CN114551870A - Hard carbon negative electrode material of sodium ion battery and preparation method thereof - Google Patents
Hard carbon negative electrode material of sodium ion battery and preparation method thereof Download PDFInfo
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- CN114551870A CN114551870A CN202111534661.9A CN202111534661A CN114551870A CN 114551870 A CN114551870 A CN 114551870A CN 202111534661 A CN202111534661 A CN 202111534661A CN 114551870 A CN114551870 A CN 114551870A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
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- 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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a hard carbon negative electrode material of a sodium ion battery and a preparation method thereof, wherein the hard carbon negative electrode material is prepared from a hard carbon source and precursor salt of active metal particles by a one-step in-situ doping calcination method, the hard carbon source is one of waste sponge, waste paper products, waste cloth and wood chips, and the waste sponge comprises a sponge made of lignocellulose, foamed plastic polymer or sponge animals; the waste paper products comprise waste books, test paper, paper drawers or hard paper boxes; the waste cloth comprises cloth products made of clothes, home textiles or artware; the wood chips include leftover materials of all wood products of a wooden factory or a furniture factory. The invention has the following advantages: the environment-friendly, safe and energy-saving composite material is beneficial to industrial large-scale production, and has high capacity, stable cycle performance and good safety performance.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a hard carbon cathode material of a sodium ion battery and a preparation method thereof.
Background
With the gradual application of lithium ion batteries in the fields of smart phones, electric automobiles and the like, the demand of lithium is rapidly increased year by year, the national lithium resource storage is very limited, uneven in distribution and high in cost, and the rapid development of low-cost and high-performance energy storage devices in China is severely restricted. The sodium element has the same group element as the lithium element, and the lithium has the similar electrochemical performance, and the reserve is abundant and the cost is low. However, the further development of sodium ion batteries lacking suitable negative electrode materials is severely restricted, wherein the hard carbon material can be prepared by cracking biomass carbon sources and can also be obtained by cracking high molecular polymers, so that the hard carbon material has the advantages of wide sources, no toxicity, environmental protection, low sodium storage potential, higher specific capacity and the like, and is widely researched.
Common sodium ion batteries use hard carbon materials, transition metals or alloy compounds as a negative electrode, and polyanion, prussian blue or oxide materials as a positive electrode. The first-turn coulomb efficiency of the sodium-ion battery based on the materials reported at present is low, the cycle performance is poor, and the preparation process is complex.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a hard carbon negative electrode material of a sodium ion battery and a preparation method thereof, which aim to solve the problems in the background art.
In order to achieve the above objects, one aspect of the present invention provides a hard carbon negative electrode material for a sodium ion battery, the hard carbon negative electrode material having a hard carbon matrix and active metal particles attached to the hard carbon matrix, the hard carbon negative electrode material being prepared by a one-step in-situ doping calcination method using a hard carbon source selected from the group consisting of sponge, wooden material, fabric, and paper, and a precursor salt of the active metal particles; the precursor salt of the active metal particles is selected from inorganic salts of any one of Sn, Sb, Bi, W, Nb and Ta.
Further, the sponge is selected from artificial sponge and natural sponge, and the artificial sponge is selected from lignocellulose sponge or polyurethane foam plastic sponge.
Further, the hard carbon source waste material, the waste material is selected from used materials or scrap materials.
Further, the wooden material is selected from wood chips, strands or pieces, such as leftover material of all wood products of a wooden or furniture factory.
Further, the fabric is selected from natural cotton fabric, natural wool fabric, natural silk fabric, natural hemp fabric, artificial fiber fabric or blended fabric, such as cloth product made of clothes, coral fleece, home textiles or artware.
Further, the paper is selected from the group consisting of already-oiled paper or not-oiled paper, cardboard, and carton. Such as books, test papers, newspapers, toilet paper, packing boxes, hard paper boxes, etc.
Preferably, the hard carbon source is waste sponge made of lignocellulose.
Preferably, the active metal particles are one or more of Sn, Sb, Bi, W, Nb and Ta metal particles.
Preferably, the precursor salt of the metal particle comprises SnCl4·5H2O、SnC2O4、SnCl2、SnSO4、SbCl3、SbCl5、Sb(NO3)3、Bi(NO3)3、BiCl3、Bi2(SO4)3、WCl3、WCl5、WCl6、WOCl4、NbCl5、TaCl5One or more of them.
Preferably, the active metal particles are Sn.
Preferably, the precursor salt of the active metal particles is SnCl4·5H2O。
Further, the active metal particle size is 50-2000nm, preferably 400-1200nm, such as 600nm, 800nm, 1000 nm.
Further, the one-step in-situ doping calcination method is to mix, adsorb and dry the hard carbon source and the solution containing the precursor salt of the active metal particles, and then calcine the mixture.
Further, the temperature of the calcination is 600-.
Further, the mass of the active metal particles is 1 wt% to 20 wt%, preferably 5 wt% to 19 wt%, and more preferably 7 wt% to 13 wt% of the anode material, for example, the proportion of the active metal particles in the anode material is 10 wt%.
The invention also provides a preparation method of the hard carbon negative electrode material of the sodium ion battery, which comprises the following steps:
the method comprises the following steps: cleaning and drying the hard carbon source to obtain a clean hard carbon source;
step two: mixing precursor salt of the active metal particles with a mixed solution of an organic solvent containing ammonia water and water to obtain a solution of the precursor salt of the active metal particles; dissolving in organic solvent, stirring and ultrasonically treating until the organic solvent is completely dissolved, then adding ammonia water which is the organic solvent, ultrasonically stirring until the organic solvent is completely dissolved, adding deionized water, and uniformly mixing to obtain a mixed solution;
step three: fully soaking the hard carbon source obtained in the step one in the mixed solution obtained in the step two, and drying to remove the solvent;
step four: and calcining and carbonizing the material obtained in the step three at the temperature of 600-2500 ℃ in a reducing atmosphere to obtain the active metal particle doped hard carbon material.
Further, the cleaning method in the first step is an acid cleaning method.
Further, the organic solvent in the second step is selected from one or more of methanol, absolute ethyl alcohol, acetone, isopropanol, ethyl acetate and butyl acetate.
Further, the ratio of the organic solution to the ammonia water in the second step is 7-15: 1.
Further, in the second step, the mass ratio of the hard carbon source to the precursor salt of the active metal particles in the mixed solvent is 100: 0.75-19.69. Preferably 100: 3-10, more preferably 100: 5-8.
In yet another aspect, the present invention provides a negative electrode for a sodium ion battery, the negative electrode comprising the hard carbon negative electrode material of the present invention.
Further, the negative electrode is composed of the active material made of the hard carbon negative electrode material, a conductive agent and a binder, and a negative electrode current collector.
Further, the conductive agent is conductive carbon black.
Further, the binder is selected from the group consisting of polytetrafluoroethylene, hexafluoropropylene, and polyvinyl fluoride.
Further, the ratio of the hard carbon negative electrode material, the conductive agent and the binder is 5-15:0.5-2:0.5-2, preferably 8:1: 1.
In a further aspect of the invention, there is provided a sodium ion battery comprising a negative electrode for a sodium ion battery as described above.
Preferably, the sodium-ion battery is made of the negative electrode, the separator, the electrolyte and the positive electrode for the sodium-ion battery of the present invention.
After the technical scheme is adopted, the invention has the beneficial effects that:
(1) according to the hard carbon negative electrode material for the sodium ion battery, waste sponge, waste paper products, waste cloth, wood dust and the like are used as carbon sources, and active metal particles and the hard carbon material are doped together through a simple one-step calcining carbonization method, so that the interlayer spacing is enlarged, the sodium storage sites are increased, the contribution is made to the capacity and the rate capability of the battery, the production cost of the negative electrode material is low, and the production cost of the sodium ion battery is reduced;
(2) the hard carbon negative electrode material for the sodium ion battery adopts low-cost waste sponge, waste paper products, waste cloth, sawdust and the like as carbon sources, the material source is wide, the safety of the reaction process is high, the interlayer spacing of the prepared negative electrode material is large, sodium ions are easy to embed and separate, the problem of slow dynamics of the battery is solved, and the cycle performance and the rate capability of the battery can be improved;
(3) the hard carbon cathode material of the sodium ion battery adopts Sn, Sb, Bi, W, Nb and Ta as active metal particles, has abundant reserves in China, is easy to obtain, safe and nontoxic, is simple and easy to realize in the doping process, increases the interlayer spacing and sodium storage sites for the hard carbon cathode material, and improves the performance of the sodium ion battery;
(4) the preparation process of the hard carbon cathode material of the sodium ion battery does not generate toxic and harmful substances in the reaction process, is environment-friendly, safe and energy-saving, and is beneficial to industrial large-scale production;
(5) the hard carbon cathode material of the sodium ion battery takes waste sponge, waste paper products, waste cloth, sawdust and the like with low cost as carbon sources, takes Sn, Sb, Bi, W, Nb and Ta metal particles as doping active metals, dopes the active metal particles into the hard carbon material by a simple, convenient and feasible one-step calcination carbonization method to obtain the hard carbon material, fills hard carbon micropores with pseudometallic Na clusters, and then Na+Intercalation between layers of hard carbon domains, subsequent Na trapping by defects, etc+The hard carbon is sufficiently electrochemically oxidized while Na is also occupied+The hard carbon cathode material of the sodium ion battery is environment-friendly and safe, has a simple production process and low cost, has excellent electrochemical performance, higher capacity and stable cycle performance, and has good safety performance.
Drawings
FIG. 1 is a schematic structural diagram of a hard carbon negative electrode material of a sodium ion battery according to the present invention;
as shown in the figure: 1. a layer of hard carbon material; 2. active metal particles.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1: preparation method of sodium ion battery containing hard carbon negative electrode material
Preparing a hard carbon negative electrode material: washing 100g of waste lignocellulose sponge with acid, washing with clear water, drying, and mixing 6.5g of SnCl4·5H2Dissolving O in 320mL of methanol, stirring and ultrasonically treating until the O is completely dissolved, and then adding a solvent with the volume ratio of 15:1, ultrasonically stirring the ammonia water until the ammonia water is completely dissolved, and adding 960mL of deionized water to mix uniformly; soaking sponge in the obtained mixed solution, and soaking sponge in the mixed solution by using good water absorbability of spongeDrying in the solution at 100 deg.C for 48 h; calcining and carbonizing the alloy at 1200 ℃ in a CO atmosphere to obtain the hard carbon material doped with Sn metal particles.
Preparing a negative electrode: adding 0.4g of the obtained hard carbon material, 0.05g of conductive carbon black and 0.05g of polytetrafluoroethylene into 1mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; then the slurry is evenly coated on the surface of the carbon-coated aluminum foil and dried in vacuum. And cutting the dried electrode slice into a circular slice with the diameter of 12mm, and compacting the circular slice to be used as a negative electrode for standby.
Preparing a diaphragm: the glass fiber diaphragm is cut into a circular piece with the diameter of 16mm, and the circular piece is dried to be used as the diaphragm for standby.
Preparing an electrolyte: weighing 1.6g of sodium hexafluorophosphate, adding the sodium hexafluorophosphate into 5mL of a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (the volume ratio is 1:1:1), stirring until the sodium hexafluorophosphate is completely dissolved, and fully stirring uniformly to obtain an electrolyte for later use (the electrolyte concentration is 1M).
Preparing a positive electrode: adding 0.24g of expanded graphite, 0.03g of carbon black and 0.03g of polyvinylidene fluoride into 0.5mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; and then uniformly coating the slurry on the surface of the copper foil and performing vacuum drying. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a positive electrode for standby.
Assembling: and in a glove box protected by inert gas, tightly stacking the prepared positive electrode, the diaphragm and the negative electrode in sequence, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button type shell to finish the assembly of the sodium-ion battery.
Comparative example 1: comparative example 1 and example 1 negative electrode material preparation is the same as the sodium ion battery assembly process except that the negative electrode material of comparative example 1 is not doped with active metal particles, see table 1 for details.
Comparative example 2: comparative example 2 shows that the hard carbon negative electrode material prepared by taking kelp as a carbon source in the invention of other documents is used as a negative electrode of a sodium ion battery, and the performance difference is specifically shown in table 1;
electrochemical performance tests of the secondary battery provided in example 1 of the present invention were performed, and the results and the comparison results of the electrochemical performance tests were shown in table 1, compared with the performances of the hard carbon negative electrode material not doped with active metal particles in comparative example 1 and the hard carbon negative electrode materials prepared in other documents in comparative example 2.
Table 1: example 1 compares the performance with comparative examples 1 and 2
As can be seen from table 1, the performance of the negative electrode material doped with Sn metal particles is better than the specific capacity, the first coulombic efficiency and the cycle performance of the hard carbon negative electrode material prepared by other preparation methods, and the preparation method is not complicated, and is more excellent than the performance of the negative electrode material not doped with active metal particles.
Examples 2 to 8: examples 2-8 were prepared the same as example 1 for the anode material and the sodium ion battery assembly process, except for the carbon source of the anode material, see table 2 for details.
Table 2: comparison of negative electrode Performance for different carbon sources
As can be seen from table 2, compared with comparative examples 1 and 2, the negative electrode material prepared from the materials such as wood material, sponge, paper, fabric, plastic, etc. and Sn metal particles according to the present invention achieves higher specific capacity, first coulombic efficiency and lower capacity attenuation, and increases cycle number.
Different carbon sources also have influence on the performance of the negative electrode material, wherein the performance of the negative electrode material prepared by using the sponge made of wood fiber is the most excellent.
Examples 9 to 13: examples 9-13 the hard carbon anode material of example 1 was prepared in the same manner as in the sodium ion battery assembly process, except that only the anode was doped with the type of metal particles, see table 3 for details.
Table 3: comparison of the performances of the negative electrodes with differently doped metal particles
As can be seen from table 3, compared to comparative examples 1 and 2, the negative electrode material prepared by adding the metal particles according to the present invention achieves a higher specific capacity, a first coulombic efficiency, and a lower capacity fade, and increases the cycle number. The performance of the cathode material with Sn metal particles added into different doped metal particles is the best, the storage amount of Sn is the most abundant on the earth, and the cost is the lowest, so that the cathode material can be the most preferable scheme.
Examples 14 to 23: examples 14-23 the hard carbon anode material of example 1 was prepared the same as the sodium ion battery assembly process, except at the anode material carbonization temperature, see table 4 for details.
Table 4: comparison of negative electrode Performance at different calcination carbonization temperatures
From table 4, it can be seen that the calcination temperature is in the range of 600-. While not wishing to be bound by theory, it is possible that the effect of temperature on the size of the active metal particles is due to the comparison of different calcination carbonization temperatures, the performance of the negative electrode material is best at 1200 ℃.
Examples 24 to 30: examples 24-30 the hard carbon anode material of example 1 was prepared the same as the sodium ion battery assembly process except for the amount of active metal particles doped in the anode material only, see table 5 for details.
Table 5: comparison of negative electrode Performance with different amounts of active Metal doping
It can be seen from table 5 that the doping amount of the active metal particles in the range of 1 wt% to 20 wt% achieves higher specific capacity, first coulombic efficiency and lower capacity fade for the obtained product relative to the materials of the comparison documents 1 and 2, and the cycle number is increased. Wherein the electrochemical performance of the cathode material is the most excellent when the content is 10 wt%.
Examples 31 to 35: examples 31-35 were prepared identically to the hard carbon anode material of example 1 and the sodium ion battery assembly process, except for the size of the anode material active metal particles, see table 6 for details.
Table 6: comparison of negative electrode Performance for different active Metal particle sizes
It can be seen from table 6 that the active metal particle size in the range of 50nm to 2000nm achieved better electrochemical performance than the comparative example, where the material performance obtained using the conditions of example 1 was optimal.
Examples 36 to 44: examples 36-44 the hard carbon anode material of example 1 was prepared the same as the sodium ion battery assembly process, except for the precursor salt of the active metal particles of the anode material only, see table 7 for details.
Table 7: comparison of negative electrode performances of different active metal particle precursor salts
From Table 7, it can be seen that the same active metal particlesThe performance of the cathode materials prepared from different precursor salts is different, the difference of the cathode materials prepared from the precursor salts of different active metal particles is larger, wherein the precursor salt SnCl of the Sn metal particles4·5H2The performance of the cathode material prepared from O is best.
The hard carbon cathode material of the sodium ion battery prepared by the invention takes waste sponge, waste paper, waste cloth, sawdust and the like with low cost as carbon sources and takes Sn, Sb, Bi, W, Nb and Ta as active metal particles, the obtained cathode material has low cost and environmental protection, the capacity is improved, and the energy storage mechanism in the sodium ion battery is as follows: filling hard carbon micropores with metalloid Na clusters during charging, Na+Na is easily captured by interlamination and defects embedded in hard carbon micro-regions+The process of occupying the position of the hard carbon enables sodium ions to enter the negative electrode, the electrochemical oxidation reaction of the hard carbon is fully carried out, and Na is simultaneously added+An alloying reaction with the active metal particles occurs to achieve energy storage. The sodium ion battery has the advantages that the problems of limited lithium ion resources and high cost are relieved, the anode and cathode materials are simple, cheap and easily available, environment-friendly and safe, the production process is simple, and the cost is low, so that the sodium ion battery has high specific capacity, high cycle performance and high safety.
The present invention and its embodiments have been described above, and the description is not intended to be limiting, and the drawings are only one embodiment of the present invention, and the actual structure is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The hard carbon cathode material of the sodium ion battery is characterized in that the hard carbon cathode material is provided with a hard carbon matrix and active metal particles attached to the hard carbon matrix, and the hard carbon cathode material is prepared by a hard carbon source and precursor salts of the active metal particles through a one-step in-situ doping calcination method, wherein the hard carbon source is selected from sponge, a wooden material, a fabric or paper; the precursor salt of the active metal particles is selected from inorganic salts of any one of Sn, Sb, Bi, W, Nb and Ta;
preferably, the hard carbon source is selected from waste materials selected from used materials or scrap materials.
2. The hard carbon negative electrode material according to claim 1, wherein the sponge is selected from the group consisting of artificial sponges and natural sponges, the artificial sponges being selected from the group consisting of lignocelluloses sponges and polyurethane foam sponges;
the wood material is selected from wood chips, strands or pieces, such as the scrap of all wood products of a wood or furniture mill;
the fabric is selected from natural cotton fabric, natural wool fabric, natural silk fabric, natural hemp fabric, artificial fiber fabric or blended fabric;
the paper is selected from the group consisting of paper that has been subjected to mimeographing or paper, cardboard, carton that has not been subjected to mimeographing.
3. The hard carbon negative electrode material as claimed in claim 1, wherein the hard carbon source is selected from the group consisting of leftover materials of all wood products of manufacturing plants or furniture factories, waste natural sponges, waste lignocelluloses sponges, waste polyurethane foam plastic sponges, waste clothes, coral velvet, cloth products made of home textiles or artware, books, test papers, newspapers, toilet paper, packing boxes and hard paper boxes.
4. The hard carbon anode material of claim 1, wherein the active metal particles are one or more of Sn, Sb, Bi, W, Nb, Ta metal particles;
preferably, the precursor salt of the metal particles is selected from SnCl4·5H2O、SnC2O4、SnCl2、SnSO4、SbCl3、SbCl5、Sb(NO3)3、Bi(NO3)3、BiCl3、Bi2(SO4)3、WCl3、WCl5、WCl6、WOCl4、NbCl5、TaCl5One or more of them.
5. The hard carbon anode material according to claim 1, wherein the active metal particle size is 50-2000nm, preferably 400-1200 nm.
6. The hard carbon anode material of claim 1, wherein the one-step in-situ doping calcination method comprises mixing, adsorbing, drying, and calcining a hard carbon source and a solution containing a precursor salt of the active metal particles;
preferably, the temperature of calcination is 600-.
7. The hard carbon anode material according to claim 1, wherein the mass of the active metal particles is 1 to 20 wt%, preferably 5 to 19%, more preferably 7 to 13% of the hard carbon anode material.
8. The method for preparing the hard carbon anode material of the ion battery in any one of claims 1 to 7, which is characterized by comprising the following steps:
the method comprises the following steps: cleaning and drying the hard carbon source to obtain a clean hard carbon source;
step two: mixing precursor salt of the active metal particles with a mixed solution of an organic solvent containing ammonia water and water to obtain a solution of the precursor salt of the active metal particles; dissolving in organic solvent, stirring and ultrasonically treating until the organic solvent is completely dissolved, then adding ammonia water which is the organic solvent, ultrasonically stirring until the organic solvent is completely dissolved, adding deionized water, and uniformly mixing to obtain a mixed solution;
step three: fully soaking the hard carbon source obtained in the step one in the mixed solution obtained in the step two, and drying to remove the solvent;
step four: calcining and carbonizing the material obtained in the step three at the temperature of 600-2500 ℃ in a reducing atmosphere to obtain a hard carbon material doped with active metal particles;
preferably, the organic solvent in the second step is one or more selected from methanol, absolute ethyl alcohol, acetone, isopropanol, ethyl acetate and butyl acetate;
preferably, the ratio of the organic solution to the ammonia water in the second step is 7-15: 1;
preferably, the mass ratio of the hard carbon source to the precursor salt of the active metal particles in the mixed solvent in the second step is 100: 0.75-19.69; more preferably 100: 3-10.
9. A negative electrode for a sodium ion battery, characterized in that the negative electrode comprises a negative electrode active material of the hard carbon negative electrode material according to any one of claims 1 to 7;
preferably, the negative electrode is composed of a negative electrode active material made of the above hard carbon negative electrode material, a conductive agent and a binder, and a negative electrode current collector;
preferably, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, carbon fibers or graphene;
preferably, the binder is selected from one or more of polytetrafluoroethylene, hexafluoropropylene, polyvinyl fluoride, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins (polybutadiene, polyvinyl chloride, polyisoprene, etc.);
preferably, the ratio of the hard carbon anode material, the conductive agent and the binder is 5-15:0.5-2:0.5-2, more preferably 8:1: 1.
10. A sodium-ion battery characterized by comprising the negative electrode for a sodium-ion battery according to claim 9;
preferably, the sodium ion battery is made of the negative electrode for sodium ion battery, the separator, the electrolyte and the positive electrode according to any one of claims 1 to 7.
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| CN115321514A (en) * | 2022-08-29 | 2022-11-11 | 惠州亿纬锂能股份有限公司 | Hard carbon material and preparation method and application thereof |
| CN115676802A (en) * | 2022-08-26 | 2023-02-03 | 四川佰思格新能源有限公司 | Hard carbon negative electrode material of sodium ion battery and preparation method thereof |
| CN116169288A (en) * | 2023-03-09 | 2023-05-26 | 湖南钠能时代科技发展有限公司 | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
| WO2023109660A1 (en) * | 2021-12-15 | 2023-06-22 | 深圳先进技术研究院 | Hard carbon negative electrode material for sodium-ion battery and preparation method therefor |
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| CN117208888B (en) * | 2023-09-04 | 2024-02-27 | 博路天成新能源科技有限公司 | Manufacturing process of hard carbon negative electrode material for sodium ion battery |
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| CN114551870A (en) * | 2021-12-15 | 2022-05-27 | 深圳先进技术研究院 | Hard carbon negative electrode material of sodium ion battery and preparation method thereof |
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| WO2023109660A1 (en) * | 2021-12-15 | 2023-06-22 | 深圳先进技术研究院 | Hard carbon negative electrode material for sodium-ion battery and preparation method therefor |
| CN114843524A (en) * | 2022-06-17 | 2022-08-02 | 珠海冠宇电池股份有限公司 | Modified current collector and non-negative sodium metal battery comprising same |
| CN115676802A (en) * | 2022-08-26 | 2023-02-03 | 四川佰思格新能源有限公司 | Hard carbon negative electrode material of sodium ion battery and preparation method thereof |
| CN115676802B (en) * | 2022-08-26 | 2024-02-27 | 四川佰思格新能源有限公司 | Hard carbon negative electrode material of sodium ion battery and preparation method thereof |
| CN115321514A (en) * | 2022-08-29 | 2022-11-11 | 惠州亿纬锂能股份有限公司 | Hard carbon material and preparation method and application thereof |
| CN116169288A (en) * | 2023-03-09 | 2023-05-26 | 湖南钠能时代科技发展有限公司 | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
| CN116169288B (en) * | 2023-03-09 | 2024-03-05 | 湖南钠能时代科技发展有限公司 | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
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