CN115117339A - Hard carbon material and preparation method and application thereof - Google Patents
Hard carbon material and preparation method and application thereof Download PDFInfo
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- CN115117339A CN115117339A CN202210807312.8A CN202210807312A CN115117339A CN 115117339 A CN115117339 A CN 115117339A CN 202210807312 A CN202210807312 A CN 202210807312A CN 115117339 A CN115117339 A CN 115117339A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 62
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 24
- 229920002472 Starch Polymers 0.000 claims abstract description 22
- 238000003723 Smelting Methods 0.000 claims abstract description 20
- 239000008107 starch Substances 0.000 claims abstract description 20
- 235000019698 starch Nutrition 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 229920002261 Corn starch Polymers 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000008120 corn starch Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Substances O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000004976 Solanum vernei Nutrition 0.000 claims description 2
- 241000352057 Solanum vernei Species 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 229940100486 rice starch Drugs 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 33
- 238000003763 carbonization Methods 0.000 abstract description 31
- 238000011282 treatment Methods 0.000 abstract description 28
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000009830 intercalation Methods 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000008707 rearrangement Effects 0.000 abstract description 4
- 239000011165 3D composite Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000005554 pickling Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 239000012299 nitrogen atmosphere Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000002427 irreversible effect Effects 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
Abstract
The invention discloses a hard carbon material and a preparation method and application thereof, and belongs to the field of battery materials. The hard carbon material has the aperture of 0.5-20 nm and the true density of 1.3-2.26 g/cm 3 Specific surface area is less than or equal to 5m 2 (iv) g. The preparation method of the hard carbon material comprises the steps of firstly carrying out composite smelting on a nano-framework template material and starch to form a primary three-dimensional composite structure precursor, carrying out pre-carbonization treatment at a specific temperature to convert the precursor into a stable three-dimensional aromatized cubic network structure, carrying out acid pickling treatment to remove the nano-framework template material in situ, leaving a certain number of pores in the carbon cubic network structure, further carrying out high-temperature carbonization to carry out structural rearrangement, and carrying out self-repair on the pore structure on the surface to form a closed pore structureThe porous structure is finally reserved, the specific surface area of the product is reduced, and the problem of low initial de-intercalation efficiency can be effectively improved when the porous structure is applied to the negative electrode material of the sodium-ion battery.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a hard carbon material as well as a preparation method and application thereof.
Background
In constructing a new energy society, large-scale electricity storage is a key technology in numerous applications. However, the existing electrochemical system is mainly a secondary lithium battery system, and due to the lack of lithium resources on the earth and the shortage caused by the wide collection and use of the lithium resources, the existing secondary lithium battery system cannot realize large-scale energy storage application, and the development of the next generation of energy storage battery system with excellent comprehensive performance is urgently needed.
The sodium and the lithium belong to the same group of elements, have similar physicochemical properties with the lithium, and have the characteristics of abundant resources, environmental friendliness and low price (30-40 times lower than that of lithium raw material lithium carbonate). In addition, the electrode potential (Na) of sodium ions + Na) is more lithium-ion (Li) + the/Li) is 0.3V higher, and has more stable electrochemical performance and safety performance. However, the ionic radius (r ═ 0.113nm) of sodium ions is larger than that of lithium ions (r ═ 0.076nm), so that sodium ions are relatively stable in a rigid lattice, and almost no sodium intercalation capacity exists in a regular graphite structure, high-temperature graphitized carbon mesophase microsphere. The hard carbon can be partially pyrolyzed to obtain the reversible sodium intercalation capacity of nearly 280mAh/g, but the initial irreversible capacity is higher and the dynamic performance is poor. Generally speaking, the irreversible capacity problem of the hard carbon material sodium intercalation can be improved by structure optimization and specific surface area reduction, but the improvement degree of the prior art is still not considerable enough.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a hard carbon material and a preparation method thereof, the preparation method takes starch and a nano framework template material as raw materials to obtain a precursor by smelting, and then sequentially carries out series steps of pre-carbonization, template removal, high-temperature carbonization and the like, and the high-performance hard carbon material can be finally obtained without introducing additional processing equipment or secondary processing carbon source.
In order to achieve the purpose, the invention adopts the technical scheme that:
a hard carbon material, the aperture of the hard carbon material is 0.5-20 nm, and the true density is 1.3-2.26 g/cm 3 Specific surface area is less than or equal to 5m 2 /g。
The product prepared by the preparation method of the hard carbon material has the advantages of rich pore structure, stable carbon skeleton structure and small specific surface area, and when the hard carbon material is applied to a negative electrode material of a sodium ion battery, the irreversible sodium ion amount consumed by generating an SEI film in the initial sodium de-intercalation process is reduced, and the initial reversible specific capacity and the initial coulombic efficiency are effectively improved.
Another object of the present invention is to provide a sodium ion battery, wherein the negative electrode material of the sodium ion battery is prepared from the hard carbon material of the present invention.
Still another object of the present invention is to provide a method for preparing the hard carbon material, comprising the steps of:
(1) mixing and smelting the nano-framework template material and starch to be uniform in a protective atmosphere, and cooling to obtain a precursor A; the mass ratio of the nano-framework template material to the starch is 1: (5-20); the particle size of the nano-framework template material is 1-80 nm;
(2) heating the precursor A to 400-700 ℃ under a protective atmosphere for pre-carbonization for 4-8 h to obtain pre-carbonized carbon powder B;
(3) and (3) removing the nano framework template material from the pre-carbonized carbon powder B by acid washing, transferring to protective atmosphere, heating to 1000-1500 ℃ at a heating rate of 1-5 ℃, and carbonizing for 0.5-6 h to obtain the hard carbon material.
The preparation method of the hard carbon material comprises the steps of firstly carrying out composite smelting on a nano-framework template material and starch, wrapping the gelatinized starch outside the nano-framework template material and supporting the gelatinized starch by the nano-framework template material to form a three-dimensional composite structure, carrying out pre-carbonization treatment at a specific temperature on a precursor, further forming a new carbon chain section structure in the microstructure of the precursor, macroscopically converting the microstructure into a stable three-dimensional aromatized cubic network structure, leaving a certain number of pore structures in the carbon cubic network structure after the uniformly distributed nano-framework template material is removed in situ through acid washing treatment, carrying out high-temperature carbonization subsequently, setting a special temperature zone and a special heating rate, enabling the material to be subjected to structural rearrangement, starting self-repairing of the pore structure on the surface, generating a certain degree of tension retraction phenomenon and finally forming closed pores, and finally keeping the rich pore structures in the interior, the specific surface area of the product is reduced, and when the product is applied to the negative electrode material of the sodium-ion battery, the problem that the initial de-intercalation efficiency is low (caused by the fact that a large-area SEI film is generated due to overlarge specific surface area of the negative electrode material) in the initial de-intercalation process of the sodium ions of the existing product can be effectively improved. On the other hand, in the method, the shape and the appearance of the finally prepared hard carbon material are also influenced by the particle size of the nano-framework template material, if the particle size is too large, the initially generated pore structure is directly too large, and the self-repairing degree at the subsequent high temperature is limited.
Meanwhile, the inventor finds that if the precursor is not pre-carbonized before high-temperature carbonization, the chain segment structure generated in the material is directly fractured in the high-temperature pyrolysis process, so that the structure collapses, presents an undesirable sheet structure and is difficult to apply to sodium ion deintercalation; even if the pre-carbonization treatment is carried out, the self-repairing degree of the pore structure is related to the carbonization temperature and the heating rate in the subsequent high-temperature carbonization process, and if the carbonization condition is not selected properly, ideal pore structure tension retraction is difficult to realize.
Preferably, the nano framework template material is at least one of nano metal oxide, nano nonmetal oxide, nano halide, nano metal simple substance and nano nonmetal simple substance.
More preferably, the nano framework template material is at least one of nano magnesium oxide, nano zinc oxide, nano aluminum oxide, nano molybdenum dioxide, nano titanium dioxide, nano iron oxide, nano silicon dioxide, nano selenium dioxide, nano magnesium chloride, nano zinc chloride, nano iron simple substance, nano copper simple substance, nano silver simple substance, nano gold simple substance, nano silicon simple substance, nano selenium simple substance, nano antimony simple substance and nano sulfur simple substance.
More preferably, the mass ratio of the nanostruckle template material to the starch is 1: (10-20).
The preferable nano framework template material has high stability when being mixed with starch, does not generate obvious reaction, and can be fully used as a framework template to be compounded with the starch to form a precursor.
Preferably, the particle size of the nano framework template material is 10-40 nm.
Preferably, the starch is at least one of potato starch, corn starch, wheat starch, sweet potato starch, tapioca starch, rice starch and purple potato starch.
Preferably, the protective atmosphere in the step (1) is any one of nitrogen, argon and helium, the temperature during mixing and smelting is 200-235 ℃, the time is 4-20 hours, and the mixing speed is 100-500 rpm.
Under the smelting environment, the nano-framework template material can be fully wrapped in gelatinized starch and uniformly dispersed.
Preferably, the rate of temperature rise in the step (2) is 5-10 ℃/min.
At the heating rate, the carbon molecular chain in the starch is rearranged to form a new chain segment structure after series reactions such as dehydration, deoxidation and the like, and then is converted into a stable cubic network structure.
Preferably, the acid washing solution used in the acid washing treatment in the step (3) is at least one of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution and a hydrofluoric acid solution, the acid washing treatment time is 2-8 hours, and the temperature is 50-80 ℃.
It should be noted that the pre-carbonized carbon powder B of the present invention is not limited to the above treatment when removing the nano-framework template material, and can be equally replaced and used for some treatments that can also remove the nano-framework template material without affecting the carbon material in the material, for example, when the nano-framework template material is made of nano-silica with high purity, an alkaline solution can be selected and used in combination to remove the nano-framework template material according to actual conditions.
Preferably, the protective atmosphere in step (3) is any one of nitrogen, argon and helium.
The invention has the beneficial effects that the invention provides a hard carbon material and a preparation method thereof, the method comprises the steps of firstly carrying out composite smelting on a nanometer framework template material and starch to form a primary three-dimensional composite structure precursor, carrying out pre-carbonization treatment on the precursor at a specific temperature, further forming a new carbon chain section structure in the microstructure of the precursor, and carrying out macroscopic transformation to a stable three-dimensional aromatic cyclization cubic network structure, wherein after the nanometer framework template material is removed in situ through pickling treatment, a certain number of pore structures are left in the carbon cubic network structure, further carrying out structural rearrangement on the material after high-temperature carbonization at specific conditions, carrying out self-repair on the pore structure on the surface, finally forming closed pores, and finally reducing the specific surface area of the product while keeping the rich pore structure inside. When the method is applied to the negative electrode material of the sodium-ion battery, the problem of low initial de-intercalation efficiency of the conventional product caused by excessive irreversible consumption of sodium ions by an SEI (solid electrolyte interphase) film can be effectively solved. The invention also provides a sodium ion battery prepared by further applying the hard carbon material.
Drawings
FIG. 1 is a scanning electron microscope image of a pre-carbonized powder B in example 1 after acid washing to remove a nano-sized framework template material;
FIG. 2 is a scanning electron micrograph of a hard carbon material according to example 1 of the present invention;
FIG. 3 is a pore size distribution diagram of the pre-carbonized powder B after the acid washing treatment to remove the nano-skeleton template material in embodiment 1 of the present invention;
FIG. 4 is a graph showing the distribution of pore diameters of the hard carbon material according to example 1 of the present invention;
FIG. 5 is an XRD pattern of a hard carbon material according to example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of a hard carbon material according to comparative example 2 of the present invention;
FIG. 7 is a schematic view of a hard carbon material according to comparative example 2 of the present invention;
FIG. 8 is a pore size distribution diagram of a hard carbon material according to comparative example 3 of the present invention;
fig. 9 is a first charge-discharge curve diagram of the hard carbon material of example 1 of the present invention applied to a negative electrode material of a sodium ion battery.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments designed for the implementation of the present invention are common reagents and instruments unless otherwise specified.
Example 1
An embodiment of the hard carbon material and the preparation method thereof in this embodiment includes the following steps:
(1) under the nitrogen atmosphere, a mixture of 20g of nano-framework template material nano-zinc chloride (with the particle size of 10-40 nm) and 100g of corn starch is mixed and smelted in a smelting furnace at 230 ℃ for 8 hours at the rotating speed of 200rpm until the mixture is uniform, and the mixture is cooled to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 500 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere for pre-carbonization for 6h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and (3) carrying out acid washing treatment on the pre-carbonized carbon powder B by using 2mol/L hydrochloric acid solution at 60 ℃ for 4 hours to remove the nano framework template material, then washing the pre-carbonized carbon powder B by using deionized water, drying the pre-carbonized carbon powder B at 80 ℃ for 10 hours, transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, and heating the pre-carbonized carbon powder B to 1400 ℃ at a heating rate of 5 ℃ for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
Example 2
An embodiment of the hard carbon material and the preparation method thereof in this embodiment includes the following steps:
(1) mixing and smelting a mixture of 10g of nano titanium dioxide (with the particle size of 15-30 nm) and 100g of corn starch in a smelting furnace at 220 ℃ for 10h at the rotating speed of 200rpm until the mixture is uniform, and cooling to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 700 ℃ at a speed of 5 ℃/min under the nitrogen atmosphere for pre-carbonization for 4h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and (3) carrying out acid washing treatment on the pre-carbonized carbon powder B for 3h at 70 ℃ by using 2mol/L hydrochloric acid solution to remove the nano framework template material, washing the pre-carbonized carbon powder B clean by using deionized water, drying the pre-carbonized carbon powder B for 10h at 80 ℃, transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, and heating the pre-carbonized carbon powder B to 1200 ℃ at a heating rate of 2 ℃ for high-temperature carbonization for 4h to obtain the hard carbon material.
Example 3
An embodiment of the hard carbon material and the preparation method thereof in this embodiment includes the following steps:
(1) under the nitrogen atmosphere, mixing and smelting a mixture of 5g of nano-selenium powder (with the particle size of 10-40 nm) of a nano-framework template material and 100g of corn starch in a smelting furnace at 210 ℃ at the rotating speed of 200rpm for 18h until the mixture is uniform, and cooling to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 600 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere for pre-carbonization for 5h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and (3) carrying out acid washing treatment on the pre-carbonized carbon powder B for 2h at 80 ℃ by using 2mol/L hydrochloric acid solution to remove the nano framework template material, washing the pre-carbonized carbon powder B clean by using deionized water, drying the pre-carbonized carbon powder B for 10h at 80 ℃, transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, and heating the pre-carbonized carbon powder B to 1400 ℃ at a heating rate of 5 ℃ for high-temperature carbonization for 3h to obtain the hard carbon material.
Example 4
The difference between this example and example 1 is only that the amount of nano zinc chloride added is 10 g.
Comparative example 1
A method of preparing a hard carbon material, comprising the steps of:
(1) smelting 100g of a mixture of corn starch in a smelting furnace at 230 ℃ for 8h at a rotating speed of 200rpm in a nitrogen atmosphere, and cooling to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 400 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere for pre-carbonization for 2h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, raising the temperature to 1200 ℃ at a temperature raising rate of 5 ℃, and carrying out high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
Comparative example 2
A method of preparing a hard carbon material, comprising the steps of:
(1) mixing and smelting a mixture of 20g of nano-framework template material nano-zinc chloride (with the particle size of 10-40 nm) and 100g of corn starch in a smelting furnace at 230 ℃ for 8 hours at the rotating speed of 200rpm until the mixture is uniform, and cooling to 50 ℃ to obtain a precursor A;
(3) and (3) carrying out acid washing treatment on the precursor A for 4h at 60 ℃ by using 2mol/L hydrochloric acid solution to remove the nano-framework template material, washing the precursor A with deionized water, drying the precursor A for 10h at 80 ℃, transferring the precursor A to a nitrogen atmosphere, heating the precursor A to 1400 ℃ at a heating rate of 5 ℃, and carrying out high-temperature carbonization treatment for 3h to obtain the hard carbon material.
Comparative example 3
A method of preparing a hard carbon material, comprising the steps of:
(1) under the nitrogen atmosphere, a mixture of 20g of nano-framework template material nano-zinc chloride (with the particle size of 10-40 nm) and 100g of corn starch is mixed and smelted in a smelting furnace at 230 ℃ for 8 hours at the rotating speed of 200rpm until the mixture is uniform, and the mixture is cooled to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 500 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere for pre-carbonization for 6h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and (3) carrying out acid washing treatment on the pre-carbonized carbon powder B for 4 hours at 60 ℃ by using 2mol/L hydrochloric acid solution to remove the nano framework template material, washing the pre-carbonized carbon powder B clean by using deionized water, drying the pre-carbonized carbon powder B for 10 hours at 80 ℃, transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, and heating the pre-carbonized carbon powder B to 1400 ℃ at a heating rate of 10 ℃ for high-temperature carbonization for 3 hours to obtain the hard carbon material.
Comparative example 4
The comparative example differs from example 1 only in that the temperature at the time of the high-temperature carbonization treatment in the step (3) is 800 ℃.
Comparative example 5
The comparative example is different from example 1 only in that the nano zinc chloride is added in an amount of 25 g.
Comparative example 6
The comparative example is different from the example 1 only in that the particle size of the nano zinc chloride is 100-150 nm.
Comparative example 7
A method of preparing a hard carbon material, comprising the steps of:
(1) under the nitrogen atmosphere, a mixture of 20g of nano-framework template material nano-zinc chloride (with the particle size of 10-40 nm) and 100g of corn starch is mixed and smelted in a smelting furnace at 230 ℃ for 8 hours at the rotating speed of 200rpm until the mixture is uniform, and the mixture is cooled to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 800 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere for pre-carbonization for 3h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and (3) carrying out acid washing treatment on the pre-carbonized carbon powder B for 4 hours at 60 ℃ by using 2mol/L hydrochloric acid solution to remove the nano framework template material, washing the pre-carbonized carbon powder B clean by using deionized water, drying the pre-carbonized carbon powder B for 10 hours at 80 ℃, transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, and heating the pre-carbonized carbon powder B to 1400 ℃ at a heating rate of 5 ℃ for high-temperature carbonization for 3 hours to obtain the hard carbon material.
Comparative example 8
A method of preparing a hard carbon material, comprising the steps of:
(1) under the nitrogen atmosphere, a mixture of 20g of nano-framework template material nano-zinc chloride (with the particle size of 10-40 nm) and 100g of corn starch is mixed and smelted in a smelting furnace at 230 ℃ for 8 hours at the rotating speed of 200rpm until the mixture is uniform, and the mixture is cooled to 50 ℃ to obtain a precursor A;
(2) putting the precursor A into a sintering furnace, heating to 300 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere for pre-carbonization for 10h, and cooling to 50 ℃ to obtain pre-carbonized carbon powder B;
(3) and (3) carrying out acid washing treatment on the pre-carbonized carbon powder B by using 2mol/L hydrochloric acid solution at 60 ℃ for 4 hours to remove the nano framework template material, then washing the pre-carbonized carbon powder B by using deionized water, drying the pre-carbonized carbon powder B at 80 ℃ for 10 hours, transferring the pre-carbonized carbon powder B to a nitrogen atmosphere, and heating the pre-carbonized carbon powder B to 1400 ℃ at a heating rate of 5 ℃ for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
Effect example 1
In order to verify the preferable morphology and structure of the product obtained by the preparation method of the hard carbon material, the product obtained in each stage of the method in example 1 is subjected to scanning electron microscope observation, specific surface and pore size distribution test and XRD test, and the result is shown in figures 1-5. As can be seen from fig. 1 and 2, the pre-carbonized powder B obtained in the present invention undergoes acid washing treatment to remove the material of the nano-framework template, and then in-situ generates rich pore structures, which are distributed on the surface and inside of the material, while the hard carbon material particles after high temperature carbonization treatment are uniform and do not have agglomeration phenomenon; the pore size distribution of the sample is mainly concentrated in 100-150 nm before high-temperature carbonization, and after further high-temperature carbonization treatment, the pore structure generates a self-repairing phenomenon of tension retraction, and the pore size distribution is changed into micropores concentrated below 5 nm. As can be seen from the XRD pattern of the final product, the product has no residue of the nano-skeleton template material or other impurities generated, and only the characteristic peak of carbon is shown in the XRD pattern.
Effect example 2
Based on the test results of effect example 1, the specific surface area test and statistics were performed on the final product and the staged product (powder before high-temperature carbonization treatment) of each example and comparative example, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, the specific surface area of the pre-carbonized carbon powder B obtained by the preparation method of each example after acid washing is large, and after high-temperature carbonization, the self-repair of the pore structure occurs due to the structural rearrangement of the material itself, so that the specific surface area of the final product is significantly reduced, and the true density of the product is relatively reduced (in a certain range, the closed pore volume is in inverse proportion to the true density) because the closed pores are formed on the surface after the self-repair. In contrast, the product of comparative example 1 does not introduce any structural modification component, the specific surface area is small before high-temperature carbonization, after high-temperature carbonization, the specific surface area of the product is remarkably increased, a large amount of sodium ions are consumed to form an SEI film, and the irreversible capacity is high and the first effect is low. The product of comparative example 2 was not pre-carbonized during the preparation process, and although new segment structures could still be formed, these structures were not stable, but resulted in the collapse of the microstructure of the product and the formation of sheet-like structures, as shown in fig. 6, while the product also appeared in an expanded state macroscopically after high-temperature carbonization, as shown in fig. 7. The high-temperature carbonization conditions set in comparative examples 3 and 4 are not preferable, and although the specific surface area of the final product is reduced compared to that of the product before high-temperature carbonization, the self-healing degree of the pore structure is insufficient, wherein as can be seen from the pore size distribution diagram of the product shown in fig. 8, the pore size of the product is mainly distributed within 1000 to 1500nm, which is greatly different from that of the hard carbon material according to the embodiment of the present invention. The products of comparative examples 5 and 6 have excessive specific surface area and pore structure of the sample after pre-carbonization due to excessive use of the template agent and excessive particle size, and the high-temperature carbonization specific surface area is not reduced much subsequently, because the self-repairing function of the material is to utilize the tension retraction of the material in the processes of pyrolysis and carbonization, but the 'repairing' capability is limited, and when the pore structure is excessive, the purpose of reducing the specific surface area is not achieved. The product of the comparative example 7 has over-high pre-carbonization temperature, and the structure tends to be stabilized, so that the self-repairing effect of the subsequent material is not obvious, and the change of the specific surface area is not large. The product of comparative example 8 has a low pre-carbonization temperature, which results in an unobvious change of the specific surface area before and after pre-carbonization, and an unstable structure inside the structure is not completely removed, which results in an obvious increase of the specific surface area during subsequent high-temperature carbonization, because in the high-temperature carbonization process, unstable functional groups in the material undergo a series of very complex reactions such as chain scission, dehydration, decarboxylation, condensation, etc., to form a pore structure, and meanwhile, the structure is further stabilized to finally form the hard carbon material containing the pore structure.
Further, the products of each example and comparative example are applied to a sodium ion half cell for performance test, and the specific steps are as follows:
the hard carbon material, sodium carboxymethyl cellulose and Super P conductive carbon black obtained in the example/the comparative example are mixedAnd polymer binder are mixed according to the mass ratio of 95:2:1:2 and are prepared into slurry by deionized water, the slurry is coated on copper foil and is dried and cut to obtain a carbon negative plate, sodium metal is used as a counter electrode and a reference electrode, and NaClO is used as a reference electrode 4 The method comprises the steps of taking a mixed solution of ethylene carbonate and propylene carbonate dissolved in a volume ratio of 1:1 as an electrolyte, assembling the mixed solution into a button half cell under a protective atmosphere, and then carrying out an electrochemical performance test under a working voltage of 0-2V and a current density of 0.1C, wherein the results are shown in Table 2.
TABLE 2
It can be seen from table 2 that the specific capacity of the products of the embodiments during the first charging after the first discharging to generate the SEI film can reach 330mAh/g, and the first charging and discharging efficiency also reaches more than 85%, which indicates that the hard carbon material of the present invention can provide sufficient deintercalation sites for sodium ions to ensure a higher specific capacity, and can significantly reduce the amount of irreversible sodium ions consumed during the first fully charged process of the SEI film and ensure a higher coulomb efficiency due to the structural optimization when used as a sodium ion battery negative electrode material. As can be seen from the first charge-discharge curve of the sodium ion battery prepared from the product obtained in example 1 in fig. 9, a corresponding platform generated by the SEI film appears during the first discharge of the curve, and a high specific charge capacity is still maintained, which indicates that not only an adequate SEI film is generated on the electrode sheet, but also a high reversible specific capacity is ensured, and the electrochemical performance is excellent. In contrast, the comparative products still cannot avoid the large irreversible sodium ion consumption loss caused by the SEI film generation due to the structure that is difficult to achieve the ideal effect.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The hard carbon material is characterized in that the aperture of the hard carbon material is 0.5-20 nm, and the true density is 1.3-2.26 g/cm 3 Specific surface area is less than or equal to 5m 2 /g。
2. A sodium ion battery, wherein a negative electrode material in the sodium ion battery is prepared from the hard carbon material according to claim 1.
3. The method for preparing a hard carbon material according to claim 1, comprising the steps of:
(1) mixing and smelting the nano-framework template material and starch to be uniform in a protective atmosphere, and cooling to obtain a precursor A; the mass ratio of the nano-framework template material to the starch is 1: (5-20); the particle size of the nano-framework template material is 1-80 nm;
(2) heating the precursor A to 400-700 ℃ under a protective atmosphere for pre-carbonization for 4-8 h to obtain pre-carbonized carbon powder B;
(3) and (3) removing the nano framework template material from the pre-carbonized carbon powder B by acid washing, transferring to protective atmosphere, heating to 1000-1500 ℃ at a heating rate of 1-5 ℃, and carbonizing for 0.5-6 h to obtain the hard carbon material.
4. The method for preparing a hard carbon material according to claim 3, wherein the nano-skeleton template material is at least one of a nano-metal oxide, a nano-nonmetal oxide, a nano-halide, a nano-metal simple substance, and a nano-nonmetal simple substance.
5. The method for preparing a hard carbon material according to claim 4, wherein the nano-skeleton template material is at least one of nano-magnesia, nano-zinc oxide, nano-alumina, nano-molybdenum dioxide, nano-titanium dioxide, nano-iron oxide, nano-silica, nano-selenium dioxide, nano-magnesium chloride, nano-zinc chloride, nano-iron simple substance, nano-copper simple substance, nano-silver simple substance, nano-gold simple substance, nano-silicon simple substance, nano-selenium simple substance, nano-antimony simple substance, and nano-sulfur simple substance.
6. The method of preparing a hard carbon material according to claim 3, wherein the mass ratio of the nano-skeleton template material to the starch is 1: (10-20).
7. The method for preparing a hard carbon material according to claim 3, wherein the nano-skeleton template material has a particle size of 10 to 40 nm.
8. The method for preparing a hard carbon material according to claim 3, wherein the starch is at least one of potato starch, corn starch, wheat starch, sweet potato starch, tapioca starch, rice starch, and purple potato starch.
9. The method for preparing a hard carbon material according to claim 3, wherein the protective atmosphere in the step (1) is any one of nitrogen, argon and helium, the temperature during mixing and melting is 200-235 ℃, the time is 4-20 h, and the mixing speed is 100-500 rpm.
10. The method for preparing a hard carbon material according to claim 3, wherein the rate of temperature rise in the step (2) is 5 to 10 ℃/min.
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| CN115974045A (en) * | 2022-12-06 | 2023-04-18 | 江西师范大学 | Method for preparing hard carbon by chemical gel synergistic basic metal oxide template method and application thereof |
| WO2024007461A1 (en) * | 2022-07-08 | 2024-01-11 | 广东邦普循环科技有限公司 | Hard carbon material, preparation method therefor and use thereof |
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| CN109921018A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material |
| CN112225194B (en) * | 2020-09-24 | 2022-03-01 | 中国科学院化学研究所 | Hard carbon material and preparation method and application thereof |
| CN113800496A (en) * | 2021-08-06 | 2021-12-17 | 深圳市德方纳米科技股份有限公司 | Hard carbon material and preparation method and application thereof |
| CN114497545A (en) * | 2021-12-01 | 2022-05-13 | 广东邦普循环科技有限公司 | Hard carbon negative electrode material and preparation method and application thereof |
| CN115117339A (en) * | 2022-07-08 | 2022-09-27 | 广东邦普循环科技有限公司 | Hard carbon material and preparation method and application thereof |
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| WO2024007461A1 (en) * | 2022-07-08 | 2024-01-11 | 广东邦普循环科技有限公司 | Hard carbon material, preparation method therefor and use thereof |
| CN115974045A (en) * | 2022-12-06 | 2023-04-18 | 江西师范大学 | Method for preparing hard carbon by chemical gel synergistic basic metal oxide template method and application thereof |
| CN115974045B (en) * | 2022-12-06 | 2024-02-13 | 江西师范大学 | Method for preparing hard carbon by chemical gel synergistic alkaline metal oxide template method and application thereof |
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