CN116544386A - Starch-based hard carbon sodium ion battery negative electrode material, and preparation method and application thereof - Google Patents
Starch-based hard carbon sodium ion battery negative electrode material, and preparation method and application thereof Download PDFInfo
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- 229920002472 Starch Polymers 0.000 title claims abstract description 105
- 235000019698 starch Nutrition 0.000 title claims abstract description 103
- 239000008107 starch Substances 0.000 title claims abstract description 103
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 62
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 49
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 title claims description 17
- 239000010405 anode material Substances 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 35
- 230000003213 activating effect Effects 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 230000032050 esterification Effects 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 4
- 240000001085 Trapa natans Species 0.000 claims description 4
- 235000014364 Trapa natans Nutrition 0.000 claims description 4
- 235000009165 saligot Nutrition 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 2
- 240000002853 Nelumbo nucifera Species 0.000 claims description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 2
- 229920008262 Thermoplastic starch Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000004628 starch-based polymer Substances 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000000463 material Substances 0.000 abstract description 20
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 5
- 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 3
- 238000005056 compaction Methods 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 239000013081 microcrystal Substances 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 16
- 239000006256 anode slurry Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 12
- 239000010431 corundum Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a starch-based hard carbon sodium ion battery anode material and a preparation method and application thereof. The preparation method comprises the following steps: s1, carrying out esterification reaction on starch and maleic anhydride, and then crushing to obtain precursor particles; s2, introducing carbon dioxide under the protection of inert atmosphere, and activating and pore-forming the precursor particles obtained in the step S1 at a certain temperature to obtain an activated pore-forming product; s3, heat treatment is carried out on the activated pore-forming product in an inert atmosphere to obtain the product. The esterification treatment ensures the original shape of the material, prevents the collapse of the structure, and increases the compaction density; then activating gas is utilized to perform activation pore-forming, a wide open nano pore structure is formed, finally high-temperature carbonization is performed, and growth/recombination of microcrystals is restrained through high Wen Shouduan, so that the previous open nano pore structure is converted into a closed pore structure, the sodium removing and embedding capabilities of a low-potential platform are remarkably enhanced, and the specific capacity of the material is further improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a starch-based hard carbon sodium ion battery negative electrode material, a preparation method and application thereof.
Background
Carbon-based materials are considered as the most promising commercial negative electrode materials because of the advantages of wide sources, abundant resources, various structures, renewable properties, no toxicity, and the like, and are distinguished from numerous sodium-storage negative electrode materials. Carbon-based materials are also widely used, and there are generally graphite, soft carbon, hard carbon, carbon nanotubes, etc., among which graphite is widely used in lithium ion batteries. However, for thermodynamic reasons, the specific capacity of sodium ion batteries in practical tests is not high, and sodium ion batteries are not suitable. Hard carbon with a highly disordered structure and a large interlayer distance and rich defects has enough sodium ion storage active sites to store a large amount of sodium ions, and thus becomes one of the most promising negative electrode materials for sodium ion batteries. However, most of hard carbon materials selected as the negative electrode of the sodium ion battery in the current research have low coulomb efficiency for the first time, short platform capacity, complex preparation method, complicated steps and high cost, so that the commercialization process of the sodium ion battery is difficult to advance.
Among the hard carbon precursors, starch is widely used as a carbon source, has low cost and is green and pollution-free, and is concerned by people. Starch exhibits an original natural spherical morphology compared to other biomass precursors, which makes it one of the candidate materials of great advantage for the preparation of spherical carbon materials. However, the application of directly carbonized starch to the negative electrode material of sodium ion batteries shows lower electrochemical performance on one hand and starch morphology is broken on the other hand, reducing the compaction density. While advances have been made to improve the performance of starch-based hard carbons by heteroatom doping or surface coating techniques, there are still many problems such as complexity of the preparation process, high energy consumption, and relatively modest electrochemical performance, which tend to be detrimental to commercial development. Therefore, on the premise of maintaining the appearance of the starch, a proper means is provided to obviously improve the sodium storage performance of the starch.
Disclosure of Invention
The invention aims at providing a starch-based hard carbon sodium ion battery anode material, a preparation method and application thereof, aiming at the defects of the prior art.
The invention discloses a preparation method of a starch-based hard carbon sodium ion battery anode material, which comprises the following steps:
s1, carrying out esterification treatment, namely carrying out esterification reaction on starch and maleic anhydride, and then crushing to obtain precursor particles;
s2, activating and pore-forming, namely introducing carbon dioxide under the protection of inert atmosphere, and activating and pore-forming the precursor particles obtained in the step S1 at a certain temperature to obtain an activated pore-forming product;
and S3, carbonizing at a high temperature, and heat-treating the activated pore-forming product obtained in the step S3 in an inert atmosphere to obtain the starch-based hard carbon sodium ion battery anode material.
In step S1, the mass ratio of the starch to the maleic anhydride is 1:1-5.
Further, in step S1, the precursor particles are prepared by dry powder hydrothermal reaction at 50-150 ℃.
Further, in the step S2, the flow ratio of the carbon dioxide to the inert gas is 1:1-5, and the total flow is 0.5-5L/(m) 3 Min), the activation temperature is 400-800 ℃, and the activation time is 1-8 h.
Further, in the step S3, the heat treatment temperature is 1300-1800 ℃, the heating rate is 1-20 ℃/min, and the heat preservation time is 0.1-10 h.
In step S1, the starch is one or more of potato starch, corn starch, wheat starch, pea starch, water chestnut starch, lotus root starch, water chestnut starch, soluble starch and thermoplastic starch.
Further, in step S1, the precursor particles have a particle size of 40 to 500 mesh.
Further, in the steps S2 and S3, the inert gas is argon and/or nitrogen.
The starch-based hard carbon sodium ion battery anode material prepared by the preparation method is provided.
A negative electrode plate prepared from the starch-based hard carbon sodium ion battery negative electrode material is provided.
The preparation method comprises the steps of carrying out esterification treatment and grinding on a starch-based raw material and maleic anhydride to obtain precursor particles, then activating the precursor particles by using an activating gas in a gas activation pore-forming mode to carry out pore-forming treatment, and finally carrying out high-temperature carbonization to obtain a starch-based hard carbon sodium ion battery anode material used for an excellent sodium ion battery; the esterification ensures the original shape of the material, prevents the collapse of the structure, thereby increasing the compaction density and ensuring the commercialized condition of the material; then activating gas is utilized to perform activation pore-forming, a wide open nano pore structure is formed, finally high-temperature carbonization is performed, and growth/recombination of microcrystals is restrained through high Wen Shouduan, so that the previous open nano pore structure is converted into a closed pore structure, the sodium removing and embedding capabilities of a low-potential platform are remarkably enhanced, and the specific capacity of the material is further improved.
The first charge and discharge efficiency of the starch-based hard carbon sodium ion battery anode material prepared by the invention can reach more than 90%, and the reversible capacity is 400mAh g 1 The above has excellent electrochemical properties.
Drawings
FIG. 1 is an SEM image of a sample obtained in comparative example 1;
FIG. 2 is an SEM image of a sample obtained in comparative example 2;
FIG. 3 is an SEM image of a sample obtained in example 3;
FIG. 4 is an SEM image of a sample obtained in example 4;
FIG. 5 is an SEM image of a sample obtained in comparative example 3;
FIG. 6 is an XRD pattern of the samples obtained in the above examples;
FIG. 7 is a graph showing the results of the performance test of the sample obtained in example 3 as a negative electrode material for sodium ion batteries;
FIG. 8 is a graph showing the results of performance test of the sample obtained in comparative example 1 as a negative electrode material for sodium ion batteries;
FIG. 9 is a graph showing the results of performance test of the sample obtained in comparative example 2 as a negative electrode material for sodium ion batteries;
FIG. 10 is a graph showing the results of the performance test of the sample obtained in example 4 as a negative electrode material for sodium ion batteries;
FIG. 11 is a graph showing the results of performance test of the sample obtained in comparative example 3 as a negative electrode material for sodium ion batteries;
fig. 12 is a graph showing the results of performance test of the sample obtained in comparative example 4 as a negative electrode material for sodium ion batteries.
Detailed Description
The following are specific embodiments of the present invention and the technical solutions of the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
Preparing a starch-based hard carbon sodium ion battery anode material:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:1, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Activating: and (2) placing the precursor particles obtained in the step (1) into a corundum crucible, placing the corundum crucible into an open atmosphere tube furnace, heating to 800 ℃ at a speed of 2 ℃/min under the protection of argon atmosphere, then introducing activating gas, wherein the flow ratio of the activating gas to the inert gas is 1:2, and preserving heat for 1h to obtain an activating product.
3) Carbonizing: and under the protection of argon atmosphere, heating the activated product obtained in the step 2) to 1400 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
Example 2
The starch-based hard carbon sodium ion battery anode material of the embodiment is prepared by the following method:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:3, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Activating: and (3) placing the precursor particles obtained in the step (1) into a corundum crucible, placing the corundum crucible into an open atmosphere tube furnace, heating to 500 ℃ at a speed of 2 ℃/min under the protection of argon atmosphere, then introducing activating gas, wherein the flow ratio of the activating gas to the inert gas is 1:5, and preserving heat for 1h to obtain an activating product.
3) Carbonizing: and under the protection of argon atmosphere, heating the activated product obtained in the step 2) to 1600 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
Example 3
The starch-based hard carbon sodium ion battery anode material of the embodiment is prepared by the following method:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:5, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Activating: and (3) placing the precursor particles obtained in the step (1) into a corundum crucible, placing the corundum crucible into an open atmosphere tube furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of argon atmosphere, then introducing activating gas, wherein the flow ratio of the activating gas to the inert gas is 1:5, and preserving heat for 1h to obtain an activating product.
3) Carbonizing: and under the protection of argon atmosphere, heating the activated product obtained in the step 2) to 1300 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
4) Preparation of a negative electrode: the preparation method comprises the steps of adopting the starch-based hard carbon sodium ion battery anode material as an anode active material to prepare an anode electrode plate, uniformly grinding the anode material, a conductive agent and a binder according to a mass ratio of 8:1:1, mixing the anode material with sodium carboxymethylcellulose (water serving as a solvent) to prepare anode slurry, coating the anode slurry on a current collector, standing in a vacuum oven at 100 ℃ for 10 hours, and drying and cutting the anode slurry into a wafer-shaped anode electrode plate.
5) Half battery packAnd (3) loading: na sheet is adopted as a counter electrode, 1.0mol/LNaPF is adopted 6 And (3) using DIGL YME as electrolyte, and assembling the glove box of the starch-based negative electrode plate in an argon atmosphere into a button cell.
In the preparation method, an SEM image of the obtained starch-based hard carbon sodium ion battery anode material is shown in fig. 3. Showing a pronounced globular structure. The XRD patterns of the obtained starch-based hard carbon sodium ion battery anode material are shown in fig. 6, and two broad diffraction peaks which respectively correspond to the diffraction crystal faces (002) and (101) appear at about 22 degrees and 43 degrees, so that the material of the embodiment belongs to a carbon material. The electrochemical properties are shown in FIG. 7 at 25mAh g 1 The reversible specific capacity is 452mAh g at the current density of (2) 1 The platform capacity below 0.1V is 372mAh g 1 The first-turn coulombic efficiency was 89.07%, showing excellent electrochemical performance.
Example 4
The starch-based hard carbon sodium ion battery anode material of the embodiment is prepared by the following method:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:5, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Activating: and (3) placing the precursor particles obtained in the step (1) into a corundum crucible, placing the corundum crucible into an open atmosphere tube furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of argon atmosphere, then introducing activating gas, wherein the flow ratio of the activating gas to the inert gas is 1:5, and preserving heat for 1h to obtain an activating product.
3) Carbonizing: and under the protection of argon atmosphere, heating the activated product obtained in the step 2) to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
4) Preparation of a negative electrode: the preparation method comprises the steps of adopting the starch-based hard carbon sodium ion battery anode material as an anode active material to prepare an anode electrode plate, uniformly grinding the anode material, a conductive agent and a binder according to a mass ratio of 8:1:1, mixing the anode material with sodium carboxymethylcellulose (water serving as a solvent) to prepare anode slurry, coating the anode slurry on a current collector, standing in a vacuum oven at 100 ℃ for 10 hours, and drying and cutting the anode slurry into a wafer-shaped anode electrode plate.
5) And (3) half-cell assembly: na sheet is adopted as a counter electrode, 1.0mol/LNaPF is adopted 6 And (3) using DIGL YME as electrolyte, and assembling the glove box of the starch-based negative electrode plate in an argon atmosphere into a button cell.
In the preparation method, an SEM image of the obtained starch-based hard carbon sodium ion battery anode material is shown in fig. 3. Showing a pronounced globular structure. The XRD patterns of the obtained starch-based hard carbon sodium ion battery anode material are shown in fig. 6, and two broad diffraction peaks which respectively correspond to the diffraction crystal faces (002) and (101) appear at about 22 degrees and 43 degrees, so that the material of the embodiment belongs to a carbon material. The electrochemical properties are shown in FIG. 10, at 25mAh g 1 At a current density of 421mAh g 1 The platform capacity below 0.1V is 328mAh g 1 The first circle coulomb efficiency is 95.5%
Comparative example 1
Preparing a starch-based hard carbon sodium ion battery anode material:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:5, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Activating: and (3) placing the precursor particles obtained in the step (1) into a corundum crucible, placing the corundum crucible into an open atmosphere tube furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of argon atmosphere, then introducing activating gas, wherein the flow ratio of the activating gas to the inert gas is 1:5, and preserving heat for 1h to obtain an activating product.
3) Carbonizing: and under the protection of argon atmosphere, heating the activated product obtained in the step 2) to 900 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
4) Preparation of a negative electrode: the preparation method comprises the steps of adopting the starch-based hard carbon sodium ion battery anode material as an anode active material to prepare an anode electrode plate, uniformly grinding the anode material, a conductive agent and a binder according to a mass ratio of 8:1:1, mixing the anode material with sodium carboxymethylcellulose (water serving as a solvent) to prepare anode slurry, coating the anode slurry on a current collector, standing in a vacuum oven at 100 ℃ for 10 hours, and drying and cutting the anode slurry into a wafer-shaped anode electrode plate.
5) And (3) half-cell assembly: na sheet is adopted as a counter electrode, 1.0mol/LNaPF is adopted 6 And (3) using DIGL YME as electrolyte, and assembling the glove box of the starch-based negative electrode plate in an argon atmosphere into a button cell.
In the preparation method, an SEM image of the obtained starch-based hard carbon sodium ion battery anode material is shown in fig. 1, and the obtained starch-based hard carbon sodium ion battery anode material shows an obvious spherical structure. The XRD patterns of the obtained starch-based hard carbon sodium ion battery anode material are shown in fig. 6, and two broad diffraction peaks which respectively correspond to the diffraction crystal faces (002) and (101) appear at about 22 degrees and 43 degrees, so that the material of the embodiment belongs to a carbon material. The electrochemical properties are shown in FIG. 8, at 25mAh g 1 At a current density of 136mAh g 1 The platform capacity below 0.1V is 63mAh g 1 The first circle coulombic efficiency was 60.38%.
Comparative example 2
The starch-based hard carbon sodium ion battery anode material of the embodiment is prepared by the following method:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:5, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Activating: and (3) placing the precursor particles obtained in the step (1) into a corundum crucible, placing the corundum crucible into an open atmosphere tube furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of argon atmosphere, then introducing activating gas, wherein the flow ratio of the activating gas to the inert gas is 1:5, and preserving heat for 1h to obtain an activating product.
3) Carbonizing: and under the protection of argon atmosphere, heating the activated product obtained in the step 2) to 1100 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
4) Preparation of a negative electrode: the preparation method comprises the steps of adopting the starch-based hard carbon sodium ion battery anode material as an anode active material to prepare an anode electrode plate, uniformly grinding the anode material, a conductive agent and a binder according to a mass ratio of 8:1:1, mixing the anode material with sodium carboxymethylcellulose (water serving as a solvent) to prepare anode slurry, coating the anode slurry on a current collector, standing in a vacuum oven at 100 ℃ for 10 hours, and drying and cutting the anode slurry into a wafer-shaped anode electrode plate.
5) And (3) half-cell assembly: na sheet is adopted as a counter electrode, 1.0mol/LNaPF is adopted 6 And (3) using DIGL YME as electrolyte, and assembling the glove box of the starch-based negative electrode plate in an argon atmosphere into a button cell.
In the preparation method, an SEM image of the obtained starch-based hard carbon sodium ion battery anode material is shown in fig. 2. Showing a pronounced globular structure. The XRD patterns of the obtained starch-based hard carbon sodium ion battery anode material are shown in fig. 6, and two broad diffraction peaks which respectively correspond to the diffraction crystal faces (002) and (101) appear at about 22 degrees and 43 degrees, so that the material of the embodiment belongs to a carbon material. The electrochemical properties are shown in FIG. 9 at 25mAh g 1 At a current density of 151mAh g 1 The platform capacity below 0.1V is 82mAh g 1 The first circle coulombic efficiency was 64.66%.
Comparative example 3
The starch-based hard carbon sodium ion battery anode material of the embodiment is prepared by the following method:
1) Pretreatment of starch-based raw materials: putting a certain amount of soluble starch into a container, putting the container filled with the soluble starch into a vacuum drying oven for drying at 100 ℃ for 24 hours, then taking out the container, adding the container into a reaction kettle according to the mass ratio of the starch to maleic anhydride of 1:5, carrying out dry powder hydrothermal reaction at 100 ℃ to obtain a precursor material, and crushing to obtain precursor particles, wherein the particle size of the precursor is about 400 meshes.
2) Carbonizing: and under the protection of argon atmosphere, heating the precursor particles obtained in the step 1) to 1300 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain the starch-based hard carbon sodium ion battery anode material.
Preparation of a negative electrode: the preparation method comprises the steps of adopting the starch-based hard carbon sodium ion battery anode material as an anode active material to prepare an anode electrode plate, uniformly grinding the anode material, a conductive agent and a binder according to a mass ratio of 8:1:1, mixing the anode material with sodium carboxymethylcellulose (water serving as a solvent) to prepare anode slurry, coating the anode slurry on a current collector, standing in a vacuum oven at 100 ℃ for 10 hours, and drying and cutting the anode slurry into a wafer-shaped anode electrode plate.
And (3) half-cell assembly: na sheet is adopted as a counter electrode, 1.0mol/LNaPF is adopted 6 And (3) using DIGL YME as electrolyte, and assembling the glove box of the starch-based negative electrode plate in an argon atmosphere into a button cell.
The electrolyte in the above embodiment may be selected from NaClO 4 、NaPF 6 NaTFSI and NaBF 4 Any one or a combination of non-aqueous solvents selected from the group consisting of ethylene carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, diglyme and ethylene glycol dimethyl ether.
In the preparation method, an SEM diagram of the obtained starch-based hard carbon sodium ion battery anode material is shown in fig. 4. Showing a pronounced globular structure. The XRD patterns of the obtained starch-based hard carbon sodium ion battery anode material are shown in fig. 6, and two broad diffraction peaks which respectively correspond to the diffraction crystal faces (002) and (101) appear at about 22 degrees and 43 degrees, so that the material of the embodiment belongs to a carbon material. The electrochemical properties are shown in FIG. 11, at 25mAh g 1 At a current density of 296mAh g 1 The platform capacity below 0.1V is 210mAh g 1 The first circle coulombic efficiency was 88.43%.
Comparative example 4
The activation step was omitted from example 4, and the other steps were the same as in example 4.
The electrochemical properties are shown in FIG. 12, at 25mAh g 1 The reversible specific capacity is 280mAh g at the current density of (2) 1 The platform capacity below 0.1V is 200mAh g 1 The first circle coulombic efficiency was 89.02%.
As can be seen from the above examples and comparative examples: the difference in carbonization temperature causes a difference in electrochemical properties of the materials. On the premise of the same carbonization temperature, carbon dioxide is added for activation, so that the electrochemical performance of the material is improved, and a novel method is provided for preparing the negative electrode material of the sodium ion battery.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.
Claims (10)
1. A preparation method of a starch-based hard carbon sodium ion battery anode material is characterized by comprising the following steps: the method comprises the following steps:
s1, carrying out esterification treatment, namely carrying out esterification reaction on starch and maleic anhydride, and then crushing to obtain precursor particles;
s2, activating and pore-forming, namely introducing carbon dioxide under the protection of inert atmosphere, and activating and pore-forming the precursor particles obtained in the step S1 at a certain temperature to obtain an activated pore-forming product;
and S3, carbonizing at a high temperature, and heat-treating the activated pore-forming product obtained in the step S3 in an inert atmosphere to obtain the starch-based hard carbon sodium ion battery anode material.
2. The method of manufacturing according to claim 1, wherein: in the step S1, the mass ratio of the starch to the maleic anhydride is 1:1-5.
3. The method of manufacturing according to claim 1, wherein: in the step S1, precursor particles are prepared by dry powder hydrothermal method at 50-150 ℃.
4. The method of manufacturing according to claim 1, wherein: in the step S2, the flow ratio of the carbon dioxide to the inert gas is 1:1-5, and the total flow is 0.5-5L/(m) 3 Min), the activation temperature is 400-800 ℃, and the activation time is 1-8 h.
5. The method of manufacturing according to claim 1, wherein: in the step S3, the heat treatment temperature is 1300-1800 ℃, the heating rate is 1-20 ℃/min, and the heat preservation time is 0.1-10 h.
6. The method of manufacturing according to claim 1, wherein: in the step S1, the starch is one or more of potato starch, corn starch, wheat starch, pea starch, water chestnut starch, lotus root starch, water chestnut starch, soluble starch and thermoplastic starch.
7. The method of manufacturing according to claim 1, wherein: in step S1, the particle size of the precursor particles is 40-500 meshes.
8. The method of manufacturing according to claim 1, wherein: in the steps S2 and S3, the inert gas is argon and/or nitrogen.
9. A starch-based hard carbon sodium ion battery negative electrode material prepared by the preparation method of any one of claims 1-8.
10. A negative electrode sheet prepared using the starch-based hard carbon sodium ion battery negative electrode material of claim 9.
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| CN117384323B (en) * | 2023-12-12 | 2024-03-08 | 成都锂能科技有限公司 | Starch-based precursor material and preparation method and application thereof |
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