CN117613245A - Metal-coated heteroatom doped hard carbon composite material, preparation method thereof and sodium ion battery - Google Patents
Metal-coated heteroatom doped hard carbon composite material, preparation method thereof and sodium ion battery Download PDFInfo
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- CN117613245A CN117613245A CN202311764277.7A CN202311764277A CN117613245A CN 117613245 A CN117613245 A CN 117613245A CN 202311764277 A CN202311764277 A CN 202311764277A CN 117613245 A CN117613245 A CN 117613245A
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- hard carbon
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- heteroatom
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 66
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 21
- 235000009496 Juglans regia Nutrition 0.000 claims abstract description 15
- 235000020234 walnut Nutrition 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000013077 target material Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001197 polyacetylene Polymers 0.000 claims abstract description 6
- 239000004793 Polystyrene Substances 0.000 claims abstract description 3
- 229920002223 polystyrene Polymers 0.000 claims abstract description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 241000758789 Juglans Species 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 229940083982 sodium phytate Drugs 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 abstract 2
- 240000007049 Juglans regia Species 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 239000010410 layer Substances 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 16
- 239000003575 carbonaceous material Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 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 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- -1 polyethylene propylene Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011847 coal-based material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 101150047356 dec-1 gene Proteins 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/626—Metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a metal-coated heteroatom doped hard carbon composite material, a preparation method thereof and a sodium ion battery, and belongs to the technical field of batteries. The preparation method of the metal-coated heteroatom doped hard carbon composite material comprises the following steps: 1) Uniformly mixing walnut shells and a pore-forming agent, and carbonizing under an inert atmosphere to obtain a first precursor material; 2) The precursor material is subjected to heat preservation in an acid gas atmosphere, and then subjected to heat preservation in an alkaline gas atmosphere, so that a pre-composite material M is obtained; 3) Uniformly mixing the pre-composite material with a sulfur source and/or a nitrogen source, and then preserving heat at 700-1100 ℃ for 1-6h to obtain a pre-composite material N; the sulfur source is at least one of thiourea, vulcanized polyacetylene, multi-vulcanized carboyne, multi-thio polystyrene, vulcanized polyvinyl chloride and multi-thio benzene; 4) And (3) performing magnetron sputtering treatment on the pre-composite material N by adopting a transition metal target material. The metal-coated heteroatom-doped hard carbon composite material has higher energy density and better cycle performance.
Description
Technical Field
The invention relates to a metal-coated heteroatom doped hard carbon composite material, a preparation method thereof and a sodium ion battery, and belongs to the technical field of batteries.
Background
The current society has higher and higher requirements on new energy development, and the lithium ion battery plays an important role in the field of power batteries and the field of energy storage batteries. However, as the application scale of lithium ion batteries is larger and larger, the cost of lithium ion batteries is also higher and higher. Batteries that are less costly to develop have also been the subject of industry research.
Sodium ion batteries are less costly than lithium ion batteries and also have excellent performance. Hard carbon materials are considered to be one of the most promising negative materials for sodium ion batteries due to their large interlayer spacing and high specific surface area. At present, the performances of the positive electrode material and the negative electrode material of the sodium ion battery are both provided with a larger improvement space. Hard carbon is amorphous carbon which is difficult to graphitize, and has the characteristics of multiple pores, disordered layer structure, good material isotropy and the like in the hard carbon, but the first efficiency of the hard carbon is lower due to the larger specific surface area and the more pores of the hard carbon, and the energy density of the hard carbon is lower when the hard carbon is applied to a full battery. Therefore, the improvement of the first efficiency of the hard carbon material is one of the main measures for improving the energy density of the battery, and the improvement of the first efficiency is mainly improved in terms of reducing defects on the surface of the material, doping of the material, coating of the material, and the like.
The Chinese patent publication No. CN114639816A discloses a high first-time efficiency hard carbon composite material, wherein the composite material has a core-shell structure, a core is made of a hard carbon material, an intermediate layer is a lithium carbonate composite layer coating the core, and a shell is an amorphous carbon layer coating the intermediate layer; the mass ratio of the middle layer is 5.92-15% and the mass ratio of the outer layer is 1.25-10% based on 100% of the mass ratio of the composite material; the thickness of the lithium carbonate composite layer is 1-100 nm; the lithium carbonateThe composite layer consists of 95-99% of lithium carbonate and 1-5% of lithium sheets; the outer layer is an amorphous carbon layer, which is 1500-1600cm -1 Diffraction peaks are arranged nearby, and the thickness is 0.5-2 mu m.
The first efficiency of the material applied to the lithium ion battery is improved, but the improvement amplitude is not large, and the density deviation of the surface of the material causes the structural stability deviation in the circulation process.
Disclosure of Invention
The invention provides a metal-coated heteroatom doped hard carbon composite material, a preparation method thereof and a sodium ion battery, which are used for solving the problem of poor cycle performance of the sodium ion battery in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a metal-coated heteroatom-doped hard carbon composite material is of a core-shell structure, wherein the core is hard carbon doped with sulfur and/or nitrogen, the shell is amorphous carbon containing transition metal elements, and the mass of the shell accounts for 1-10% of the mass of the composite material.
The mass ratio of the transition metal element to the amorphous carbon in the shell is 1-10:90-99. The transition metal is any one of silver, nickel, copper and titanium. The shell may be composed of a transition metal simple substance and amorphous carbon, or may be composed of an oxide of a transition metal and amorphous carbon.
A preparation method of a metal-coated heteroatom doped hard carbon composite material comprises the following steps:
1) Uniformly mixing walnut shells and a pore-forming agent, and carbonizing under an inert atmosphere to obtain a first precursor material; the pore-forming agent is at least one of sodium acetate, sodium phytate, sodium carbonate and sodium bicarbonate;
2) The precursor material prepared in the step 1) is kept at 100-200 ℃ for 30-120min in an acid gas atmosphere, and then kept at 200-300 ℃ for 30-120min in an alkaline gas atmosphere, so as to obtain a pre-composite material M;
the acid gas is at least one of hydrogen sulfide, nitrogen dioxide, sulfur dioxide and hydrogen chloride;
the alkaline gas is at least one of ammonia, phosphine and hydrazine;
3) Uniformly mixing the pre-composite material M prepared in the step 2) with a sulfur source and/or a nitrogen source, and then preserving heat at 700-1100 ℃ for 1-6 hours to obtain a pre-composite material N; the sulfur source is at least one of thiourea, vulcanized polyacetylene, multi-vulcanized carboyne, multi-thio polystyrene, vulcanized polyvinyl chloride and multi-thio benzene;
the nitrogen source is at least one of melamine, urea, aniline, pyrrole and dopamine;
4) Performing magnetron sputtering treatment on the pre-composite material N in the step 3) by adopting a transition metal target material to obtain the composite material N; the transition metal is any one of silver, nickel, copper and titanium.
In the step 1), walnut shells are firstly washed by water, then crushed into fine powder and washed by distilled water again.
The inert atmosphere in step 1) is argon or nitrogen.
The carbonization temperature in the step 1) is 1000-1500 ℃. The carbonization time is 1-6h.
In the step 1), the mass ratio of the walnut shell to the pore-forming agent is 100:1-10.
In the step 2), the acid gas atmosphere is introduced with the acid gas at the flow rate of 10-100 mL/min.
In the step 2), the alkaline gas atmosphere is introduced with acid gas at a flow rate of 10-100 mL/min.
The mass ratio of the pre-composite material to the sulfur source or the nitrogen source in the step 3) is 100:1-10. Or the mass ratio of the sum of the mass of the sulfur source and the mass of the nitrogen source to the pre-composite material is 1-10:100.
The transition metal target in the step 4) comprises transition metal and polyvinylidene fluoride. The mass ratio of the transition metal to the polyvinylidene fluoride is 100:5-15.
And 4) vacuumizing during magnetron sputtering in the step 4), and then introducing argon. The degree of vacuum after evacuation was 1X 10 -3 Pa-1Pa. The vacuum degree after argon is introduced is 1-100Pa.
The current in the magnetron sputtering treatment in the step 4) is 100-500mA.
The voltage during the magnetron sputtering treatment in the step 4) is 1000-2000V.
The time for the magnetron sputtering treatment in the step 4) is 10-120min.
The sodium ion battery comprises a battery shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are arranged in the battery shell, wherein the negative electrode comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, the negative electrode material layer comprises a negative electrode active substance, and the negative electrode active substance is the metal-coated heteroatom doped hard carbon composite material.
The beneficial effects are that:
when the composite material is prepared, the walnut shell precursor material is subjected to surface treatment by adopting acid gas and alkaline gas, so that the surface or the inner core of the walnut shell precursor material forms more abundant chemical groups and more stable and complex hole structures of the structure, the sodium storage performance or the lithium storage performance of the material is improved, and the energy density is further improved.
Furthermore, the invention adopts a magnetron sputtering method to deposit metal or metal oxide on the surface of the material particles, and carbonizes to obtain the amorphous carbon deposition layer containing metal elements, and the deposition layer has the advantages of low resistivity, high density, stable structure and the like, and can promote the circulation of the material and the power performance thereof.
Drawings
Fig. 1 is an SEM image of the metal-clad heteroatom doped hard carbon composite of example 1.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention easier to understand, the invention is described in detail below with reference to specific embodiments.
Example 1
The preparation method of the metal-coated heteroatom doped hard carbon composite material comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 5g of sodium acetate, and carbonizing for 3 hours at 1200 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) Transferring the precursor material B into a tube furnace, introducing hydrogen sulfide gas with the flow rate of 50mL/min, preserving heat at the temperature of 1500 ℃ for 60min, then introducing ammonia gas with the flow rate of 50mL/min, and preserving heat at the temperature of 250 ℃ for 60min to obtain a precursor material C;
3) Uniformly mixing 100g of precursor material C with 5g of thiourea, and then heating to 900 ℃ for carbonization for 3 hours to obtain a heteroatom doped hard carbon material;
4) Mixing 100g of metallic silver and 10g of polyvinylidene fluoride by using a magnetron sputtering method, briquetting and taking the mixture as a target, putting the heteroatom doped hard carbon material prepared in the step 3) into a magnetron sputtering cavity to serve as a matrix, and adjusting the vacuum degree in the cavity to be 5 x 10 -3 And (3) Pa, introducing argon, keeping the pressure in the cavity at 5Pa, regulating the current of the target material at 200mA and the voltage at 1500V, sputtering for 60min, and cooling to room temperature after finishing to obtain the metal-coated heteroatom doped hard carbon composite material.
The sodium ion battery of this embodiment is button cell, including the battery case, be provided with positive plate, negative plate, diaphragm, electrolyte in the battery case, the negative plate includes negative current collector and sets up the negative material layer at negative current collector surface, and the negative material layer is by negative active material and conductive agent SP, binder LA132, water through mixing thick liquid, coating, drying, rolling and prepare, and the negative active material is foretell metal cladding heteroatom doped hard carbon combined material. The positive plate is sodium plate. The electrolyte is NaPF 6 The solution is a mixed solvent obtained by mixing EC and DEC in a volume ratio of 1:1, wherein the NaPF is a mixed solvent 6 The concentration was 1.1mol/L. The membrane is a polyethylene propylene (PEP) composite membrane.
Example 2
The preparation method of the metal-coated heteroatom doped hard carbon composite material comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 1g of sodium phytate, and carbonizing for 6 hours at 1000 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) Transferring the precursor material B into a tube furnace, introducing sulfur dioxide gas with the flow rate of 10mL/min, preserving heat at the temperature of 200 ℃ for 120min, then introducing phosphine gas with the flow rate of 10mL/min, and preserving heat at the temperature of 300 ℃ for 120min to obtain a precursor material C;
3) Uniformly mixing 100g of precursor material C with 1g of vulcanized polyacetylene, and then heating to 700 ℃ for carbonization for 6 hours to obtain a heteroatom doped hard carbon material;
4) Mixing 100g of metallic copper and 10g of polyvinylidene fluoride by using a magnetron sputtering method, briquetting and taking the mixture as a target, putting the heteroatom doped hard carbon material prepared in the step 3) into a magnetron sputtering cavity to serve as a matrix, and adjusting the vacuum degree in the cavity to be 1 x 10 -3 And (3) Pa, introducing argon, keeping the pressure in the cavity at 1Pa, regulating the current of the target material at 100mA and the voltage at 1000V, sputtering for 120min, and cooling to room temperature after finishing to obtain the metal-coated heteroatom doped hard carbon composite material.
The sodium ion battery of this example was a button cell, and the negative electrode active material was the metal-clad heteroatom-doped hard carbon composite of this example, otherwise the same as in example 1.
Example 3
The preparation method of the metal-coated heteroatom doped hard carbon composite material comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 10g of sodium carbonate, and carbonizing for 1h at 1500 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) Transferring the precursor material B into a tube furnace, introducing hydrogen chloride gas with the flow rate of 100mL/min, preserving heat at the temperature of 100 ℃ for 30min, then introducing hydrazine gas with the flow rate of 100mL/min, and preserving heat at the temperature of 200 ℃ for 30min to obtain a precursor material C;
3) Uniformly mixing 100g of precursor material C with 10g of melamine, and then heating to 1100 ℃ for carbonization for 1h to obtain a heteroatom doped hard carbon material;
4) 100g of metallic nickel and 10g of polyvinylidene fluoride are subjected to a magnetron sputtering methodMixing alkene, briquetting and using as target material, placing the heteroatom doped hard carbon material prepared in the step 3) into a magnetron sputtering cavity to be used as a matrix, and regulating the vacuum degree in the cavity to be 1 x 10 -2 And (3) Pa, introducing argon, keeping the pressure in the cavity at 10Pa, regulating the current of the target material at 100mA and the voltage at 1000V, sputtering for 10min, and cooling to room temperature after finishing to obtain the metal-coated heteroatom doped hard carbon composite material.
The sodium ion battery of this example was a button cell, and the negative electrode active material was the metal-clad heteroatom-doped hard carbon composite of this example, otherwise the same as in example 1.
Example 4
The preparation method of the metal-coated heteroatom doped hard carbon composite material comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 5g of sodium acetate, and carbonizing for 2 hours at 1200 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) Transferring the precursor material B into a tube furnace, introducing hydrogen chloride gas with the flow rate of 100mL/min, preserving heat at the temperature of 100 ℃ for 30min, then introducing hydrazine gas with the flow rate of 100mL/min, and preserving heat at the temperature of 200 ℃ for 30min to obtain a precursor material C;
3) Uniformly mixing 100g of precursor material C with 10g of melamine, and then heating to 1100 ℃ for carbonization for 1h to obtain a heteroatom doped hard carbon material;
4) Mixing 100g of nickel oxide and 10g of polyvinylidene fluoride by using a magnetron sputtering method, briquetting and taking the mixture as a target, putting the heteroatom doped hard carbon material prepared in the step 3) into a magnetron sputtering cavity to serve as a matrix, and adjusting the vacuum degree in the cavity to be 1 x 10 -1 And (3) Pa, introducing argon, keeping the pressure in the cavity at 50Pa, regulating the current of the target material at 100mA and the voltage at 1000V, sputtering for 10min, and cooling to room temperature after finishing to obtain the metal-coated heteroatom doped hard carbon composite material.
The sodium ion battery of this example was a button cell, and the negative electrode active material was the metal-clad heteroatom-doped hard carbon composite of this example, otherwise the same as in example 1.
Example 5
The preparation method of the metal-coated heteroatom doped hard carbon composite material comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 5g of sodium phytate, and carbonizing for 2 hours at 1100 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) Transferring the precursor material B into a tube furnace, introducing sulfur dioxide gas with the flow rate of 100mL/min, preserving heat at the temperature of 200 ℃ for 30min, then introducing phosphine gas with the flow rate of 100mL/min, and preserving heat at the temperature of 300 ℃ for 30min to obtain a precursor material C;
3) Uniformly mixing 100g of precursor material C with 5g of polythiopolystyrene and 5g of dopamine, and then heating to 1200 ℃ for carbonization for 1h to obtain a heteroatom doped hard carbon material;
4) Mixing 100g of nickel oxide and 10g of polyvinylidene fluoride by using a magnetron sputtering method, briquetting and taking the mixture as a target, putting the heteroatom doped hard carbon material prepared in the step 3) into a magnetron sputtering cavity to serve as a matrix, and adjusting the vacuum degree in the cavity to be 1 x 10 -1 And (3) Pa, introducing argon, keeping the pressure in the cavity at 50Pa, regulating the current of the target material at 100mA and the voltage at 1000V, sputtering for 10min, and cooling to room temperature after finishing to obtain the metal-coated heteroatom doped hard carbon composite material.
The sodium ion battery of this example was a button cell, and the negative electrode active material was the metal-clad heteroatom-doped hard carbon composite of this example, otherwise the same as in example 1.
Comparative example 1
The preparation method of the composite material of the comparative example comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 5g of sodium acetate, and carbonizing for 3 hours at 1200 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) And (3) uniformly mixing 100g of the precursor material B prepared in the step (1) with 1g of vulcanized polyacetylene, heating to 700 ℃ for carbonization for 6 hours, and cooling to room temperature to obtain the modified polyacetylene.
Comparative example 2
The preparation method of the composite material of the comparative example comprises the following steps:
1) Cleaning and crushing walnut shells, then washing with distilled water, and drying at 80 ℃ to obtain a raw material A; uniformly mixing 100g of raw material A with 5g of sodium acetate, and carbonizing for 3 hours at 1200 ℃ under the condition of introducing argon inert gas to obtain a precursor material B;
2) Transferring the precursor material B into a tube furnace, introducing hydrogen sulfide gas with the flow rate of 50mL/min, preserving heat at the temperature of 1500 ℃ for 60min, then introducing ammonia gas with the flow rate of 50mL/min, and preserving heat at the temperature of 250 ℃ for 60min to obtain a precursor material C;
3) Transferring the precursor material C prepared in the step 2) into a tube furnace, heating to 900 ℃ under the argon atmosphere, carbonizing for 3 hours, and cooling to room temperature to obtain the product.
Experimental example
(1) SEM test
The hard carbon composite material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the composite material has a granular structure, the size distribution is reasonable, and the grain diameter is between (5 and 10) mu m.
(2) Physical and chemical properties
Referring to the test method in GB/T-245332019 lithium ion battery graphite cathode material, the hard carbon composite materials prepared in examples 1-5 and comparative examples 1-2 were subjected to particle size, tap density, specific surface area, interlayer spacing, specific capacity and first efficiency tests. The test results are shown in Table 1 below.
As can be seen from table 1, the hard carbon composite material prepared in the examples has a slightly smaller particle size, a larger tap density and a larger specific surface area than those in the comparative examples, which has better processability and exhibits better electrochemical properties when the battery is prepared.
(3) Button cell testing
The hard carbon composites obtained in examples 1 to 5 and comparative examples 1 to 2 were assembled as negative electrode materials into button cells A1, A2, A3, A4, A5, B1, B2, respectively, according to the following steps:
and adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the mixture to obtain the negative electrode plate. The adhesive is LA132 adhesive, the conductive agent is SP, the solvent is secondary distilled water, the mass volume ratio of the anode material, SP, LA132 and secondary distilled water is 90g:4g:6g:220mL; the electrolyte adopts NaPF 6 EC+DEC (volume ratio of EC to DEC 1:1, concentration of 1.1 mol/L). The metallic sodium sheet is used as a counter electrode, and the diaphragm adopts a polyethylene propylene (PEP) composite film.
The battery assembly was carried out in an argon-filled glove box, and electrochemical performance was carried out on a wuhan blue electric CT2001A type battery tester with a charge-discharge voltage ranging from 0V to 2.0V and a charge-discharge rate of 0.1C. The button cell was also tested for its rate (2C, 0.1C) and cycle performance (0.1C/0.1C, 100 times).
The test data are detailed in table 1.
TABLE 1
As can be seen from table 1, the metal-coated heteroatom-doped hard carbon composite material prepared in example 1 has high specific capacity and first efficiency, and the reason for this is probably that the specific capacity of the electronic conductivity enhancing material doped with the silver enhancing material in the hard carbon material is exerted and the rate performance is improved, and at the same time, the irreversible capacity is reduced by doping lithium with the coal-based material to enhance the first efficiency.
3) Soft package battery
The silver-doped hard carbon composite materials prepared in examples 1 to 5 and comparative examples 1 to 2 were used as negative electrode materials, and layered oxides (NaFe 1/3 Mn 1/3 Ni 1/3 O 2 ) As positive electrode, naPF 6 (solvent)For EC and DEC, the volume ratio of the two is 1:1, naPF 6 A concentration in the electrolyte of 1.3 mol/L) is an electrolyte. Celebard 2400 was used as the septum. 2Ah soft package batteries C1, C2, C3, C4, C5, D1 and D2 are prepared.
And (3) multiplying power performance test:
the rate performance of the pouch cell was tested according to the following conditions: the charging and discharging voltage ranges from 1.5V to 4.0V, the temperature is 25+/-3.0 ℃, the charging is carried out at 0.5C,1.0C and 3.0C, the discharging is carried out at 1.0C, and the charging proportion and the constant current ratio of the battery are tested.
The test results are shown in Table 2.
TABLE 2
| Model number | Multiplying power | 0.5C | 1C | 3C |
| Example 1 | Constant current ratio (%) | 99.69 | 97.36 | 95.26 |
| Example 2 | Constant current ratio (%) | 99.29 | 97.18 | 95.32 |
| Example 3 | Constant current ratio (%) | 99.68 | 97.98 | 95.79 |
| Example 4 | Constant current ratio (%) | 99.31 | 97.04 | 95.01 |
| Example 5 | Constant current ratio (%) | 99.39 | 97.12 | 95.27 |
| Comparative example 1 | Constant current ratio (%) | 97.37 | 95.45 | 80.43 |
| Comparative example 2 | Constant current ratio (%) | 97.94 | 95.99 | 81.48 |
As can be seen from table 2, the rate charging performance of the soft pack batteries in examples 1 to 5 was significantly better than that of comparative examples 1 to 2, i.e., the charging time was shorter. The reasons for this may be: sodium ion migration is required in the battery charging process, and the doping of the material of the embodiment improves the constant current ratio of the material by improving the intercalation and deintercalation rate of sodium ions in the charging and discharging processes by a sodium compound; while doping silver promotes the electronic conductivity of the material and improves power performance.
And (3) testing the cycle performance:
the cycling performance of the pouch cell was tested as follows: the charge and discharge current is 1C/1C, the voltage range is 2-4.0V, and the cycle number is 500.
The test results are shown in Table 3.
TABLE 3 Table 3
As can be seen from table 3, the cycling performance of lithium ion batteries prepared using the metal-clad heteroatom-doped hard carbon composites obtained in examples 1-5 was significantly better at each stage than the comparative example. Experimental results show that the sodium salt doped compound of the material disclosed by the invention can be used for increasing the quantity of sodium ions in the charge and discharge processes and improving the cycle performance; meanwhile, the material of the embodiment has high specific surface area, so that the liquid retention performance of the material is improved, and the cycle performance is further improved.
Claims (10)
1. The metal-coated heteroatom doped hard carbon composite material is characterized in that the metal-coated heteroatom doped hard carbon composite material is of a core-shell structure, the core is hard carbon doped with sulfur and/or nitrogen, the shell is amorphous carbon containing transition metal elements, and the mass of the shell accounts for 1-10% of the mass of the composite material.
2. The preparation method of the metal-coated heteroatom doped hard carbon composite material is characterized by comprising the following steps of:
1) Uniformly mixing walnut shells and a pore-forming agent, and carbonizing under an inert atmosphere to obtain a first precursor material; the pore-forming agent is at least one of sodium acetate, sodium phytate, sodium carbonate and sodium bicarbonate;
2) The precursor material prepared in the step 1) is kept at 100-200 ℃ for 30-120min in an acid gas atmosphere, and then kept at 200-300 ℃ for 30-120min in an alkaline gas atmosphere, so as to obtain a pre-composite material M;
the acid gas is at least one of hydrogen sulfide, nitrogen dioxide, sulfur dioxide and hydrogen chloride;
the alkaline gas is at least one of ammonia, phosphine and hydrazine;
3) Uniformly mixing the pre-composite material M prepared in the step 2) with a sulfur source and/or a nitrogen source, and then preserving heat at 700-1100 ℃ for 1-6 hours to obtain a pre-composite material N; the sulfur source is at least one of thiourea, vulcanized polyacetylene, multi-vulcanized carboyne, multi-thio polystyrene, vulcanized polyvinyl chloride and multi-thio benzene;
the nitrogen source is at least one of melamine, urea, aniline, pyrrole and dopamine;
4) Performing magnetron sputtering treatment on the pre-composite material N in the step 3) by adopting a transition metal target material to obtain the composite material N; the transition metal is any one of silver, nickel, copper and titanium.
3. The method for preparing a metal-coated heteroatom doped hard carbon composite according to claim 2, characterized in that the carbonization temperature in step 1) is 1000-1500 ℃.
4. The method for preparing a metal-coated heteroatom doped hard carbon composite according to claim 2, characterized in that the carbonization time in step 1) is 1-6 hours.
5. The method for preparing the metal-coated heteroatom-doped hard carbon composite material according to claim 2, wherein the mass ratio of the walnut shell to the pore-forming agent in the step 1) is 100:1-10.
6. The method for preparing a metal-coated heteroatom doped hard carbon composite according to any one of claims 2-5, characterized in that the mass ratio of pre-composite M to sulfur source or nitrogen source in step 3) is 100:1-10.
7. The method for preparing a metal-coated heteroatom-doped hard carbon composite according to any one of claims 2-5, wherein the mass ratio of the sum of the mass of the sulfur source and the mass of the nitrogen source to the mass of the pre-composite is 1-10:100.
8. The method for preparing a metal-coated heteroatom-doped hard carbon composite according to any one of claims 2-5, wherein the current during the magnetron sputtering treatment in step 4) is 100-500mA; the voltage during the magnetron sputtering treatment in the step 4) is 1000-2000V.
9. The method for preparing a metal-coated heteroatom-doped hard carbon composite according to any one of claims 2-5, wherein the time for the magnetron sputtering treatment in step 4) is 10-120min.
10. The sodium ion battery comprises a battery shell, and a positive electrode, a negative electrode, a diaphragm and electrolyte which are arranged in the battery shell, wherein the negative electrode comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, and the negative electrode material layer comprises a negative electrode active substance.
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