coating layer includes amorphous carbon, a fast ion conductor and a metal oxide, and the metal oxide includes 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 compactly, the energy density of the material is improved, and the graphite and amorphous carbon, the fast ion conductor and metal oxide in the coating layer have synergistic effect, so that the first discharge capacity, the first charge-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 metal oxide, and 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 without layering.
Preferably, the cladding layer is doped with nitrogen atoms, so that the impedance of the material is further reduced.
In a third aspect, the present invention provides a lithium ion battery, wherein a 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 invention has higher first discharge capacity and first charge-discharge efficiency as well as good quick charge performance and cycle performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polymer decomposition and the metal salt generation 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, iron oxide and the like) has the catalytic action, and can provide the catalytic action for the subsequent magnetron sputtering high-temperature generation of amorphous carbon.
(2) Under the condition of magnetron sputtering, part of organic solvent, functional additive and residual polymer of the catalyst-containing graphite precursor are decomposed to generate amorphous carbon which is coated on the surface of graphite, so that the quick charging performance of the material is improved; meanwhile, the functional additive can generate a synergistic effect with a subsequent fast ion conductor subjected to magnetron sputtering at a high temperature, so that the fast ion conductor is promoted to be deposited on the surface of the graphite more uniformly and compactly.
(3) The amorphous carbon generated after magnetron sputtering and the fast ion conductor deposited on the surface of the graphite generate a synergistic effect, so that the electronic and ionic conductivity of the material is improved, and the first efficiency and the fast charging performance of the material are improved; meanwhile, compared with the traditional liquid phase/solid phase coating material, the magnetron sputtering material has the advantages of high deposition density, high efficiency, controllable process, thinner coating 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 prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
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 and filtering, sintering at 400 ℃ for 3h, and crushing to obtain a porous graphite complex;
(2) adding 3g of ferric chloride and 1g of hexadecyl dimethyl ammonium chloride into 300g of carbon tetrachloride organic solution, uniformly dispersing, adding 100g of porous graphite complex, transferring into a reaction kettle, carrying out soaking reaction at 100 ℃ and 2Mpa for 3 hours, filtering, and carrying out vacuum drying at 80 ℃ for 24 hours to obtain a graphite precursor containing a catalyst;
(3) by magnetron sputtering with Li 5 FeO 4 Using graphite precursor as matrix, under the condition of that the distance between substrate of matrix and target material is 30mm and under the condition of sputtering atmosphere nitrogen gas its working pressure of vacuum chamber is 5X 10 -1 Pa, the deposition rate is 5A/min, the deposition time is 10min, and a fast ion conductor grows on the surface of the substrate 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 100g of artificial graphite, 1g of nickel carbonate and 5g of polyacrylic acid into 500mL of carbon tetrachloride solution, uniformly dispersing, filtering, sintering at 300 ℃ for 6h, 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 at 50 ℃ and 3Mpa for 6h, filtering, and carrying out vacuum drying at 80 ℃ for 24h to obtain a catalyst-containing graphite precursor;
(3) by magnetron sputtering with Li 2 Mn 2 O 4 Using graphite precursor as matrix, under the condition of that the distance between substrate of matrix and target material is 10mm and under the condition of sputtering atmosphere argon gas the working pressure of vacuum chamber is 1.0X 10 -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 for uniform dispersion, 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 N, uniformly dispersing the mixture in N-dimethyl pyrrolidone, adding 100g of porous graphite complex, transferring the porous graphite complex into a reaction kettle, carrying out soaking reaction at the temperature of 150 ℃ and the pressure of 1Mpa for 1h, filtering, and carrying out vacuum drying at the temperature of 80 ℃ for 24h to obtain a catalyst-containing graphite precursor;
(3) adopting magnetron sputtering method, taking lithium fluoride as target material, taking graphite precursor as matrix, under the condition that the distance between the substrate of the matrix and the target material is 50mm, under the condition of sputtering atmosphere ammonia gas in vacuum chamberWorking air pressure of 10X 10 -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 of the artificial graphite, the nickel carbonate and the polyvinyl alcohol in the step (1) are replaced by the following mass: the procedure of example 1 was repeated except for using 100g of artificial graphite, 6g of nickel carbonate and 4g of polyvinyl alcohol.
Example 5
Except that the mass of the artificial graphite, the nickel carbonate and the polyvinyl alcohol in the step (1) are replaced by: the procedure of example 1 was repeated except for using 100g of artificial graphite, 1g of nickel carbonate and 11g of polyvinyl alcohol.
Example 6
The contents of the iron chloride, the hexadecyl dimethyl ammonium chloride and the carbon tetrachloride are replaced by: the procedure of example 1 was repeated, except for 6g of ferric chloride, 0.4g of cetyldimethylammonium chloride and 550mL of carbon tetrachloride.
Example 7
The contents of the iron chloride, the hexadecyl dimethyl ammonium chloride and the carbon tetrachloride are replaced by: the procedure is as in example 1 except for 0.8g of ferric chloride, 2.5g of cetyldimethylammonium chloride and 90mL of carbon tetrachloride.
Example 8
The same procedure as in 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 same procedure as in example 3 was repeated except that the deposition time in the magnetron sputtering was 0.5 min.
Example 10
The procedure of example 1 was repeated, except that the nickel carbonate of step (1) was replaced with cobalt nitrate.
Comparative example 1
The process was carried out in the same manner as in example 1 except that the graphite precursor prepared in step (2) was directly transferred to a tube furnace without the operation of step (3), heated to 850 ℃ in an argon atmosphere, carbonized for 3 hours, and then pulverized to obtain a graphite composite material.
Comparative example 2
The process is the same as example 1 except that the operation of step (3) is not performed, and the graphite precursor prepared in step (2) is coated with the fast ion conductor in a liquid phase manner;
the liquid phase is specifically as follows: mixing Li 5 FeO 4 Preparing a solution, mixing the solution with the graphite precursor, filtering, drying, carbonizing at 800 ℃ for 3h, 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 carried out, and the procedure of step (3) was carried out directly after the porous graphite composite body was prepared in step (1).
Comparative example 4
The procedure of example 1 was repeated, except that the step (1) was not performed, and artificial graphite was used instead of the porous graphite composite material in the step (2).
And (3) performance testing:
button cell and its physical and chemical test
(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 button cells were assembled respectively as follows:
adding a binder, a conductive agent and a 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 a negative electrode sheet. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the negative electrode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4: 220. The lithium metal sheet is taken as a counter electrode, a Polyethylene (PE) film, a polypropylene (PP) film or a polyethylene propylene (PEP) composite film is taken as a diaphragm, and LiPF is taken 6 /EC+DEC(LiPF 6 With a concentration of 1.3mol/L, with a volume ratio of EC to DEC of 1:1) as electrolyte, the cell assembly was carried out in a glove box filled with argon.
(2) The prepared button cell is respectively installed on a Wuhan blue electricity CT2001A type cell tester, charging and discharging are carried out at 0.1C multiplying power, the charging and discharging voltage range is 0.005-2.0V, the first discharging capacity and the first discharging efficiency are measured, and the multiplying power discharging capacity of 3C is measured.
The powder conductance and the specific surface area of the negative electrode material are tested according to the national standard GB/T-245359-2019 graphite negative electrode material for lithium ion batteries, and the test results are shown in Table 1:
TABLE 1
Fig. 1 shows that the fast ion conductor-coated graphite composite material prepared in example 1 of the present invention is in the form of particles, the particle size of the obtained material is 10-20 μm, and the bright substance contained on the surface of the obtained material is a fast ion conductor, as can be seen from fig. 1.
It can be known from table 1 that the discharge capacity of the fast ion conductor coated graphite composite materials prepared in examples 1 to 10 is significantly higher than that of comparative examples 1 to 4, and the graphite material prepared by the preparation method of the present application has the fast ion conductor, amorphous carbon and metal oxide coated on the surface, so that the consumption of lithium ions in the charging and discharging process can be reduced, and the first efficiency and rate capability can be improved.
Second, laminate Battery testing
(1) Negative electrodes were prepared from 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, and ternary material (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) Preparing a positive electrode from a positive electrode material by using LiPF 6 (the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/L) is electrolyte, and Celegard2400 is a diaphragm to prepare the 2Ah flexible package battery.
When the negative electrode is prepared, the binder, the conductive agent and the solvent are added into the negative electrode material, the negative electrode slurry is prepared by stirring and mixing evenly, the slurry of the negative electrode slurry is coated on the copper foil, and the negative electrode sheet 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 negative electrode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4: 220.
When the anode is prepared, adding a binder, a conductive agent and a solvent into an anode material, stirring and mixing uniformly to prepare anode slurry, coating the anode slurry on an aluminum foil, drying, rolling, and cutting to prepare an anode sheet, wherein the binder is PVDF, the conductive agent is SP and the solvent is N-methylpyrrolidone. The weight ratio of the anode material, the conductive agent, the binder and the solvent is 93:3:4: 140.
(2) Rate capability test
The charging and discharging voltage range is 2.8-4.2V, the testing temperature is 25 +/-3.0 ℃, charging is carried out at 1.0C, 2.0C, 3.0C and 5.0C respectively, 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
As can be seen from table 2, the rate charging performance of the pouch cell of the embodiment of the present invention is significantly better than that of the comparative example, and the charging time is shorter, which indicates that the fast ion conductor coated graphite composite material of the present invention has good fast charging performance. The reason is that the rapid ion conductor with high lithium ion conductivity is deposited on the surface of the material by a magnetron sputtering method, so that the material with high density and good uniformity is obtained, and the constant current ratio of the battery, namely the rapid charging performance, is improved.
(3) Cycle performance test
The following experiments were carried out on the soft-packed batteries prepared using the fast ion conductor-coated graphite composite material prepared in 1 to 10 and the graphite material of comparative examples 1 to 4 as the negative electrode material: the capacity retention rate is tested by sequentially performing 100 times, 300 times and 500 times of charge-discharge cycles with the charge-discharge multiplying power of 2C/2C and the voltage range of 2.8-4.2V, and the results are shown in Table 3:
TABLE 3
As can be seen from table 3, the preparation method of the present invention, which coats amorphous carbon, fast ion conductor and metal oxide on the surface of graphite, improves the stability of the surface structure of the material during the charging and discharging processes, 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.
Compared with the examples 4-5, the graphite, the metal salt and the polymer in proper proportion are adopted in the invention, so that the quick charging performance and the cycle performance of the material can be further improved, and the cycle performance is influenced by the fact that the metal salt content is higher and the polymer content is lower in the example 4; in example 5, the content of metal salt is low, the content of polymer is high, and the quick charging performance is affected; thus, the material of example 1 has better fast fill and cycle performance.
As can be seen from the comparison between the example 1 and the examples 6 to 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 body in proper proportions; in example 6, the contents of the catalyst and the organic solvent are high, and the content of the functional additive is low, so that the cycle performance is influenced; in example 7, the contents of the catalyst and the organic solvent are low, and the content of the functional additive is high, so that the quick charging performance is influenced; thus, the fast charge and cycle performance of example 1 is better.
By comparing the embodiment 1 with the embodiment 8 and comparing the embodiment 3 with 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 charging performance; in the embodiment 8, the deposition rate is too high, so that the surface compactness of the deposited material is influenced; the deposition time in example 9 is too short, which affects the coating quality and adversely affects the reduction of the impedance, and therefore, the materials in examples 1 and 3 have better coating quality, fast charge and cycle performance.
As can be seen from the comparison between the embodiment 1 and the comparative examples 1-2, the rapid ion conductor is coated on the surface of the graphite by adopting the magnetron sputtering method, so that the amorphous carbon formed by magnetron sputtering can act synergistically, the electronic and ionic conductivity of the material is further improved, and the rapid charging performance is improved; in comparative example 1, the fast ion conductor is not coated by a magnetron sputtering method, but the graphite precursor is directly carbonized without the cooperative matching of the fast ion conductor, and the capacity retention rates of 100 times, 300 times and 500 times are all lower than those of example 1; although the fast ion conductor is coated in the comparative example 2, the fast ion conductor is coated in a liquid phase mode, so that the efficiency is low, the process is uncontrollable, the coating is not uniform, and the fast ion conductor cannot achieve a compact deposition effect, so that the cycle performance of the comparative example 2 is remarkably inferior to that of the example 1.
It can be seen from the comparison between example 1 and comparative example 3 that the soaking reaction in the present invention without adding catalyst, functional additive and organic solvent can not form sufficient amorphous carbon on the graphite surface, which affects the synergy between the fast ion conductor and 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.
It can be known from the comparison between example 1 and comparative example 4 that, in the present invention, no metal salt such as nickel salt, cobalt salt, iron salt, etc. and polymer are added, which makes it difficult to form a porous graphite composite with micron/millimeter pores, and affects the liquid retention capability of the material and thus the cycle performance, therefore, the fast charge performance and the cycle performance of comparative example 4 are significantly inferior to those of example 1.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A preparation method of a fast ion conductor coated graphite composite material is characterized by comprising the following steps:
(1) mixing graphite, metal salt and polymer, and sintering to obtain a porous graphite complex;
the metal salt comprises any one or the combination of at least two of nickel salt, cobalt salt and iron 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 the surface of the graphite precursor with the fast ion conductor 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 the graphite, the metal salt and the polymer in the step (1) is 100 (1-5) to (5-10);
preferably, the nickel salt in step (1) comprises any one of nickel carbonate, nickel chloride, nickel sulfate and nickel nitrate or a combination of at least two of the nickel carbonate, the nickel chloride, the nickel sulfate and the nickel nitrate;
preferably, the cobalt salt in step (1) comprises any one of cobalt chloride, cobalt nitrate and cobalt sulfate or a combination of at least two of the cobalt salt and the cobalt nitrate;
preferably, the iron salt in step (1) comprises any one of ferric chloride, ferric sulfate and ferric nitrate or a combination of at least two of the foregoing;
preferably, the polymer in step (1) comprises any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethylcellulose and polyvinylidene fluoride.
3. The method according to claim 1 or 2, wherein the sintering temperature in step (1) is 300-500 ℃;
preferably, the sintering time in the step (1) is 1-6 h;
preferably, the sintering of step (1) is performed in an air atmosphere.
4. The preparation method according to any one of claims 1 to 3, 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;
preferably, the catalyst in step (2) comprises any one of or a combination of at least two of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate and ferric nitrate;
preferably, the functional additive in step (2) comprises any one or a combination of at least two of hexadecyl dimethyl ammonium chloride, dodecyl dimethyl amine oxide and octadecyl trimethyl ammonium chloride;
preferably, the organic solvent in step (2) comprises any one of carbon tetrachloride, cyclohexane, xylene, N-dimethylpyrrolidone, cyclohexanone and isobutanol or a combination of at least two thereof.
5. The method according to any one of claims 1 to 4, wherein the temperature of the soaking reaction in the step (2) is 50 to 150 ℃;
preferably, the pressure of the soaking reaction in the step (2) is 1-3 MPa;
preferably, the soaking reaction time in the step (2) is 1-6 h.
6. The production method according to any one of claims 1 to 5, wherein the step (3) is carried out in the following manner:
performing magnetron sputtering by taking a fast ion conductor as a target material and the graphite precursor as a matrix, and coating the fast ion conductor on the surface of the graphite precursor to obtain the fast ion conductor coated graphite composite material;
preferably, the distance between the target and the substrate is 10-50 mm;
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;
preferably, the vacuum chamber of magnetron sputtering has a gas pressure of 1 × 10 -1 ～10×10 -1 Pa；
Preferably, the deposition rate of the magnetron sputtering is 0.01-10A/min;
preferably, the deposition time of the magnetron sputtering is 1-30 min;
preferably, the fast ion 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.
7. The production method according to any one of claims 1 to 6, characterized by comprising:
(1) mixing graphite, metal salt and polymer in a mass ratio of (1-5) to (5-10) of 100, and sintering for 1-6 hours in an air atmosphere at the sintering temperature of 300-500 ℃ to obtain a porous graphite composite;
the metal salt comprises any one or the combination of at least two of nickel salt, cobalt salt and iron salt, and the polymer comprises any one or the combination of at least two of polyvinyl alcohol, polyacrylic acid, polytetrafluoroethylene, sodium polymethylcellulose and polyvinylidene fluoride;
(2) adding a catalyst and a functional additive into an organic solvent, uniformly dispersing, adding the porous graphite complex, mixing, performing a soaking reaction at a temperature of 50-150 ℃ and a pressure of 1-3 MPa for 1-6 h, 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 composite is (1-5): 0.5-2): 100-500): 100, the catalyst comprises any one or 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 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 combination of at least two of carbon tetrachloride, cyclohexane, xylene, N-dimethyl pyrrolidone, cyclohexanone and isobutanol;
(3) taking a fast ion conductor as a target material, taking the graphite precursor as a matrix, and carrying out magnetron sputtering with the distance between the target material and the matrix being 10-50 mm, 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 the 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.
8. The fast ion conductor coated graphite composite material prepared by the preparation method of any one of claims 1 to 7, 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.
9. The fast ion conductor coated graphite composite of claim 8, wherein the coating is further doped with nitrogen atoms.
10. A lithium ion battery comprising the fast ion conductor coated graphite composite material according to claim 8 or 9 in its negative electrode.
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