CN115626630A - Biomass carbon negative electrode material for sodium ion battery and preparation method and application thereof - Google Patents
Biomass carbon negative electrode material for sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN115626630A CN115626630A CN202211388183.XA CN202211388183A CN115626630A CN 115626630 A CN115626630 A CN 115626630A CN 202211388183 A CN202211388183 A CN 202211388183A CN 115626630 A CN115626630 A CN 115626630A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 171
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 71
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 116
- 238000001354 calcination Methods 0.000 claims abstract description 69
- 239000010426 asphalt Substances 0.000 claims abstract description 50
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 241001122767 Theaceae Species 0.000 claims abstract description 26
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 35
- 238000000227 grinding Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 238000010306 acid treatment Methods 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000009656 pre-carbonization Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000011734 sodium Substances 0.000 abstract description 12
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
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- 238000003786 synthesis reaction Methods 0.000 abstract description 2
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- 238000003756 stirring Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 238000001914 filtration Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 10
- 239000008213 purified water Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 229910021384 soft carbon Inorganic materials 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000009829 pitch coating Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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Abstract
According to the invention, the biomass carbon cathode material for the sodium-ion battery with excellent sodium storage performance is prepared through simple multiple calcination, asphalt coating and carbonization treatment processes, is a low-cost, easily-synthesized, green and environment-friendly biomass hard carbon material synthesis process taking tea seed shells and asphalt as raw materials, has the characteristics of simple operation, strong repeatability, expandability and low cost, has a rich pore structure and a proper interlayer spacing, and shows excellent electrochemical performance. The biomass carbon negative electrode material for the sodium ion battery prepared in the embodiment 3 of the invention has the first charge capacity of 310.5mAh g ‑1 First effect 92.5%, circulateAfter 50 weeks, the capacity is hardly attenuated, which shows that the cycle performance is excellent and meets the industrialization requirement.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a biomass carbon negative electrode material for a sodium ion battery and a preparation method and application thereof.
Background
Lithium ion batteries are widely used in practical production and life due to their advantages of light weight, high energy density, no memory effect, etc. However, lithium resources in the crust are scarce and are unevenly distributed worldwide, and meanwhile, the price of the lithium resources is greatly increased due to the continuous increase of market demand, so that the lithium resources are difficult to be used for large-scale power grid energy storage. Based on this, sodium ion batteries are the best alternative to lithium ion batteries with their cost and resource advantages.
The negative electrode material with low development cost, high theoretical specific capacity and good stability is the key for realizing the application of the sodium-ion battery in an energy storage system, wherein the hard carbon material has larger interlayer spacing and disordered structure, and shows excellent sodium storage performance when being used as the negative electrode material of the sodium-ion battery. The hard carbon prepared by using biomass as a raw material has the characteristics of wide sources, simple preparation and low cost and is always concerned. The reported biomass hard carbon materials mainly comprise bagasse, straws, peanut shells, cherry petals, corn cobs, orange peels and the like, but when the biomass hard carbon materials are applied to a sodium ion battery negative electrode material, the first coulombic efficiency and specific capacity of the biomass hard carbon materials are difficult to meet the requirements of commercial sodium ion battery negative electrode materials.
Disclosure of Invention
The biomass carbon negative electrode material for the sodium ion battery prepared by the method provided by the invention has the advantages of high coulombic efficiency and specific capacity for the first time, wide raw material source and low cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a biomass carbon negative electrode material for a sodium ion battery, which comprises the following steps:
(1) Sequentially carrying out first calcination, crushing and screening on tea seed shells to obtain a preliminary biomass carbon material;
(2) Sequentially carrying out acid treatment, alkali treatment, washing and first drying on the primary biomass carbon material obtained in the step (1) to obtain a pretreated biomass carbon material;
(3) Performing second calcination on the pretreated biomass carbon material obtained in the step (2) to obtain a secondary calcined biomass carbon material;
(4) Sequentially carrying out alkali mixed grinding and third calcination on the secondary calcined biomass carbon material obtained in the step (3) to obtain a modified biomass hard carbon material;
(5) Mixing the modified biomass hard carbon material obtained in the step (4) with the asphalt coating solution, and then carrying out secondary drying to obtain a precursor material;
(6) And (5) sequentially carrying out pre-carbonization and carbonization treatment on the precursor material obtained in the step (5) to obtain the biomass carbon negative electrode material for the sodium-ion battery.
Preferably, the first calcination in step (1) is performed in an inert atmosphere, the temperature of the first calcination is 180 to 650 ℃, the temperature rise rate of the first calcination is 1.5 to 32 ℃/min, and the time of the first calcination is 0.5 to 6 hours.
Preferably, the particle size of the primary biomass carbon material in the step (1) is 80-600 meshes.
Preferably, the acid treatment time in the step (2) is 3-9 h, and the acid treatment temperature is 20-90 ℃.
Preferably, the second calcination in step (3) is performed in an inert atmosphere, the temperature of the second calcination is 700-1700 ℃, the temperature rise rate of the second calcination is 1.5-12 ℃/min, and the time of the second calcination is 1-12 h.
Preferably, the mass ratio of the biomass carbon material subjected to secondary calcination in the step (4) to the alkali used for alkali mixed grinding is 1:0.5 to 5; the temperature of the third calcination is 400-900 ℃, the temperature rise speed of the third calcination is 2-22 ℃/min, and the time of the third calcination is 0.5-3 h.
Preferably, the amount of the asphalt in the asphalt coating liquid in the step (5) is 5wt% to 35wt% of the amount of the modified biomass hard carbon material.
Preferably, the pre-carbonization in the step (6) is carried out in an inert atmosphere, the pre-carbonization temperature is 280-550 ℃, and the pre-carbonization time is 1-7 h.
The invention also provides the biomass carbon negative electrode material for the sodium ion battery, which is prepared by the preparation method in the technical scheme.
The invention also provides the biomass carbon negative electrode material for the sodium ion battery prepared by the preparation method in the technical scheme or the application of the biomass carbon negative electrode material for the sodium ion battery in the negative electrode material for the sodium ion battery.
The invention provides a preparation method of a biomass carbon cathode material for a sodium ion battery, which comprises the steps of sequentially carrying out first calcination, crushing and screening on tea seed shells to obtain a preliminary biomass carbon material, carrying out preliminary decomposition and carbonization on a carbon-containing compound in the tea seed shells of the biomass material, and fixing the form of the material; sequentially carrying out acid treatment, alkali treatment, washing and first drying on the preliminary biomass carbon material to fully remove impurities in the preliminary biomass carbon material and reduce ash content including potassium, calcium, magnesium, silicon, sodium and the like to obtain a pretreated biomass carbon material; carrying out secondary calcination on the pretreated biomass carbon material to obtain a secondary calcined biomass carbon material, and improving the graphitization degree of the pretreated biomass carbon material by utilizing the secondary calcination, enlarging the interlayer spacing, improving the specific surface area, facilitating the embedding and the separation of sodium ions, and improving the reversible capacity, the first coulombic efficiency and the cycling stability of the biomass carbon negative electrode material for the sodium-ion battery; sequentially carrying out alkali mixed grinding and third calcining on the secondary calcined biomass carbon material to obtain a modified biomass hard carbon material, wherein alkali used in the alkali mixed grinding can react with carbon in the secondary calcined biomass carbon material to generate gas and other substances, the escape of the gas can increase holes in the material, and the other substances can be treated by corresponding acid or alkali solution to leave holes, so that the regulation and the reformation of a hole structure are realized, the sodium storage performance of the final biomass carbon cathode material for the sodium ion battery can be improved, and the specific capacity of the final biomass carbon cathode material can be improved; will be provided withThe modified biomass hard carbon material is mixed with the asphalt coating liquid, the modified biomass hard carbon material is shaped and coated by utilizing the asphalt in the asphalt coating liquid, the conductivity of the biomass carbon negative electrode material for the sodium ion battery prepared subsequently is improved, the specific surface area is reduced, the migration of sodium ions is facilitated, the rate capability is improved, and a precursor material is obtained after drying; the precursor material is pre-carbonized, so that the coating effect of the pitch on the biomass hard carbon material is further improved, and then the carbonization treatment is utilized to promote the pitch coated on the surface of the precursor material to be completely carbonized, so that the conductivity of the finally prepared biomass carbon cathode material for the sodium ion battery can be improved, the initial coulombic efficiency is improved, and better cycle performance and rate capability are obtained. The method provided by the invention takes the tea seed shells with rich sources and low price as the raw materials, and uses the asphalt for modification, the process is simple, the cost is low, the prepared biomass carbon negative electrode material for the sodium ion battery has the advantages of hard carbon and soft carbon materials in the sodium ion battery, has high capacity of the hard carbon and high conductivity of the soft carbon, has excellent sodium insertion and sodium removal capabilities, can simultaneously realize high first effect, high specific capacity, high rate performance and stable cycle performance when being used in the sodium ion battery, has good electrochemical performance, can meet various performance requirements of the negative electrode material of the sodium ion battery, and has wide application prospect. The results of the examples show that the biomass carbon anode material for the sodium ion battery prepared in example 3 of the invention is rich in micropores, and the existence of the pitch carbon can be more beneficial to the intercalation/deintercalation of sodium ions, so that the biomass carbon anode material has good electrochemical performance, and the first charge capacity of the biomass carbon anode material is 310.5mAh g -1 The first effect is 92.5%, and the capacity is hardly attenuated after 50 weeks of circulation, which shows that the cycle performance is excellent and meets the industrial requirements.
Drawings
Fig. 1 is a scanning electron microscope image of a biomass carbon negative electrode material for a sodium ion battery prepared in example 3 of the present invention;
fig. 2 is an electrochemical test chart of the biomass carbon negative electrode material for the sodium ion battery prepared in example 3 of the present invention.
Detailed Description
The invention provides a preparation method of a biomass carbon negative electrode material for a sodium ion battery, which comprises the following steps:
(1) Sequentially carrying out first calcination, crushing and screening on tea seed shells to obtain a preliminary biomass carbon material;
(2) Sequentially carrying out acid treatment, alkali treatment, washing and first drying on the primary biomass carbon material obtained in the step (1) to obtain a pretreated biomass carbon material;
(3) Performing second calcination on the pretreated biomass carbon material obtained in the step (2) to obtain a secondary calcined biomass carbon material;
(4) Sequentially carrying out alkali mixed grinding and third calcination on the secondary calcined biomass carbon material obtained in the step (3) to obtain a modified biomass hard carbon material;
(5) Mixing the modified biomass hard carbon material obtained in the step (4) with the asphalt coating solution, and then carrying out second drying to obtain a precursor material;
(6) And (5) sequentially carrying out pre-carbonization and carbonization treatment on the precursor material obtained in the step (5) to obtain the biomass carbon negative electrode material for the sodium-ion battery.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
According to the invention, tea seed shells are sequentially subjected to primary calcination, crushing and sieving to obtain a primary biomass carbon material.
In the invention, the tea seed shells are preferably obtained by sequentially carrying out purified water washing and vacuum drying on a tea seed shell raw material.
The invention removes impurities on the surface of the tea seed shell raw material by washing with purified water. In the present invention, the vacuum drying method is not particularly limited, and the purpose of removing moisture may be achieved.
In the present invention, the first calcination is preferably performed in an inert atmosphere. In the present invention, the inert atmosphere is preferably nitrogen or argon. In the present invention, the temperature of the first calcination is preferably 180 to 650 ℃, more preferably 200 to 600 ℃. In the present invention, the temperature increase rate in the first calcination is preferably 1.5 to 32 ℃/min, more preferably 2 to 30 ℃/min. In the present invention, the time for the first calcination is preferably 0.5 to 6 hours, and more preferably 1 to 5 hours. The temperature, the temperature rise rate and the time of the first calcination are controlled within the above ranges, so that the carbonaceous compounds in the biomass material tea seed shells are subjected to primary decomposition and carbonization, and the form of the material is fixed.
In the present invention, the crushing is preferably grinding. The sieving mode is not particularly limited, and the purpose of obtaining the primary biomass carbon material with the particle size of 80-600 meshes is achieved. In the present invention, the particle size of the primary biomass carbon material is preferably 80 to 600 mesh, and more preferably 100 to 500 mesh. The particle size of the primary biomass carbon material is controlled within the range, so that primary biomass carbon material particles with relatively uniform particle size are obtained, and the subsequent process is facilitated.
After the preliminary biomass carbon material is obtained, the preliminary biomass carbon material is sequentially subjected to acid treatment, alkali treatment, washing and first drying to obtain a pretreated biomass carbon material.
In the invention, the acid solution used for acid treatment is preferably HCl or HNO 3 、H 3 PO 4 、H 2 SO 4 And an aqueous solution of at least one of HF and hydrogen fluoride. In the present invention, the concentration of the acid solution is preferably 1 to 7mol/L, and more preferably 0.5 to 6mol/L. In the present invention, the mass ratio of the acid solution to the primary biomass carbon material is preferably (10 to 22): 1, and more preferably (12 to 20): 1. In the present invention, the temperature of the acid treatment is preferably 20 to 90 ℃, more preferably 25 to 85 ℃. In the present invention, the time for the acid treatment is preferably 3 to 9 hours, and more preferably 4 to 8 hours. The invention controls the mass ratio of the acid solution to the primary biomass carbon material, the acid treatment time and the temperature within the ranges, promotes the impurities to be dissolved in the acid solution, and fully removes the impurities.
In the present invention, the alkali solution used for the alkali treatment is preferably KOH, naOH, na 2 CO 3 And K 2 CO 3 An aqueous solution of at least one of (1). In the present invention, the quality of the alkali solution is excellentThe mass of the alkali solution and the primary biomass carbon material is 3-55%, and the mass is preferably 5-50%. In the present invention, the temperature of the alkali treatment is preferably 20 to 130 ℃, more preferably 25 to 120 ℃. In the present invention, the time of the alkali treatment is preferably 1 to 9 hours, more preferably 2 to 8 hours. The invention controls the time and temperature of alkali treatment in the above range, and promotes the impurities to be dissolved in the alkali solution, so as to fully remove the impurities.
In the present invention, the agent for washing is preferably purified water. The invention has no special limitation on the washing times, and can achieve the purpose of washing to obtain the neutral pretreated biomass carbon material.
In the present invention, the first drying method is preferably vacuum drying; the temperature of the primary drying is preferably 55 to 130 ℃, more preferably 60 to 120 ℃. In the present invention, the time for the first drying is preferably 10 to 38 hours, and more preferably 12 to 36 hours. The present invention controls the temperature and time of the first drying within the above ranges to remove moisture in the material.
After the pretreated biomass carbon material is obtained, the pretreated biomass carbon material is subjected to secondary calcination to obtain a secondary calcined biomass carbon material.
In the present invention, the second calcination is preferably performed in an inert atmosphere. In the present invention, the inert atmosphere is preferably nitrogen or argon. In the present invention, the temperature of the second calcination is preferably 700 to 1700 ℃, more preferably 800 to 1600 ℃. In the present invention, the temperature increase rate of the second calcination is preferably 1.5 to 12 ℃/min, more preferably 2 to 10 ℃/min. In the present invention, the time for the second calcination is preferably 1 to 12 hours, and more preferably 2 to 10 hours. The temperature, the heating rate and the time of the second calcination are controlled within the ranges, so that the graphitization degree of the pretreated biomass carbon material is improved, the interlayer spacing is enlarged, the specific surface area is improved, the intercalation and the deintercalation of sodium ions are facilitated, the reversible capacity of the biomass carbon cathode material for the sodium ion battery is improved, and the electrochemical performance of the biomass carbon cathode material is improved.
After the secondary calcined biomass carbon material is obtained, the secondary calcined biomass carbon material is sequentially subjected to alkali mixed grinding and third calcination to obtain the modified biomass hard carbon material.
In the invention, the alkali used for alkali mixed grinding is preferably KOH, naOH or Na 2 CO 3 、K 2 CO 3 At least one of (1). In the present invention, the mass ratio of the alkali used for the alkali-kneading and the secondary-calcined biomass carbon material is preferably (0.5 to 5): 1, and more preferably (1 to 3): 1. In the present invention, the temperature of the alkali treatment is preferably 20 to 90 ℃, more preferably 25 to 80 ℃. The mass ratio and the temperature of the alkali used in the alkali mixed grinding and the secondary calcined biomass carbon material are controlled within the range, and the alkali reacts with the carbon in the secondary calcined biomass carbon material to increase holes, so that the regulation and the reformation of the pore structure are realized, the sodium storage performance of the final biomass carbon cathode material for the sodium ion battery is favorably improved, and the specific capacity of the final biomass carbon cathode material is improved.
In the present invention, the third calcination is preferably performed in an inert atmosphere. In the present invention, the inert atmosphere is preferably nitrogen or argon. In the present invention, the temperature of the third calcination is preferably 400 to 900 ℃, more preferably 500 to 800 ℃. In the present invention, the temperature increase rate of the third calcination is 2 to 22 ℃/min, more preferably 3 to 20 ℃/min. In the present invention, the time for the third calcination is preferably 0.5 to 3 hours, and more preferably 0.5 to 2 hours. The temperature, the heating rate and the time of the third calcination are controlled within the ranges, so that the hole expanding treatment of the secondary calcined biomass carbon material by the alkali is realized.
After the modified biomass hard carbon material is obtained, the modified biomass hard carbon material is mixed with the asphalt coating solution, and then secondary drying is carried out to obtain the precursor material.
In the present invention, the asphalt coating liquid is preferably composed of asphalt and an organic solvent. The preparation method of the asphalt coating liquid is not particularly limited, and the technical scheme known in the field can be adopted. In the present invention, the organic solvent is preferably at least one of methanol, ethanol, ethylene glycol, butanol, acetonitrile, toluene, and tetrahydrofuran. The invention utilizes the organic solvent of the kind to dissolve the asphalt, so that all the components are uniformly mixed, and the coating effect of the asphalt on the modified biomass hard carbon material is improved.
In the present invention, the modified biomass hard carbon material and the pitch-coated liquid are preferably mixed under mechanical stirring. In the present invention, the speed of the mechanical stirring is preferably 50 to 500rpm, more preferably 60 to 450rpm. In the present invention, the mixing temperature of the modified biomass hard carbon material and the pitch coating liquid is preferably 50 to 110 ℃, and more preferably 60 to 100 ℃. The invention controls the mixing temperature of the modified biomass hard carbon material and the asphalt coating liquid within the range, so that the organic solvent is volatilized, and the asphalt can be attached to the surface of the modified biomass hard carbon material.
In the present invention, the amount of the asphalt in the asphalt coating liquid is 5 to 35wt%, and more preferably 10 to 30wt% of the amount of the modified biomass hard carbon material. According to the invention, the use amount of the asphalt in the asphalt coating liquid is controlled within the range, so that the asphalt in the asphalt coating liquid is used for shaping and coating the modified biomass hard carbon material, the conductivity of the biomass carbon negative electrode material for the sodium ion battery prepared subsequently is improved, the specific surface area is reduced, the migration of sodium ions is facilitated, and the rate capability is improved.
In the present invention, the second drying method is preferably vacuum drying. In the present invention, the temperature of the second drying is preferably 50 to 90 ℃, more preferably 60 to 80 ℃. In the present invention, the time for the second drying is preferably 3 to 7 hours, and more preferably 4 to 6 hours. The present invention controls the temperature and time of the second drying within the above ranges to remove moisture in the material.
After the precursor material is obtained, the precursor material is sequentially subjected to pre-carbonization and carbonization treatment to obtain the biomass carbon negative electrode material for the sodium ion battery.
In the present invention, the pre-carbonization apparatus is preferably a tube furnace. In the present invention, the pre-carbonization is preferably performed in an inert atmosphere. In the present invention, the inert atmosphere is preferably nitrogen or argon. In the present invention, the temperature of the pre-carbonization is preferably 280 to 550 ℃, more preferably 300 to 500 ℃. In the present invention, the time for the pre-carbonization is preferably 1 to 7 hours, more preferably 2 to 6 hours. In the present invention, the temperature increase rate of the pre-carbonization is preferably 4 to 25 ℃/min, and more preferably 5 to 20 ℃/min. The invention controls the temperature, time and heating rate of the pre-carbonization within the above range to promote the softening of the pitch coated on the surface of the precursor material and realize better coating effect.
In the present invention, the carbonization apparatus is preferably a tube furnace. In the present invention, the carbonization treatment is preferably performed in an inert atmosphere. In the present invention, the inert atmosphere is preferably nitrogen or argon. In the present invention, the temperature of the carbonization treatment is preferably 900 to 1300 ℃, and more preferably 950 to 1200 ℃. In the present invention, the time for the carbonization treatment is preferably 3 to 12 hours, and more preferably 5 to 10 hours. In the present invention, the temperature increase rate in the carbonization treatment is preferably 4 to 25 ℃/min, and more preferably 5 to 20 ℃/min. The invention controls the temperature, time and heating rate of carbonization treatment in the above range, promotes complete carbonization of the pitch coated on the surface of the precursor material, can improve the conductivity of the finally prepared biomass carbon cathode material for the sodium-ion battery, improves the initial coulombic efficiency, and obtains better cycle performance and rate capability thereof.
The method provided by the invention has the characteristics of rich sources, simple process and low cost.
The invention also provides the biomass carbon negative electrode material for the sodium ion battery, which is prepared by the preparation method in the technical scheme. In the invention, the biomass carbon negative electrode material for the sodium ion battery preferably comprises a hard carbon main body and a soft carbon modification layer.
The biomass carbon negative electrode material for the sodium ion battery prepared by the invention has the advantages of hard carbon and soft carbon materials (tea seed shells are converted into hard carbon, asphalt is converted into soft carbon) in the sodium ion battery, has high capacity of the hard carbon and high conductivity of the soft carbon, has excellent sodium intercalation and sodium removal capabilities, can simultaneously realize high first effect, high specific capacity, high rate capability and stable cycle performance when being used in the sodium ion battery, has good electrochemical performance, can meet various performance requirements of the negative electrode material of the sodium ion battery, and has wide application prospect.
The invention also provides the biomass carbon negative electrode material for the sodium ion battery prepared by the preparation method in the technical scheme or the application of the biomass carbon negative electrode material for the sodium ion battery in the negative electrode material for the sodium ion battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the biomass carbon negative electrode material for the sodium ion battery comprises the following steps:
(1) Washing a tea seed shell raw material with purified water, filtering, drying in vacuum to obtain tea seed shells, placing the tea seed shells in a tube furnace, heating from room temperature to 500 ℃ at the speed of 3 ℃/min under the argon atmosphere for first calcination for 2h, grinding, and sieving with a 100-mesh sieve to obtain a 100-mesh preliminary biomass carbon material;
(2) Placing the primary biomass carbon material obtained in the step (1) in a 2mol/L HCl aqueous solution for stirring and acid treatment for 5 hours, wherein the acid treatment temperature is 50 ℃, filtering and drying, then placing in KOH with the concentration of 25wt% at 50 ℃ for stirring and soaking for 8 hours, filtering and washing with deionized water to be neutral, filtering and drying, and transferring to a vacuum drying oven for primary drying for 12 hours at 60 ℃ to obtain a pretreated biomass carbon material;
(3) Placing the pretreated biomass carbon material obtained in the step (2) in a high-temperature tube furnace, and heating from room temperature to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere for second calcination for 2h to obtain a secondary calcined biomass carbon material;
(4) Mixing the secondary calcined biomass carbon material obtained in the step (3) with alkali in a mass ratio of 1:1, carrying out alkali mixed grinding, transferring to a tube furnace, heating from room temperature to 700 ℃ at the speed of 3 ℃/min, and carrying out third calcinationBurning for 1.5h to obtain a modified biomass hard carbon material; the alkali used in the alkali mixed grinding is K 2 CO 3 ；
(5) Pouring the modified hard carbon material obtained in the step (4) into an asphalt coating liquid, controlling the use amount of asphalt to be 20wt% of the total mass of the material, mechanically stirring for 4 hours at 60 ℃ (the stirring speed is 200 rpm), and then carrying out secondary drying for 6 hours at 80 ℃ in a vacuum drying oven to obtain a precursor material;
the asphalt coating liquid is prepared by adding asphalt into tetrahydrofuran and mechanically stirring to fully dissolve the asphalt;
(6) And (4) placing the precursor material obtained in the step (5) into a tube furnace, heating to 350 ℃ at a speed of 5 ℃/min under the argon atmosphere, carrying out pre-carbonization for 2h, and heating to 950 ℃ at a speed of 10 ℃/min, carrying out carbonization for 6h, thus obtaining the biomass carbon cathode material for the sodium-ion battery.
Example 2
The preparation method of the biomass carbon negative electrode material for the sodium ion battery comprises the following steps:
(1) Washing a tea seed shell raw material with purified water, filtering, drying in vacuum to obtain tea seed shells, placing the tea seed shells in a tube furnace, heating from room temperature to 600 ℃ at the rate of 3 ℃/min under the argon atmosphere, carrying out first calcination for 2h, grinding, and sieving with a 200-mesh sieve to obtain a primary biomass carbon material of 200 meshes;
(2) Placing the primary biomass carbon material obtained in the step (1) in a HCL solution with the concentration of 6mol/L for acid treatment for 5 hours under the condition of stirring, filtering and drying, then placing in KOH with the concentration of 30wt% for alkali treatment for 8 hours under the condition of stirring, filtering and washing with deionized water to be neutral, transferring to a vacuum drying oven for primary drying for 12 hours at the temperature of 60 ℃ to obtain a pretreated biomass carbon material;
(3) Placing the pretreated biomass carbon material obtained in the step (2) in a high-temperature tube furnace, and heating from room temperature to 1100 ℃ at the speed of 5 ℃/min under the argon atmosphere to perform secondary calcination treatment for 2h to obtain a secondary calcined biomass carbon material;
(4) Mixing the secondary calcined biomass carbon material obtained in the step (3) with alkali in a mass ratio of 1:2 carrying out alkali mixed grindingTransferring the material to a tubular furnace, heating the material from room temperature to 800 ℃ at the speed of 5 ℃/min for carrying out third calcination for 1.5h, and regulating and reforming the pore structure of the material to obtain a modified biomass hard carbon material; the alkali used in the alkali mixed grinding is K 2 CO 3 ；
(5) Pouring the modified biomass hard carbon material obtained in the step (4) into an asphalt coating liquid, controlling the use amount of asphalt to be 20wt% of the total mass of the material, mechanically stirring for 6h at 60 ℃ (the stirring speed is 300 rpm), and then carrying out secondary drying for 6h at 80 ℃ in a vacuum drying oven to obtain a precursor material;
the asphalt coating liquid is prepared by adding asphalt into tetrahydrofuran and mechanically stirring to fully dissolve the asphalt;
(6) And (4) placing the precursor material obtained in the step (5) into a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min under the argon atmosphere, pre-carbonizing for 2h, and heating to 1150 ℃ at the speed of 10 ℃/min, and carbonizing for 6h to obtain the biomass carbon cathode material for the sodium-ion battery.
Example 3
(1) Washing a tea seed shell raw material with purified water, filtering, drying in vacuum to obtain tea seed shells, placing the tea seed shells in a tube furnace, heating from room temperature to 600 ℃ at the speed of 3 ℃/min under the atmosphere of argon gas for first calcination for 3h, grinding, and sieving with a 200-mesh sieve to obtain a primary biomass carbon material of 200 meshes;
(2) Placing the primary biomass carbon material obtained in the step (1) in a HCL solution with the concentration of 6mol/L for stirring and acid treatment for 5 hours, filtering and drying, then placing in KOH with the concentration of 30wt%, stirring and alkali treatment for 8 hours, filtering and washing with deionized water to be neutral, transferring to a vacuum drying oven, and performing first drying for 12 hours at the temperature of 60 ℃ to obtain a pretreated biomass carbon material;
(3) Placing the pretreated biomass carbon material obtained in the step (2) in a high-temperature tube furnace, and heating from room temperature to 1300 ℃ at the speed of 5 ℃/min under the argon atmosphere for second calcination for 2h to obtain a secondary calcined biomass carbon material;
(4) Mixing the secondary calcined biomass carbon material obtained in the step (3) with alkali in a mass ratio of 1:1, carrying out alkali mixed grinding, transferring to a tubular furnace, heating from room temperature to 800 ℃ at the speed of 5 ℃/min, carrying out third calcination for 2h, regulating and reforming the pore structure of the material, and obtaining a modified biomass hard carbon material; the alkali used in the alkali mixed grinding is KOH;
(5) Pouring the modified biomass hard carbon material obtained in the step (4) into an asphalt coating solution, controlling the use amount of asphalt to be 10wt% of the total mass of the material, mechanically stirring for 6h at 80 ℃ (the stirring speed is 300 rpm), and then performing secondary drying for 6h at 80 ℃ in a vacuum drying oven to obtain a precursor material;
the asphalt coating liquid is prepared by adding asphalt into tetrahydrofuran and fully dissolving the asphalt by mechanical stirring;
(6) And (3) placing the precursor material obtained in the step (5) into a tube furnace, heating to 350 ℃ at a speed of 5 ℃/min under the argon atmosphere, pre-carbonizing for 2h, and heating to 1150 ℃ at a speed of 10 ℃/min, and carbonizing for 6h to obtain the biomass carbon negative electrode material for the sodium-ion battery.
The biomass carbon negative electrode material for the sodium ion battery prepared in example 3 was observed by a scanning electron microscope, and the scanning electron microscope image is shown in fig. 1. As can be seen from fig. 1, the biomass carbon negative electrode material for sodium ion batteries prepared in example 3 is rich in micropores, and the presence of the pitch carbon can be more beneficial to intercalation/deintercalation of sodium ions, so that the biomass carbon negative electrode material has good electrochemical properties.
The biomass carbon negative electrode material for the sodium ion battery prepared in example 3 was used as a negative electrode material, and a sodium sheet was used as a counter electrode, and a button cell was assembled. At 20-25 deg.C, voltage of 0.01-2V, and voltage of 0.1C (1C = 300mAg) -1 ) The charge-discharge cycle test was performed at the current density of (1) to obtain an electrochemical test chart as shown in fig. 2, and it can be seen from fig. 2 that the first charge capacity of the biomass carbon negative electrode material for sodium ion battery prepared in example 3 was 310.5mAh g -1 The first effect is 92.5%, and the capacity is hardly attenuated after 50 weeks of circulation, which shows that the cycle performance is excellent and meets the industrial requirements.
Example 4
(1) Washing a tea seed shell raw material with purified water, filtering, drying in vacuum to obtain tea seed shells, placing the tea seed shells in a tube furnace, heating from room temperature to 600 ℃ at a rate of 3 ℃/min under the nitrogen atmosphere, carrying out first calcination for 3h, grinding, and sieving with a 200-mesh sieve to obtain a primary biomass carbon material of 200 meshes;
(2) Placing the primary biomass carbon material obtained in the step (1) in a HCL solution with the concentration of 6mol/L for stirring and acid treatment for 5 hours, filtering and drying, then placing in KOH with the concentration of 30wt%, stirring and alkali treatment for 8 hours, filtering and washing with deionized water to be neutral, transferring to a vacuum drying oven, and performing first drying for 12 hours at the temperature of 60 ℃ to obtain a pretreated biomass carbon material;
(3) Placing the pretreated biomass carbon material obtained in the step (2) in a high-temperature tube furnace, and heating the pretreated biomass carbon material from room temperature to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere for second calcination for 2h to obtain a secondary calcined biomass carbon material;
(4) Mixing the secondary calcined biomass carbon material obtained in the step (3) with alkali in a mass ratio of 1:1.5, carrying out alkali mixed grinding, transferring to a tube furnace, heating from room temperature to 800 ℃ at the speed of 10 ℃/min, carrying out third calcination for 2h, regulating and reforming the pore structure of the material, and obtaining the modified biomass hard carbon material;
the alkali used for the alkali mixed grinding is KOH;
(5) Pouring the modified biomass hard carbon material obtained in the step (4) into an asphalt coating solution, controlling the use amount of asphalt to be 30wt% of the total mass of the material, mechanically stirring for 6h at 80 ℃ (the stirring speed is 300 rpm), and then performing secondary drying for 6h at 80 ℃ in a vacuum drying oven to obtain a precursor material;
the asphalt coating liquid is prepared by adding asphalt into tetrahydrofuran and fully dissolving the asphalt by mechanical stirring;
(6) And (3) placing the precursor material obtained in the step (5) into a tube furnace, heating to 350 ℃ at a speed of 5 ℃/min under the argon atmosphere, pre-carbonizing for 2h, and heating to 1150 ℃ at a speed of 10 ℃/min, and carbonizing for 6h to obtain the biomass carbon negative electrode material for the sodium-ion battery.
In summary, the biomass carbon negative electrode material for the sodium ion battery prepared in embodiment 3 of the invention is rich in micropores, and the existence of the pitch carbon can be more beneficial to the intercalation/deintercalation of sodium ions, so that the biomass carbon negative electrode material has good performanceGood electrochemical performance and the first charge capacity of 310.5mAh g -1 The first effect is 92.5%, and the capacity is hardly attenuated after 50 weeks of circulation, which shows that the cycle performance is excellent and meets the industrial requirements. The method provided by the invention prepares the biomass carbon negative electrode material for the sodium ion battery with excellent sodium storage performance through simple multiple calcination, asphalt coating and carbonization treatment processes, is a low-cost, easily-synthesized, green and environment-friendly synthesis process of a biomass hard carbon material taking tea seed shells and asphalt as raw materials, has the characteristics of simple operation, strong repeatability, expandability and low cost, has rich pore structure and proper interlayer spacing, shows excellent electrochemical performance, and is an ideal sodium ion battery negative electrode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a biomass carbon negative electrode material for a sodium ion battery comprises the following steps:
(1) Sequentially carrying out first calcination, crushing and screening on tea seed shells to obtain a preliminary biomass carbon material;
(2) Sequentially carrying out acid treatment, alkali treatment, washing and first drying on the primary biomass carbon material obtained in the step (1) to obtain a pretreated biomass carbon material;
(3) Performing second calcination on the pretreated biomass carbon material obtained in the step (2) to obtain a secondary calcined biomass carbon material;
(4) Sequentially carrying out alkali mixed grinding and third calcination on the secondary calcined biomass carbon material obtained in the step (3) to obtain a modified biomass hard carbon material;
(5) Mixing the modified biomass hard carbon material obtained in the step (4) with the asphalt coating solution, and then carrying out second drying to obtain a precursor material;
(6) And (5) sequentially carrying out pre-carbonization and carbonization treatment on the precursor material obtained in the step (5) to obtain the biomass carbon negative electrode material for the sodium-ion battery.
2. The preparation method according to claim 1, wherein the first calcination in step (1) is carried out in an inert atmosphere, the temperature of the first calcination is 180 to 650 ℃, the temperature rise rate of the first calcination is 1.5 to 32 ℃/min, and the time of the first calcination is 0.5 to 6 hours.
3. The production method according to claim 1, wherein the particle size of the preliminary biomass carbon material in the step (1) is 80 to 600 mesh.
4. The method according to claim 1, wherein the temperature of the acid treatment in the step (2) is 20 to 90 ℃ and the time of the acid treatment is 3 to 9 hours.
5. The preparation method according to claim 1, wherein the second calcination in the step (3) is carried out in an inert atmosphere, the temperature of the second calcination is 700 to 1700 ℃, the temperature rise rate of the second calcination is 1.5 to 12 ℃/min, and the time of the second calcination is 1 to 12 hours.
6. The production method according to claim 1, wherein the mass ratio of the biomass carbon material subjected to secondary calcination in the step (4) to the alkali used for alkali-mixed grinding is 1:0.5 to 5; the third calcination is carried out in an inert atmosphere, the temperature of the third calcination is 400-900 ℃, the temperature rise speed of the third calcination is 2-22 ℃/min, and the time of the third calcination is 0.5-3 h.
7. The preparation method according to claim 1, wherein the amount of the asphalt in the asphalt-coated solution in the step (5) is 5wt% to 35wt% of the amount of the modified biomass hard carbon material.
8. The method according to claim 1, wherein the pre-carbonization in the step (6) is performed in an inert atmosphere, the pre-carbonization temperature is 280 to 550 ℃, and the pre-carbonization time is 1 to 7 hours.
9. The biomass carbon negative electrode material for the sodium-ion battery prepared by the preparation method of any one of claims 1 to 8.
10. The biomass carbon negative electrode material for the sodium-ion battery prepared by the preparation method of any one of claims 1 to 8 or the biomass carbon negative electrode material for the sodium-ion battery of claim 9 is applied to the negative electrode material for the sodium-ion battery.
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