CN117174847A - Amorphous carbon coated metal doped hard carbon composite material and preparation method and application thereof - Google Patents
Amorphous carbon coated metal doped hard carbon composite material and preparation method and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 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 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 239000002194 amorphous carbon material Substances 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 239000007833 carbon precursor Substances 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 108010094020 polyglycine Proteins 0.000 claims description 3
- 229920000232 polyglycine polymer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 14
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- 238000010438 heat treatment Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
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- 239000003792 electrolyte Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
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- 239000005977 Ethylene Substances 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
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- -1 etc.) Polymers 0.000 description 3
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- 239000005720 sucrose Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910014397 LiNi1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000316887 Saissetia oleae Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
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- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to an amorphous carbon coated metal doped hard carbon composite material, a preparation method and application thereof. The composite material is of a core-shell structure, the inner core is of a metal doped hard carbon composite material, the outer shell is of a phosphorus doped amorphous carbon material, and the weight of the outer shell is 1-10wt% of the total weight of the composite material. According to the invention, a hydro-thermal method is adopted to dope metal compounds into hydrocarbon precursors, so that the prepared composite material has good uniformity, the electronic conductivity of the composite material is obviously improved, and the power is improved; and meanwhile, the porous structure formed after the metal compound of the carbonate is carbonized is utilized to improve the lithium/sodium storage capacity of the material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an amorphous carbon coated metal doped hard carbon composite material, a preparation method and application thereof.
Background
Hard carbon refers to hard graphitized carbon, one of amorphous carbon materials, and pyrolytic carbon of high molecular polymer. Common hard carbons are resinated carbons (e.g., phenolic resins, epoxy resins, polyfurfuryl alcohol, etc.), organic polymer pyrolytic carbons (e.g., PFA, PVC, PVDF, PAN, etc.), and the like. Hard carbon is paid attention to by the advantages of wide material source, good low-temperature performance, low expansion and the like, and is applied to the fields of lithium ion batteries, sodium ion batteries and the like. However, compared with graphite, hard carbon has the problems of poor electronic conductivity, many surface defects of the material, deviation of normal-temperature rate performance of the material, first low efficiency and the like. The measures for improving the first efficiency and the power performance of the hard carbon material mainly comprise: introducing nonmetallic/metallic elements, surface treatment, material doping and cladding and the like. Chinese patent CN202210327614.5 discloses a metal oxide amorphous carbon coated hard carbon composite material, and a preparation method and application thereof, wherein a hard carbon precursor material and a catalyst solution are dissolved in an organic solvent to obtain a hard carbon precursor solution; and then mixing asphalt with the organic solvent, adding a metal organic compound, adding the hard carbon precursor solution, and carbonizing to obtain the metal doped amorphous carbon coated hard carbon composite material, wherein the electronic conductivity of the inner core hard carbon is not improved by doping metal oxide in the shell, so that the power performance of the material is limited.
Disclosure of Invention
In order to improve the power performance and the coating uniformity of the hard carbon material, the invention improves the power performance by doping metal compounds in the hard carbon precursor, and further improves the coating efficiency, consistency and uniformity of the material by coating amorphous carbon through the fluidized bed technology.
The first aspect of the invention provides an amorphous carbon coated metal doped hard carbon composite material, wherein the composite material is of a core-shell structure, the inner core is of a metal doped hard carbon composite material, and the outer shell is of a phosphorus doped amorphous carbon material.
In some embodiments, the core is prepared from a feedstock comprising, by mass, 5-20% metal compounds and 80-95% hard carbon.
In some embodiments, the shell is made from a starting material comprising, by mass, 1-5% elemental phosphorus and 95-99% amorphous carbon.
The phosphorus simple substance provided by the invention comprises at least one of red phosphorus, white phosphorus and black scale.
The second aspect of the present invention provides a method for preparing an amorphous carbon coated metal doped hard carbon composite material, the method comprising the steps of:
s1, carrying out high-temperature and high-pressure reaction on an aqueous solution of hydrocarbon, a metal compound and a polymer dispersing agent in a reaction kettle to obtain a metal doped hard carbon precursor material;
s2, dipping a metal doped hard carbon precursor material into steam of a phosphorus simple substance to obtain an intermediate;
s3, transferring the intermediate into fluidized bed equipment for carbon source and fluorine source deposition to obtain the amorphous carbon coated metal doped hard carbon composite material.
In some embodiments, the mass ratio of hydrocarbon, metal compound, polymeric dispersant is 100: (10-30): (1-5).
The applicant found during the research that when the mass ratio of hydrocarbon, metal compound and polymer dispersant is 100: (10-30): and (1-5) can give consideration to energy density and power performance and further improve the consistency of the material, and when the proportion of hydrocarbon is too high, the metal compound is too low, so that the power performance of the material is reduced, otherwise, the energy density is reduced, and the reason is probably that the metal compound has high electronic conductivity and reduces impedance, and hard carbon formed after carbonization of the hydrocarbon has a sodium/lithium storage function and improves the energy density.
In some embodiments, the polymeric dispersant comprises at least one of polyacrylamide, polyacrylonitrile, polyethylenimine, polyglycine, polyacrylic acid, and has a molecular weight of 10 to 100 tens of thousands. The addition of a certain amount of dispersant in the system can act to disperse the metal compound and the polymer is a hydrocarbon, which will form amorphous carbon during subsequent carbonization to reduce resistance.
In some embodiments, the aqueous hydrocarbon solution has a concentration of 1-10wt%, and the hydrocarbon comprises at least one of glucose, sucrose, starch, lignin, cellulose, phenolic resin, polyacrylonitrile, epoxy resin.
Further, S1 comprises the steps of putting an aqueous solution of hydrocarbon, a metal compound and a polymer dispersing agent into a reaction kettle, reacting for 1-6 hours at the temperature of 100-200 ℃ and the pressure of 1-3MPa, filtering, washing with deionized water, and vacuum drying to obtain the metal doped hard carbon precursor material.
In some embodiments, the mass ratio of the metal-doped hard carbon precursor material to the elemental phosphorus is 100: (1-5). The applicant finds that doping a certain amount of phosphorus single in the precursor can effectively improve the specific capacity of the hard carbon composite material, probably because holes are formed after the phosphorus compound is carbonized to store lithium or sodium to improve the specific capacity, when the phosphorus single is excessively added, the impedance is increased, the voltage platform is increased, the power performance is reduced, and when the phosphorus single is excessively added, the effect of improving the specific capacity is not obvious.
Further, S2 comprises transferring a metal doped hard carbon precursor material into a reaction kettle, heating a phosphorus simple substance to obtain phosphorus simple substance steam, depositing the phosphorus simple substance steam on the hard carbon precursor, and cooling the phosphorus simple substance steam in an inert atmosphere to obtain an intermediate.
Preferably, the elemental phosphorus is red phosphorus.
In some embodiments, the volume ratio of the carbon source to the fluorine source is 10: (1-5).
The addition of the carbon source and the fluorine source can carry out surface modification on the prepared intermediate, reduce the surface defects of the material, improve the first efficiency and improve the cycle performance. When the fluorine source is excessively added, too many defects are caused on the surface of the material, the high-temperature storage performance is reduced, and when the fluorine source is excessively added, the structural stability of the material is improved obviously.
In some embodiments, the metal compound comprises at least one of iron oxide, titanium oxide, manganese oxide, cobalt oxide, iron carbonate, magnesium carbonate, manganese carbonate, copper carbonate, silver carbonate, cerium carbonate, lanthanum carbonate.
Further, S3 comprises transferring the intermediate into fluidized bed equipment, introducing a mixed gas of carbon source and fluorine gas, heating to 600-1000 ℃, ensuring the pressure in the cavity to be 1-3MPa, and depositing the carbon source and the fluorine source for 30-300min to obtain the amorphous carbon coated metal doped hard carbon composite material.
Further, the carbon source comprises at least one of methane, acetylene, and ethylene.
The third aspect of the invention provides the application of the amorphous carbon coated metal doped hard carbon composite material or the preparation method in the preparation of lithium batteries or sodium batteries.
Compared with the prior art, the invention has the following beneficial effects:
s1, compared with a solid-phase method or a liquid-phase method used in the prior art, the hydrothermal method is adopted to dope metal compounds into hydrocarbon precursors, the prepared composite material is good in uniformity, and water molecules are gasified under high temperature and high pressure to realize molecular-level mixing, so that the uniformity is improved, the electronic conductivity of the composite material is remarkably improved, and the power is improved; and meanwhile, the porous structure formed after the metal compound of the carbonate is carbonized is utilized to improve the lithium/sodium storage capacity of the material.
S2, doping red phosphorus into the precursor, and improving the specific capacity of the material by depending on the specific capacity of the red phosphorus and the holes formed in the carbonization process.
S3, modifying the surface of the material by the mixed gas of the carbon source and the fluorine gas to reduce the surface defect of the material, thereby improving the first efficiency and improving the cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the invention and that other drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the amorphous carbon coated metal doped hard carbon composite material prepared in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A first aspect of the present embodiment provides a method for preparing an amorphous carbon coated metal doped hard carbon composite material, the method comprising the steps of:
s1, adding 100g of glucose into 500g of deionized water to prepare a hydrocarbon water solution with the mass concentration of 5wt%, adding 20g of ferric carbonate and 3g of polyacrylamide, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 150 ℃ and the pressure of 2MPa, filtering, washing with deionized water, and vacuum-drying at the temperature of 80 ℃ for 24 hours to obtain a metal-doped hard carbon precursor material;
s2, transferring 100g of metal doped hard carbon precursor into a reaction kettle, heating 3g of red phosphorus to obtain red phosphorus steam, depositing the red phosphorus steam on the hard carbon precursor, and cooling the red phosphorus steam in an inert argon atmosphere to obtain an intermediate;
s3, transferring the intermediate into an inner cavity of the fluidized bed equipment, introducing methane/fluorine gas mixture (volume ratio, methane: fluorine gas=10:3), heating to 800 ℃, ensuring the pressure in the cavity to be 2MPa, and performing methane/fluorine source deposition for 120min to obtain the amorphous carbon coated metal doped hard carbon composite material.
The second aspect of the present embodiment provides an amorphous carbon coated metal doped hard carbon composite material, the composite material is a core-shell structure, the inner core is a metal doped hard carbon composite material, the preparation raw material comprises iron carbonate and hard carbon, the outer shell is a phosphorus doped amorphous carbon material, and the preparation raw material comprises red phosphorus and amorphous carbon.
A third aspect of the present embodiment provides an application of the amorphous carbon coated metal doped hard carbon composite material in preparing a lithium battery or a sodium battery.
Example 2
A first aspect of the present embodiment provides a method for preparing an amorphous carbon coated metal doped hard carbon composite material, the method comprising the steps of:
s1, adding 100g of sucrose into 10000g of deionized water to prepare a sucrose aqueous solution with the mass concentration of 1wt%, adding 10g of magnesium carbonate and 1g of polyethylenimine, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting for 6 hours at the temperature of 100 ℃ and the pressure of 3MPa, filtering, washing with deionized water, and vacuum-drying at the temperature of 80 ℃ for 24 hours to obtain a metal-doped hard carbon precursor material;
s2, transferring 100g of metal doped hard carbon precursor into a reaction kettle, heating 1g of red phosphorus to obtain red phosphorus steam, depositing the red phosphorus steam on the hard carbon precursor, and then cooling the red phosphorus steam in an inert argon atmosphere to obtain an intermediate;
s3, transferring the intermediate into an inner cavity of the fluidized bed equipment, introducing ethylene/fluorine gas mixture (volume ratio, ethylene: fluorine gas=10:1), heating to 600 ℃, ensuring the pressure in the cavity to be 3MPa, and carrying out ethylene/fluorine gas deposition for 300min to obtain the amorphous carbon coated metal doped hard carbon composite material.
A second aspect of this example provides an amorphous carbon coated metal doped hard carbon composite, the embodiment being as in example 1.
A third aspect of the present embodiment provides an application of the amorphous carbon coated metal doped hard carbon composite material in preparing a lithium battery or a sodium battery.
Example 3
A first aspect of the present embodiment provides a method for preparing an amorphous carbon coated metal doped hard carbon composite material, the method comprising the steps of:
s1, adding 100g of phenolic resin into 1000g of deionized water to prepare a phenolic resin aqueous solution with the mass concentration of 10wt%, adding 30g of copper carbonate and 5g of polyglycine, uniformly mixing, transferring the mixture into a high-pressure reaction kettle, reacting for 1h at the temperature of 200 ℃ and the pressure of 1MPa, filtering, washing with deionized water, and vacuum-drying at the temperature of 80 ℃ for 24h to obtain a metal-doped hard carbon precursor material;
s2, transferring 100g of metal doped hard carbon precursor into a reaction kettle, heating 5g of red phosphorus to obtain red phosphorus steam, depositing the red phosphorus steam on the hard carbon precursor, and then cooling the red phosphorus steam in an inert argon atmosphere to obtain an intermediate;
s3, transferring the intermediate into an inner cavity of the fluidized bed equipment, introducing acetylene/fluorine gas mixture (volume ratio, acetylene: fluorine gas=10:5), heating to 1000 ℃, ensuring the pressure in the cavity to be 1MPa, and performing acetylene/fluorine gas deposition for 30min to obtain the amorphous carbon coated metal doped hard carbon composite material.
In a second aspect of this example, an amorphous carbon coated metal doped hard carbon composite is provided, as in example 1.
A third aspect of the present embodiment provides an application of the amorphous carbon coated metal doped hard carbon composite material in preparing a lithium battery or a sodium battery.
Comparative example 1
This comparative example provides a method for preparing an amorphous carbon coated metal doped hard carbon composite, which is different from example 1 in that no iron carbonate or polyacrylamide is added.
Comparative example 2
This comparative example provides a method for preparing an amorphous carbon coated metal doped hard carbon composite, which is different from example 1 in that red phosphorus is not added.
Comparative example 3
This comparative example provides a method for preparing an amorphous carbon coated metal doped hard carbon composite, which is different from example 1 in that 10g of red phosphorus is added.
Performance testing
(1) SEM test
SEM test was performed on the amorphous carbon coated metal doped hard carbon composite material prepared in example 1, and the test results are shown in fig. 1. As can be seen from FIG. 1, the composite material prepared in example 1 has a spherical structure, a uniform size distribution and a particle size of 2-8. Mu.m.
(2) Physical and chemical properties and button cell testing
The amorphous carbon coated metal doped hard carbon composite materials prepared in examples and comparative examples were tested for particle size, tap density, specific surface area, interlayer spacing, trace element content, powder resistivity, and powder OI values. The trace element content is tested by EDS, the interlayer spacing is tested by XRD, and other test projects are tested according to the method of national standard GBT-24533-2019 lithium ion battery graphite cathode material. The test results are shown in Table 1.
TABLE 1
The amorphous carbon coated metal doped hard carbon composite materials in the examples and the comparative examples are used as the anode material of the lithium ion battery to be assembled into the button battery, and the specific preparation method of the anode material comprises the following steps: the binder LA132, the conductive agent SP and the solvent (double distilled water) were added to the composite material in a ratio of 90g:3g:7g:220mL, stirring and pulping, coating the slurry on a copper foil, and drying and rolling the slurry to prepare a negative electrode plate; a metal lithium sheet is used as a counter electrode; the electrolyte adopts LiPF6/EC+DEC, and the LiPF in the electrolyte 6 The electrolyte is a mixture of EC and DEC with the volume ratio of 1:1, and the concentration of the electrolyte is 1.3mol/L; the diaphragm adopts a polyethylene PE film. The button cell assembly was performed in an argon filled glove box. Electrochemical performance was performed on a wuhan blue electric CT2001A type battery tester with a charge-discharge voltage ranging from 0.00V to 2.0V and a charge-discharge rate of 0.1C, and the button cell was tested for first discharge capacity and first efficiency, while the rate performance (2C, 0.1C) and cycle performance (0.2C/0.2C, 200 times) were tested. The test results are shown in Table 2.
TABLE 2
As can be seen from tables 1 and 2, the materials prepared by the embodiments of the present invention have high specific capacity and first efficiency, and the reason for this is probably that the metal elements filled in the amorphous carbon coated metal doped hard carbon composite material improve the electronic conductivity, the multiplying power and the tap density; meanwhile, the surface defect of the material is reduced by modifying the surface of the material by the carbon source/fluorine gas mixture, the first efficiency is improved, and the cycle performance is improved.
(3) Soft package battery test
Examples and comparative examplesThe amorphous carbon coated metal-doped hard carbon composite material in the example is subjected to slurry mixing and coating to prepare a negative electrode plate, and a ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O S2. As positive electrode, with LiPF 6 (the solvent is EC+DEC, the volume ratio is 1:1, the electrolyte concentration is 1.3 mol/L) is taken as electrolyte, and a Celgard2400 membrane is taken as a diaphragm, so that the 2Ah soft-package battery is prepared.
The rate performance of the soft package battery is tested, the charging and discharging voltage ranges from 2.8V to 4.2V, the temperature is 25+/-3.0 ℃, the charging is carried out at 1.0C, 3.0C, 5.0C and 10.0C, and the discharging is carried out at 1.0C. The results are shown in Table 3.
TABLE 3 Table 3
As can be seen from table 3, the rate charging performance of the soft pack battery of the amorphous carbon coated metal doped hard carbon composite material prepared in the example is significantly better than that of the comparative example, i.e. the charging time is shorter, and the analysis reason is that: lithium ion migration is required in the battery charging process, and the metal with high electronic conductivity doped in the hard carbon of the anode material in the embodiment reduces impedance and improves rate performance.
(4) Cycle performance test
The cycle performance test conditions were: the charge and discharge current is 3C/3C, the voltage range is 2.5-4.2V, and the cycle times are 500. The test results are shown in Table 4.
TABLE 4 Table 4
| Project | Initial capacity retention (%) | Cycle 500 retention (%) |
| Example 1 | 100 | 96.12 |
| Example 2 | 100 | 96.94 |
| Example 3 | 100 | 95.80 |
| Comparative example 1 | 100 | 91.19 |
| Comparative example 2 | 100 | 92.08 |
| Comparative example 3 | 100 | 90.57 |
As can be seen from table 4, the cycle performance of the lithium ion battery prepared by using the amorphous carbon coated metal doped hard carbon composite material obtained in the example is significantly better than that of the comparative example, and the reason is probably that the surface defect of the material is reduced by modifying the surface of the material by using the carbon source/fluorine gas mixture, so that the cycle performance of the material is improved.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The amorphous carbon coated metal doped hard carbon composite material is characterized in that the composite material is of a core-shell structure, the inner core is of a metal doped hard carbon composite material, and the outer shell is of a phosphorus doped amorphous carbon material.
2. Amorphous carbon coated metal doped hard carbon composite material according to claim 1, wherein the starting materials for the preparation of the inner core comprise a metal compound and hard carbon.
3. The amorphous carbon coated metal doped hard carbon composite material according to claim 1, wherein the raw materials for preparing the shell comprise elemental phosphorus and amorphous carbon.
4. A method for preparing an amorphous carbon coated metal doped hard carbon composite material according to any one of claims 1-3, characterized in that the preparation method comprises the steps of:
s1, carrying out high-temperature and high-pressure reaction on an aqueous solution of hydrocarbon, a metal compound and a polymer dispersing agent in a reaction kettle to obtain a metal doped hard carbon precursor material;
s2, dipping a metal doped hard carbon precursor material into steam of a phosphorus simple substance to obtain an intermediate;
s3, transferring the intermediate into fluidized bed equipment for carbon source and fluorine source deposition to obtain the amorphous carbon coated metal doped hard carbon composite material.
5. The method for preparing amorphous carbon coated metal doped hard carbon composite material according to claim 4, wherein the mass ratio of hydrocarbon, metal compound and polymer dispersant is 100:
(10-30)：(1-5)。
6. the method for preparing amorphous carbon coated metal doped hard carbon composite material according to claim 4, wherein the polymer dispersant comprises at least one of polyacrylamide, polyacrylonitrile, polyethylenimine, polyglycine, and polyacrylic acid.
7. The method for preparing an amorphous carbon coated metal doped hard carbon composite material according to claim 4, wherein the mass ratio of the metal doped hard carbon precursor material to the phosphorus element is 100: (1-5).
8. The method for preparing an amorphous carbon coated metal doped hard carbon composite material according to claim 4, wherein the volume ratio of the carbon source to the fluorine source is 10: (1-5).
9. The method for preparing amorphous carbon coated metal doped hard carbon composite material according to claim 4, wherein the metal compound comprises at least one of iron oxide, titanium oxide, manganese oxide, cobalt oxide, iron carbonate, magnesium carbonate, manganese carbonate, copper carbonate, silver carbonate, cerium carbonate, lanthanum carbonate.
10. Use of the amorphous carbon coated metal doped hard carbon composite material of claim 1 or the preparation method of claim 4 for the preparation of lithium or sodium batteries.
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| CN117497729B (en) * | 2023-12-05 | 2024-05-17 | 云南坤天新能源有限公司 | Three-dimensional porous titanium-antimony doped hard carbon composite material and preparation method thereof |
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