CN117466283A - Hard carbon material with high ion diffusion coefficient and preparation method and application thereof - Google Patents
Hard carbon material with high ion diffusion coefficient and preparation method and application thereof Download PDFInfo
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- CN117466283A CN117466283A CN202311810795.8A CN202311810795A CN117466283A CN 117466283 A CN117466283 A CN 117466283A CN 202311810795 A CN202311810795 A CN 202311810795A CN 117466283 A CN117466283 A CN 117466283A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 91
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 64
- 238000009792 diffusion process Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- QJEBHEQVVLFNIE-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane-1,3,5-triol Chemical compound CC1(O)CC(O)(CC(O)(C1)C)C QJEBHEQVVLFNIE-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 1, 3, 5-triazine-2, 4, 6-triyl Chemical group 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims description 21
- 239000007833 carbon precursor Substances 0.000 claims description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000010000 carbonizing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 11
- 239000011229 interlayer Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000001133 acceleration Effects 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000013476 3D covalent-organic framework Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention particularly discloses a hard carbon material with a high ion diffusion coefficient, and a preparation method and application thereof. The invention prepares COFs by 1,3, 5-trimethyl phloroglucinol and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine, and then carries out rapid cooling to convert the pore canal structure from single directional arrangement to multi-directional and multidimensional arrangement; the hydrothermal reaction is utilized to carry out high-temperature carbonization after the surface of the COFs is coated with a carbon source, and a large amount of gas generated by the decomposition of the covalent organic framework material in the carbonization process can prevent the regular arrangement of an external carbon layer, so that the disorder degree of the external carbon is improved, and the interlayer distance of a hard carbon material is favorably improved; in addition, in the high-temperature carbonization process of the COF coated with the carbon source, the developed and mutually communicated pore channel structure can be reserved and converted into mutually connected closed pores in situ, so that the acceleration of ion transmission and the improvement of ion storage capacity are facilitated.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a hard carbon material with a high ion diffusion coefficient, a preparation method and application thereof.
Background
The hard carbon material can provide a large amount of Na due to the abundant graphite microcrystalline domain and closed cell structure + The storage sites, which allow for higher plateau capacities (< 0.1V voltage region providing more than 60% of the total capacity) and first coulombic efficiency (ICE), have received extensive attention in recent years, and are considered to be the most promising commercial negative electrode materials in the sodium ion battery field. However, na + The diffusion kinetics in the low voltage region (< 0.1V) are very slow, with a diffusion coefficient of between 10 -13 ~10 - 10 cm 2 Between/s, the ion diffusion coefficient (10) is far lower than that of the region with voltage > 0.1V -11 ~10 -9 cm 2 S) are disadvantageous for achieving high rate capability at high current densities.
Although the abundant open pore structure and defect sites are introduced into the hard carbon matrix, a large amount of Na can be adsorbed and stored + Thus effectively improving the rate capability of the sodium ion battery, but this strategy inevitably results in low ICE values, even in the disappearance of plateau regions, and finally in the sacrifice of fullEnergy density of the battery. Therefore, how to improve the hard carbon structure to promote Na + The ability to migrate rapidly in low voltage regions while maintaining high plateau capacity is critical to achieving high energy density, high power density.
Disclosure of Invention
For Na in the existing sodium ion battery + The invention provides a hard carbon material with a high ion diffusion coefficient and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
in a first aspect, the present invention provides a method for preparing a hard carbon material with a high ion diffusion coefficient, comprising the steps of:
step a, adding 1,3, 5-trimethyl phloroglucinol and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine into an organic solvent, uniformly dispersing, reacting for a first preset time at 160-175 ℃, and then carrying out rapid cooling and drying on the reaction solution to obtain a covalent organic framework material;
step b, adding the covalent organic framework material and a carbon source into an alcohol solution, reacting for a second preset time at 180-200 ℃, performing solid-liquid separation, washing and drying to obtain a hard carbon precursor material;
and c, carbonizing the hard carbon precursor material for 5-7 hours at 1100-1300 ℃ in an inert atmosphere, and cooling to obtain the hard carbon material with high ion diffusion coefficient.
Compared with the prior art, the preparation method of the high ion diffusion coefficient hard carbon material provided by the invention comprises the steps of firstly carrying out extremely rapid cooling on a covalent organic framework material prepared by a specific organic ligand, so that the pore channel structure is converted from single directional arrangement to multidirectional and multidimensional arrangement, and a framework material with a three-dimensional multistage pore structure is obtained; then coating a carbon source on the surface of a three-dimensional covalent organic framework material (3D COF) by utilizing a hydrothermal reaction, carbonizing at a high temperature under a specific condition, wherein a large amount of gas generated by decomposing the covalent organic framework material in the carbonization process can prevent the regular arrangement of an external carbon layer, thereby improving the disorder degree of the external carbon, providing more sodium storage sites by increasing the disorder degree, and simultaneouslyThe interlayer distance of the hard carbon material is also facilitated to be increased, and the expanded interlayer distance is facilitated to accelerate the rapid diffusion of sodium ions; in addition, in the high-temperature carbonization process of the 3D COF coated with the carbon source, the developed and mutually communicated pore channel structure can be reserved and converted into mutually connected closed pores in situ, so that the method is beneficial to accelerating ion transfer and improving ion storage capacity. The hard carbon material prepared by the method of the invention not only can realize Na + The rapid migration in a low-voltage area can also ensure to maintain high platform capacity, is favorable for further improving the electrochemical performance of the sodium ion battery, and has wide application prospect in the field of sodium ion batteries.
Further, in the step a, the mass ratio of the 1,3, 5-trimethylphloroglucinol to the 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine is 0.7-0.8:0.4-0.5.
The COF prepared by taking 1,3, 5-trimethyl phloroglucinol and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine as organic ligands is taken as a framework material, and the hard carbon material is prepared by high-temperature carbonization after carbon source coating, so that the hard carbon material has a pore channel structure in disordered arrangement, the disorder of external carbon is improved, and Na is promoted + The rapid transfer of the hard carbon material can also carry out functional group modification on the hard carbon, so that the electron transfer effect is enhanced, and meanwhile, the wettability of the electrolyte to the hard carbon material can also be increased, thereby being beneficial to improving the platform capacity of the hard carbon.
In the step a, the organic solvent is N, N-dimethylformamide, and the volume mass ratio of the organic solvent to the 1,3, 5-trimethylphloroglucinol is (20-30) mL (0.7-0.8) g.
1,3, 5-trimethyl phloroglucinol and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine have good solubility in a preferred organic solvent, and can promote the coordination of two organic ligands to obtain a covalent organometallic material with excellent structure.
Further, in the step a, the first preset time is 3h to 5h.
In the step a, the reaction liquid is placed in liquid nitrogen for rapid cooling, and the cooling time is 3 min-5 min.
The covalent organic framework material is rapidly cooled in liquid nitrogen, so that the structure of the covalent organic framework material can be converted into a three-dimensional structure from two dimensions, and the pore canal structure of the covalent organic framework material is converted into a multi-dimensional and mutually communicated three-dimensional network structure, thereby facilitating the promotion of Na + The rapid transfer in the pore canal effectively increases the contact area between the pore canal and the electrolyte, and is beneficial to the electrochemical promotion of the battery.
Further, in the step b, the mass ratio of the covalent organic framework material to the carbon source is 0.5-0.7:1.0-1.4.
In the step b, the alcohol solution is a mixed solution of ethanol and water in a volume ratio of 1:1-2, and the volume mass ratio of the alcohol solution to the covalent organic framework material is (50-70) mL (0.5-0.7) g.
Further, in the step b, the carbon source is one or more of glucose, sucrose, polyvinylpyrrolidone or lignin.
Further, in the step b, the second preset time is 10 h-12 h.
The optimized carbon source, the addition amount and the hydrothermal reaction condition are favorable for enabling the carbon source to uniformly coat the covalent organic framework material, enabling the thickness of the hard carbon material to be moderate, providing more storage sites and ion transmission channels for sodium ions and effectively improving the electrochemical performance of the hard carbon material.
Further, in the step c, the temperature of the carbonization is raised to 1100-1300 ℃ in a temperature programming manner, and the temperature raising rate is 5-8 ℃/min.
The preferential calcination temperature and the heating rate can lead the covalent organic framework material to decompose to generate a large amount of gas and obstruct the connection between the hard carbon graphite domains, thereby being beneficial to forming the randomly distributed graphite domains with shorter length and low graphitization degree, and shortening the ion diffusion distance while improving the interlayer spacing; in addition, the preferred calcination temperature and rate of temperature rise allow the interconnected pore structure of the covalent organic framework material to be preserved and form a rich closed cell structure in situ, thereby increasing platform capacity and first coulombic efficiency.
The inert atmosphere in the present invention is provided by an inert gas, and inert gases conventional in the art, such as argon, nitrogen, etc., may be used.
In a second aspect, the invention also provides a high ion diffusion coefficient hard carbon material prepared by the preparation method of any one of the high ion diffusion coefficient hard carbon materials.
In a third aspect, the present invention also provides a negative electrode, including the above-mentioned high ion diffusion coefficient hard carbon material.
In a fourth aspect, the invention also provides an application of the high-ion-diffusivity hard carbon material or the negative electrode in preparing a sodium ion battery, a lithium ion battery or a potassium ion battery.
In a fifth aspect, the present invention also provides a sodium ion battery comprising a high ion diffusion coefficient hard carbon material or the negative electrode described above.
The invention provides a superior hard carbon negative electrode material for sodium ion batteries, and the preparation method of the hard carbon negative electrode material has the advantages of wide raw material sources, low price, simple and feasible preparation process, capability of carrying out large-scale production, and wide application prospect, and opens up a new way for structural design and optimization of the negative electrode material of the high-performance sodium ion batteries.
The invention also provides a battery module comprising the sodium ion battery.
The hard carbon material prepared by the invention effectively solves the Na of the existing hard carbon material + The slow diffusion dynamics in the low voltage area can be realized by applying the negative electrode material to sodium ion batteries + Sodium ion batteries that can migrate rapidly in low voltage regions while maintaining high plateau capacity are excellent in performance.
Drawings
FIG. 1 is an SEM image of a hard carbon material prepared according to example 1 of the invention;
fig. 2 is an SEM image of the hard carbon material prepared in comparative example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
A preparation method of a hard carbon material comprises the following steps:
step one, dissolving 0.72g of 1,3, 5-trimethyl phloroglucinol and 0.42g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 20mL of N, N-dimethylformamide, stirring and reacting for 3 hours in an oil bath at 160 ℃, then placing the reaction liquid in liquid nitrogen for extremely rapid cooling, keeping for 4 minutes, and then drying overnight in an oven at 70 ℃ to obtain the COFs material with a 3D structure;
adding 0.5g of the prepared COFs material and 1g of glucose into a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, performing hydrothermal reaction at 180 ℃ for 10 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under the argon atmosphere, carbonizing for 5 hours, and naturally cooling to obtain the hard carbon material.
Example 2
A preparation method of a hard carbon material comprises the following steps:
step one, dissolving 0.75g of 1,3, 5-trimethyl phloroglucinol and 0.45g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 25mL of N, N-dimethylformamide, stirring and reacting for 5 hours in an oil bath at 165 ℃, then placing the reaction liquid in liquid nitrogen for extremely rapid cooling, keeping for 5 minutes, and then drying overnight in an oven at 70 ℃ to obtain the COFs material with a 3D structure;
adding 0.7g of the prepared COFs material and 1.4g of sucrose into a mixed solution of 35mL of deionized water and 35mL of absolute ethyl alcohol, performing hydrothermal reaction at 200 ℃ for 10 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1200 ℃ at a speed of 8 ℃/min under the argon atmosphere, carbonizing for 6 hours, and naturally cooling to obtain the hard carbon material.
Example 3
A preparation method of a hard carbon material comprises the following steps:
step one, dissolving 0.8g of 1,3, 5-trimethyl phloroglucinol and 0.5g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 30mL of N, N-dimethylformamide, stirring and reacting for 4 hours in an oil bath at 175 ℃, then placing the reaction liquid in liquid nitrogen for extremely rapid cooling, keeping for 3 minutes, and then drying overnight in an oven at 70 ℃ to obtain a COFs material with a 3D structure;
adding 0.6g of the prepared COFs material and 1.2g of polyvinylpyrrolidone into a mixed solution of 40mL of deionized water and 20mL of absolute ethyl alcohol, performing hydrothermal reaction at 190 ℃ for 12 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1300 ℃ at a speed of 6 ℃/min under the argon atmosphere, carbonizing for 7h, and naturally cooling to obtain the hard carbon material.
Example 4
A preparation method of a hard carbon material comprises the following steps:
step one, dissolving 0.72g of 1,3, 5-trimethyl phloroglucinol and 0.42g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 20mL of N, N-dimethylformamide, stirring and reacting for 3 hours in an oil bath at 160 ℃, then placing the reaction liquid in liquid nitrogen for extremely rapid cooling, keeping for 4 minutes, and then drying overnight in an oven at 70 ℃ to obtain the COFs material with a 3D structure;
adding 0.5g of the prepared COFs material and 1g of lignin into a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, performing hydrothermal reaction at 180 ℃ for 10 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1300 ℃ at a speed of 5 ℃/min under the argon atmosphere, carbonizing for 5 hours, and naturally cooling to obtain the hard carbon material.
Comparative example 1
This comparative example provides a method for producing a hard carbon material, which differs from example 1 only in that no liquid nitrogen extremely rapid cooling is performed, specifically comprising the steps of:
step one, dissolving 0.72g of 1,3, 5-trimethyl phloroglucinol and 0.42g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 20mL of N, N-dimethylformamide, stirring and reacting for 3 hours in an oil bath at 160 ℃, and then drying overnight in an oven at 70 ℃ to obtain a COFs material with a 3D structure;
adding 0.5g of the prepared COFs material and 1g of glucose into a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, performing hydrothermal reaction at 180 ℃ for 10 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under the argon atmosphere, carbonizing for 5 hours, and naturally cooling to obtain the hard carbon material.
Comparative example 2
The comparative example is a method for preparing a hard carbon material, which is different from example 1 only in that the hydrothermal reaction of COFs and a carbon source is replaced by physical mixing, and specifically includes the following steps:
step one, dissolving 0.72g of 1,3, 5-trimethyl phloroglucinol and 0.42g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 20mL of N, N-dimethylformamide, stirring and reacting for 3 hours in an oil bath at 160 ℃, then placing the reaction liquid in liquid nitrogen for extremely rapid cooling, keeping for 4 minutes, and then drying overnight in an oven at 70 ℃ to obtain the COFs material with a 3D structure;
ball milling 0.5g of the prepared COFs material and 1g of glucose at 150r/min for 30min to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under the argon atmosphere, carbonizing for 5 hours, and naturally cooling to obtain the hard carbon material.
Comparative example 3
This comparative example provides a method for producing a hard carbon material, which differs from example 1 only in the carbonization time in step three, and specifically includes the steps of:
step one, dissolving 0.72g of 1,3, 5-trimethyl phloroglucinol and 0.42g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine in a three-mouth bottle containing 20mL of N, N-dimethylformamide, stirring and reacting for 3 hours in an oil bath at 160 ℃, then placing the reaction liquid in liquid nitrogen for extremely rapid cooling, keeping for 4 minutes, and then drying overnight in an oven at 70 ℃ to obtain the COFs material with a 3D structure;
adding 0.5g of the prepared COFs material and 1g of glucose into a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, performing hydrothermal reaction at 180 ℃ for 10 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and thirdly, placing the prepared hard carbon precursor material into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under the argon atmosphere, carbonizing for 4 hours, and naturally cooling to obtain the hard carbon material.
Comparative example 4
The comparative example provides a preparation method of a hard carbon material, which specifically comprises the following steps:
adding 0.5g of zinc oxide powder and 1g of glucose into a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, performing hydrothermal reaction at 180 ℃ for 10 hours, centrifuging, washing, and drying in an oven at 80 ℃ for 12 hours to obtain a hard carbon precursor material;
and step two, placing the prepared hard carbon precursor material into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under argon atmosphere, carbonizing for 5 hours, and naturally cooling to obtain the hard carbon material.
Comparative example 5
The comparative example provides a preparation method of a hard carbon material, which specifically comprises the following steps:
and (3) putting 1g of glucose powder into a tube furnace, heating to 1100 ℃ at a speed of 5 ℃/min under argon atmosphere, carbonizing for 5 hours, and naturally cooling to obtain the hard carbon material.
Characterization of
An SEM image of the hard carbon material prepared in example 1 is shown in fig. 1, and an SEM image of the hard carbon material prepared in comparative example 5 is shown in fig. 2. As can be seen by comparison, the hard carbon material prepared in example 1 of the present invention has significantly shorter graphite domains, enlarged interlayer distances and abundant closed pores (labeled part in FIG. 1), while the hard carbon material prepared in comparative example 5 has longer graphite layers, narrower interlayer distances and frequent closed pores (labeled part in FIG. 2).
Application examples
The hard carbon materials prepared in examples 1 to 4 and comparative examples 1 to 5 were assembled into sodium ion half-cells, and the specific assembly steps were as follows:
grinding and mixing the hard carbon materials prepared in examples 1-4 and comparative examples 1-5 with acetylene black and sodium alginate respectively according to a mass ratio of 8:1:1, and adding water and mixing uniformly to obtain mixed slurry (solid content is 85%); coating the mixed slurry on the surface of copper foil with the coating amount of 2.3g/cm 3 Vacuum drying at 100deg.C for 12 hr to obtain coating material; cutting the coating material into small discs with the diameter of 12mm to obtain a negative electrode plate; assembling a battery with a negative electrode plate, wherein a sodium metal plate is used as a counter electrode, a diaphragm is made of glass fiber, and an electrolyte is 1mol/L NaPF 6 DME, sodium ion half cell is obtained.
And placing the assembled die battery on a Land CT2001A battery test system for electrochemical performance test, wherein the test temperature is 25 ℃, and the test electrochemical window is 0V-2.5V.
The sodium ion batteries assembled from the hard carbon materials prepared in examples 1 to 4 and comparative examples 1 to 5 were tested for ion diffusion coefficient in the low voltage region (0 to 0.1 v) at 0.5C (1c=300 mA/g), and were subjected to rate charge and discharge test at 0.1C to obtain plateau capacity and first coulomb efficiency, and the rate capacity was tested at 10A/g current density, and the results are shown in table 1.
TABLE 1
The result shows that the hard carbon material prepared by the embodiment of the invention has obviously improved ion diffusion coefficient, platform capacity, first coulombic efficiency and multiplying power capacity under high current density, and is favorable for obviously improving the performance of the sodium ion battery.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the hard carbon material with the high ion diffusion coefficient is characterized by comprising the following steps:
step a, adding 1,3, 5-trimethyl phloroglucinol and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine into an organic solvent, uniformly dispersing, reacting for a first preset time at 160-175 ℃, and then carrying out rapid cooling and drying on the reaction solution to obtain a covalent organic framework material;
step b, adding the covalent organic framework material and a carbon source into an alcohol solution, reacting for a second preset time at 180-200 ℃, performing solid-liquid separation, washing and drying to obtain a hard carbon precursor material;
and c, carbonizing the hard carbon precursor material for 5-7 hours at 1100-1300 ℃ in an inert atmosphere, and cooling to obtain the hard carbon material with high ion diffusion coefficient.
2. The method for preparing a hard carbon material with a high ion diffusion coefficient according to claim 1, wherein in the step a, the mass ratio of the 1,3, 5-trimethylphloroglucinol to the 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) -triphenylamine is 0.7-0.8:0.4-0.5; and/or
In the step a, the organic solvent is N, N-dimethylformamide, and the volume mass ratio of the organic solvent to the 1,3, 5-trimethylphloroglucinol is (20-30) mL (0.7-0.8) g.
3. The method for preparing a high ion diffusion coefficient hard carbon material according to claim 1, wherein in the step a, the first preset time is 3h to 5h; and/or
In the step a, the reaction liquid is placed in liquid nitrogen for rapid cooling, and the cooling time is 3-5 min.
4. The method for preparing a hard carbon material with a high ion diffusion coefficient according to claim 1, wherein in the step b, the mass ratio of the covalent organic framework material to the carbon source is 0.5-0.7:1.0-1.4; and/or
In the step b, the alcohol solution is a mixed solution of ethanol and water in a volume ratio of 1:1-2, and the volume mass ratio of the alcohol solution to the covalent organic framework material is (50-70) mL (0.5-0.7) g; and/or
In the step b, the carbon source is one or more of glucose, sucrose, polyvinylpyrrolidone or lignin; and/or
In the step b, the second preset time is 10-12 h.
5. The method for preparing the high-ion-diffusion-coefficient hard carbon material according to claim 1, wherein in the step c, the carbonization is heated to 1100-1300 ℃ in a temperature programming manner, and the heating rate is 5-8 ℃/min.
6. The high-ion-diffusion-coefficient hard carbon material is characterized by being prepared by the preparation method of the high-ion-diffusion-coefficient hard carbon material according to any one of claims 1 to 5.
7. A negative electrode comprising the high ion diffusion coefficient hard carbon material according to claim 6.
8. Use of the high ion diffusion coefficient hard carbon material of claim 6, or the negative electrode of claim 7, in the preparation of a sodium ion battery, a lithium ion battery or a potassium ion battery.
9. A sodium ion battery comprising the high ion diffusion coefficient hard carbon material of claim 6 or the negative electrode of claim 7.
10. A battery module comprising the sodium ion battery of claim 9.
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