CN115849337A - Hard carbon material and preparation method and application thereof - Google Patents
Hard carbon material and preparation method and application thereof Download PDFInfo
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- CN115849337A CN115849337A CN202211644281.5A CN202211644281A CN115849337A CN 115849337 A CN115849337 A CN 115849337A CN 202211644281 A CN202211644281 A CN 202211644281A CN 115849337 A CN115849337 A CN 115849337A
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- sintering
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
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- 239000002994 raw material Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
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- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 239000011268 mixed slurry Substances 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 23
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- 238000004321 preservation Methods 0.000 claims description 7
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- 239000010406 cathode material Substances 0.000 abstract description 4
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
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Abstract
The invention provides a hard carbon material and a preparation method and application thereof, belonging to the technical field of negative electrode materials. The preparation method of the hard carbon material provided by the invention comprises the following steps: sequentially carrying out first sintering and purification on a carbonaceous raw material to obtain a first precursor; mixing the first precursor, a surfactant doping source and water, and drying the obtained mixed slurry to obtain a second precursor; the doping element contained in the surfactant doping source is one or more of nitrogen, phosphorus, sulfur and boron; the mass ratio of the carbonaceous raw material to the surfactant doping source is 1:0.05 to 0.55; and carrying out second sintering on the second precursor to obtain the hard carbon material. The hard carbon material provided by the invention is used as a secondary battery cathode material and has higher specific capacity.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and particularly relates to a hard carbon material and a preparation method and application thereof.
Background
The lithium ion secondary battery has the advantages of good stability, high energy density, no memory effect and the like, and is widely applied to the fields of 3C consumer batteries, power batteries and energy storage batteries. The current commercial lithium ion secondary battery negative electrode material mainly uses a graphite negative electrode as a main material, but the theoretical specific capacity of the graphite negative electrode is lower and is only 372mAh/g. Therefore, it is an important direction of current research to develop a novel secondary battery negative electrode material with high specific capacity.
Disclosure of Invention
The invention aims to provide a hard carbon material, a preparation method and application thereof.
In order to realize the purpose of the invention, the invention provides the following technical scheme:
a method of preparing a hard carbon material, comprising the steps of:
sequentially carrying out first sintering and purification on a carbonaceous raw material to obtain a first precursor;
mixing the first precursor, a surfactant doping source and water, and drying the obtained mixed slurry to obtain a second precursor; the doping element contained in the surfactant doping source is one or more of nitrogen, phosphorus, sulfur and boron; the mass ratio of the carbonaceous raw material to the surfactant doping source is 1:0.05 to 0.55;
and carrying out second sintering on the second precursor to obtain the hard carbon material.
Preferably, the surfactant-based doping source includes one or more of polyoxyethylene alkylamine, polyoxyethylene alkylamide, alkylpolyoxyethylene ether phosphate, alkylphosphate, alkylsulfonate, alkylsulfate, alkylborate, and alkoxyborate.
Preferably, the carbonaceous feedstock comprises one or more of natural biomass material, resinous material and plant extracts.
Preferably, the temperature of the first sintering is 250-700 ℃; the heat preservation time of the first sintering is 2-5 h.
Preferably, the purification comprises one or more of water washing, alkali washing and acid washing.
Preferably, the first sintering and purifying further comprise: and carrying out particle shaping on the material obtained after the first sintering.
Preferably, the particle size D50 of the first precursor is 3 to 15 μm.
Preferably, the temperature of the second sintering is 800-1500 ℃; the heat preservation time of the second sintering is 2-10 h.
The invention also provides the hard carbon material prepared by the preparation method, which comprises a carbonaceous material and doping elements doped on the surface of the carbonaceous material and in pore channels, wherein the doping elements are one or more of nitrogen, phosphorus, sulfur and boron, and the content of the doping elements in the hard carbon material is 0.5-5.5 wt%; the interlayer spacing of the 002 surface of the hard carbon material is 0.35-0.42 nm.
The invention also provides application of the hard carbon material in a secondary battery cathode material.
The invention provides a preparation method of a hard carbon material, which comprises the following steps: sequentially carrying out first sintering and purification on a carbonaceous raw material to obtain a first precursor; mixing the first precursor, a surfactant doping source and water, and drying the obtained mixed slurry to obtain a second precursor; the doping element contained in the surfactant doping source is one or more of nitrogen, phosphorus, sulfur and boron; the mass ratio of the carbonaceous raw material to the surfactant doping source is 1:0.05 to 0.55; and carrying out second sintering on the second precursor to obtain the hard carbon material. The invention adopts the surfactant doping source, can infiltrate on the surface of the carbonaceous raw material and in the pore canal, further can effectively dope, and selects the surfactant doping source to effectively increase the interlayer spacing of the carbonaceous material relative to the inorganic doping source, thereby being beneficial to providing more active sites, improving the adhesiveness and the deposition capacity of doping elements on the surface of the carbonaceous material and the pore canal, and taking the hard carbon material as the cathode material of the secondary battery, thereby having higher specific capacity. The embodiment result shows that the first reversible capacity of the hard carbon material prepared by the invention is more than 400mAh/g through element doping, and the hard carbon material has higher specific capacity; in addition, in a lithium ion battery test system, the initial coulombic efficiency is more than 83%. Meanwhile, the raw materials used for preparing the hard carbon material are low in price, and the preparation process and equipment are mature, so that the method is suitable for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a graph showing a first charge and discharge curve of a hard carbon material prepared in example 1;
fig. 2 is a 500-fold SEM image of the hard carbon material prepared in example 1;
fig. 3 is a 5000-fold SEM image of the hard carbon material prepared in example 1;
fig. 4 is an EDS diagram of the hard carbon material prepared in example 1.
Detailed Description
The invention provides a preparation method of a hard carbon material, which comprises the following steps:
sequentially carrying out first sintering and purification on a carbonaceous raw material to obtain a first precursor;
mixing the first precursor, a surfactant doping source and water, and drying the obtained mixed slurry to obtain a second precursor; the doping element contained in the surfactant doping source is one or more of nitrogen, phosphorus, sulfur and boron; the mass ratio of the carbonaceous raw material to the surfactant doping source is 1:0.05 to 0.55;
and carrying out second sintering on the second precursor to obtain the hard carbon material.
In the present invention, unless otherwise specified, each of the preparation starting materials used is a commercially available product well known to those skilled in the art.
According to the invention, a carbonaceous raw material is subjected to first sintering and purification in sequence to obtain a first precursor. In the present invention, the carbonaceous feedstock preferably comprises one or more of natural biomass materials, resinous materials and plant extracts. In the invention, the natural biomass material is preferably one or more of apricot shells, walnut shells, rice hulls, peanut shells, corn cobs, pistachio shells, coconut shells, jujube shells, li Ke, wood, bamboos, hazelnuts and straws; the resin material is preferably one or more of phenolic resin, epoxy resin, furfural resin and acrylic resin; the plant extract is preferably one or more of starch, sucrose, glucose, cellulose, maltose and natural rubber.
In the present invention, the temperature of the first sintering is preferably 250 to 700 ℃, more preferably 500 to 650 ℃; the holding time for the first sintering is preferably 2 to 5 hours, and more preferably 4 to 5 hours. In the present invention, the first sintering is preferably carried out in a protective atmosphere; the protective gas providing the protective atmosphere is preferably one of nitrogen, helium, neon and argon, and more preferably nitrogen.
In the present invention, the purification preferably includes one or more of water washing, alkali washing and acid washing, and more preferably acid washing and water washing are sequentially performed or alkali washing and water washing are sequentially performed.
In the present invention, the acid reagent used for the acid washing preferably includes one or more of hydrofluoric acid, sulfurous acid, phosphoric acid, nitrous acid, sulfuric acid, hydrochloric acid, and nitric acid, and more preferably hydrochloric acid; the concentration of the acid reagent is preferably 0.2 to 2mol/L, more preferably 0.5 to 1.5mol/L, and still more preferably 1mol/L. In the invention, the alkaline reagent used for alkaline washing preferably comprises one or more of sodium hydroxide solution, lithium hydroxide solution, calcium hydroxide solution and potassium hydroxide solution, and more preferably sodium hydroxide solution; the concentration of the alkali agent is preferably 0.5 to 5mol/L, more preferably 1 to 2.5mol/L, and further preferably 2mol/L. In the invention, the water washing preferably adopts deionized water; the water wash is preferably washed to neutrality. In the present invention, the purification has an effect of removing calcium, magnesium and magnetic substances in the carbonaceous raw material.
In the present invention, it is preferable that the first sintering and the purification further include: and carrying out particle shaping on the material obtained after the first sintering. In the present invention, the particle shaping preferably includes sequentially pulverizing and classifying. In the invention, the equipment used for crushing is preferably one or two of a hammer crusher, a double-roller crusher and a jet mill, and is more preferably a jet mill; the equipment adopted for grading is preferably a grader. In the present invention, the pulverization is preferably performed such that the particle size D50 of the material is 3 to 15 μm, more preferably 6 to 10 μm, and further preferably 6 to 8 μm; the classification is preferably carried out so that the particle size D10 of the material is not less than 3 μm, more preferably 3 to 5 μm, still more preferably 3.5 to 4.2 μm, and still more preferably 3.8 to 4.1. Mu.m.
In the present invention, the particle size D50 of the first precursor is preferably 3 to 15 μm, and more preferably 6 to 10 μm.
After the first precursor is obtained, the first precursor, the surfactant doping source and water are mixed, and the obtained mixed slurry is dried to obtain a second precursor. In the present invention, the surfactant-based doping source preferably includes one or more of polyoxyethylene alkylamine, polyoxyethylene alkylamide, alkylpolyoxyethylene ether phosphate, alkylphosphate, alkylsulfonate, alkylsulfate, alkylpborate, and alkoxyborate, more preferably alkylsulfonate and alkylphosphate; when the surfactant-based doping source is an alkyl sulfonate and an alkyl phosphate, the mass ratio of the alkyl sulfonate to the alkyl phosphate is preferably 1:0.5 to 1.5. In the invention, the surfactant doping source is selected to be more beneficial to effective doping compared with an inorganic doping source, and the specific capacity of the hard carbon material can be further improved.
In the present invention, the water preferably includes deionized water 。
In the present invention, the mass ratio of the carbonaceous raw material to the surfactant-based dopant source is preferably 1:0.05 to 0.55, more preferably 1:0.05 to 0.25, more preferably 1:0.07 to 0.15, more preferably 1:0.09 to 0.1. In the present invention, the specific capacity of the hard carbon material can be effectively increased by controlling the mass ratio of the carbonaceous raw material to the surfactant-based dopant source within the above range.
In the present invention, the mixing manner of the first precursor, the surfactant-based dopant source, and the water is not particularly limited, and a mixing manner known in the art may be used. In the present invention, the temperature of the drying is preferably 90 to 115 ℃, more preferably 100 to 105 ℃; the drying time is preferably 2 to 3.5 hours.
And after a second precursor is obtained, carrying out second sintering on the second precursor to obtain the hard carbon material. In the present invention, the temperature of the second sintering is preferably 800 to 1500 ℃, more preferably 950 to 1250 ℃, and further preferably 1000 to 1150 ℃; the holding time for the second sintering is preferably 2 to 10 hours, and more preferably 2 to 4 hours. In the present invention, the second sintering is preferably performed in a protective atmosphere; the protective gas providing the protective atmosphere is preferably one of nitrogen, helium, neon and argon, and more preferably nitrogen. In the invention, the surfactant doping source and the carbonaceous raw material are uniformly mixed and then sintered, the surfactant doping source can be infiltrated on the surface of the carbonaceous raw material and in the pore canal, the adhesiveness and the deposition amount of the doping source on the surface of the carbonaceous raw material and in the pore canal are improved, and the effective embedding of doping elements is facilitated during sintering.
The invention also provides the hard carbon material prepared by the preparation method, which comprises a carbonaceous material and doping elements doped on the surface of the carbonaceous material and in pore channels, wherein the doping elements are one or more of nitrogen, phosphorus, sulfur and boron, and the content of the doping elements in the hard carbon material is 0.5-5.5 wt%, preferably 0.8-5.23 wt%, and further preferably 3.3-4.0 wt%; the interlayer spacing of the 002 surface of the hard carbon material is 0.35-0.42 nm, preferably 0.35-0.39 nm; the specific surface area of the hard carbon material is preferably 1 to 20m 2 (ii) g, more preferably 2 to 10m 2 (ii)/g; the hard carbon materialThe particle size D50 of the material is preferably from 2 to 20 μm, more preferably from 3 to 15 μm.
The invention also provides application of the hard carbon material in a secondary battery cathode material.
In the present invention, the secondary battery preferably includes a lithium ion secondary battery, a sodium ion secondary battery, a potassium ion secondary battery, a supercapacitor, or a nickel metal hydride battery, and more preferably a lithium ion secondary battery or a sodium ion secondary battery.
For further explanation of the present invention, the hard carbon materials provided in the present invention will be described in detail with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 5kg of apricot shells, performing first sintering for 4h at the temperature of 500 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain 1.5kg of sintered materials;
crushing the sintering material by using a jet mill until the granularity D50 of the material is 6 +/-1 mu m, grading by using a grader until the granularity D10 of the material is 3.5 mu m, pickling the obtained material by using hydrochloric acid with the concentration of 1mol/L, and washing by using deionized water until the filtrate is neutral to obtain 1kg of a first precursor;
mixing 1kg of the first precursor, 450g of alkyl phosphate (with the phosphorus content of 8.84%) and 1kg of water, uniformly stirring, and drying at 105 ℃ for 2 hours to obtain a second precursor;
and (3) carrying out second sintering on the second precursor for 2.5h at 1150 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain 1.1kg of hard carbon material.
Example 2
Weighing 5kg of starch, performing heat preservation at 650 ℃ in a nitrogen atmosphere for first sintering for 4h, and cooling to room temperature to obtain 1.5kg of sintered material;
crushing the sintering material by using a jet mill until the granularity D50 of the material is 8 +/-1 mu m, grading by using a grader until the granularity D10 of the material is 4.2 mu m, and washing the obtained material by using deionized water until filtrate is neutral to obtain 1kg of a first precursor;
mixing 1kg of the first precursor, 380g of alkyl sulfonate (with the sulfur content of 11.1%) and 1kg of water, uniformly stirring, and drying at 100 ℃ for 3.5h to obtain a second precursor;
and (3) carrying out second sintering on the second precursor for 3h at the temperature of 1000 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain 0.95kg of hard carbon material.
Example 3
Weighing 5kg of phenolic resin, carrying out heat preservation at 500 ℃ in a nitrogen atmosphere for first sintering for 4h, and cooling to room temperature to obtain 1.5kg of sintered material;
crushing the sintering material by using a jet mill until the granularity D50 of the material is 6 +/-1 mu m, grading by using a grader until the granularity D10 of the material is 3.8 mu m, performing alkali washing on the obtained material by using a sodium hydroxide solution with the concentration of 2mol/L, and washing by using deionized water until the filtrate is neutral to obtain 1kg of a first precursor;
mixing 1kg of the first precursor, 390g of alkyl borate (with boron content of 3.47%) and 1kg of water, uniformly stirring, and drying at 105 ℃ for 2h to obtain a second precursor;
and (3) carrying out second sintering on the second precursor for 4h at 950 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain 1.35kg of hard carbon material.
Example 4
Weighing 5kg of straws, carrying out heat preservation at 500 ℃ in a nitrogen atmosphere for first sintering for 4h, and cooling to room temperature to obtain 1.5kg of sintered material;
crushing the sintering material by using a jet mill until the granularity D50 of the material is 10 +/-1 mu m, grading by using a grader until the granularity D10 of the material is 4.1 mu m, pickling the obtained material by using hydrochloric acid with the concentration of 1mol/L, and washing by using deionized water until the filtrate is neutral to obtain 1kg of a first precursor;
mixing 1kg of the first precursor, 220g of alkyl sulfonate (with the sulfur content of 11.1%), 360g of alkyl phosphate (with the phosphorus content of 8.84%) and 1kg of water, uniformly stirring, and drying at 105 ℃ for 2 hours to obtain a second precursor;
and (3) carrying out second sintering on the second precursor for 2h at 1250 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain 1.12kg of hard carbon material.
Comparative example 1
A hard carbon material was prepared with reference to the method of example 1, except that the alkyl phosphate was omitted.
Comparative example 2
A hard carbon material was prepared according to the method of example 1, except that the acid washing and water washing steps were omitted.
Comparative example 3
A hard carbon material was prepared by referring to the method of example 1, except that the amount of the alkyl phosphate (phosphorus content: 8.84%) used in this comparative example was 50g.
Comparative example 4
A hard carbon material was prepared by referring to the method of example 1, except that "450g of alkyl phosphate (phosphorus content: 8.84%)" was replaced with "148g of phosphoric acid having a concentration of 85 wt%".
Test example 1
SEM and EDS analyses of the hard carbon material prepared in example 1 were performed using JSM-7160 scanning electron microscope energy spectrometer of japan electronics, and the EDS results are shown in fig. 4 and the SEM results are shown in fig. 2 to 3. As can be seen from fig. 2 to 4, the hard carbon material prepared in example 1 has a relatively regular morphology and is effectively doped with phosphorus.
Test example 2
The specific surface area of the material was measured using Kang Da NOVA4000e, usa, and the results are shown in table 1. As can be seen from table 1, the hard carbon material prepared by the present invention has a smaller specific surface area.
Test example 3
Mixing the hard carbon materials obtained in examples 1-4 and comparative examples 1-4 with conductive carbon black and a binder in pure water according to a mass ratio of 96. Assembling a button type half cell in a glove box filled with argon, wherein a counter electrode is a metal lithium sheet, a diaphragm is PE, and electrolyte is1mol/L LiPF 6 Solution (solvent is a mixture of EC and DMC in a volume ratio of 1:1). The button half cell was subjected to charge-discharge test (test equipment was LAND cell test system of Blueelectronics, inc., wuhan city), with a test procedure of 0.2C DC to0V, 0.05C DC to0V,0V CV 50uA,0.01C DC to0V,0V CV 2uA, rest 10min,0.2C CC to 2V. The first reversible capacity and the first efficiency of the hard carbon materials in the examples and comparative examples were measured, and the results are shown in table 1.
Table 1 preparation conditions and physical and electrochemical performance test data of hard carbon materials in examples and comparative examples
Comparing example 1 with comparative example 1, it can be seen that the first reversible capacity of the prepared hard carbon material is 388mAh/g without any doping source treatment, the first efficiency is 82.2%, and the specific capacity is smaller than that of the hard carbon material prepared by the present invention. From the test results, it can be known that element doping of the carbon raw material can effectively improve the specific capacity of the hard carbon material.
As can be seen from comparison between example 1 and comparative example 2, the hard carbon material prepared without purification had many impurities such as magnetic foreign substances, the first reversible capacity was 407mAh/g, the first efficiency was 78.8%, and the specific capacity was smaller than that of the hard carbon material prepared according to the present invention. From the above test results, it is understood that the specific capacity of the hard carbon material can be effectively improved by purifying the carbonaceous raw material.
Comparing example 1 with comparative example 3, it can be seen that the dosage of the doping source is too low, the first reversible capacity is 411mAh/g, the first efficiency is 80.8%, and the specific capacity is smaller than that of the hard carbon material prepared by the invention. From the above test results, it is understood that the specific capacity of the hard carbon material can be effectively improved by controlling the surfactant-based doping source within the range of the present invention.
Comparing example 1 with comparative example 4, it can be seen that only part of the prepared hard carbon material is effectively doped by doping with the inorganic non-surfactant phosphorus source, the first reversible capacity is 397mAh/g, and the specific capacity is smaller than that of the hard carbon material prepared by the invention. From the above test results, it is understood that the use of the surfactant-based dopant source enables effective element doping and increases the specific capacity of the hard carbon material, as compared with the inorganic dopant source.
As can be seen from Table 1, the hard carbon material prepared by the method provided by the invention can change various parameter indexes of the hard carbon material by adopting different carbonaceous raw materials and doping elements, the first reversible capacity is more than 430mAh/g, and the first efficiency is more than 83%.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A method of preparing a hard carbon material comprising the steps of:
sequentially carrying out first sintering and purification on a carbonaceous raw material to obtain a first precursor;
mixing the first precursor, a surfactant doping source and water, and drying the obtained mixed slurry to obtain a second precursor; the doping element contained in the surfactant doping source is one or more of nitrogen, phosphorus, sulfur and boron; the mass ratio of the carbonaceous raw material to the surfactant doping source is 1:0.05 to 0.55;
and carrying out second sintering on the second precursor to obtain the hard carbon material.
2. The method of claim 1, wherein the surfactant-based dopant source comprises one or more of polyoxyethylene alkylamine, polyoxyethylene alkylamide, alkylpolyoxyethylene ether phosphate, alkylphosphate, alkylsulfonate, alkylsulfate, alkylborate, and alkoxyborate.
3. The method of claim 1, wherein the carbonaceous feedstock comprises one or more of a natural biomass material, a resinous material, and a plant extract.
4. The method according to claim 1, wherein the temperature of the first sintering is 250 to 700 ℃; the heat preservation time of the first sintering is 2-5 h.
5. The method of claim 1, wherein the purifying comprises one or more of water washing, alkali washing, and acid washing.
6. The method of claim 1, further comprising, between the first sintering and the purifying: and carrying out particle shaping on the material obtained after the first sintering.
7. The method according to claim 6, wherein the particle size D50 of the first precursor is 3 to 15 μm.
8. The method according to claim 1, wherein the temperature of the second sintering is 800 to 1500 ℃; the heat preservation time of the second sintering is 2-10 h.
9. The hard carbon material prepared by the preparation method of any one of claims 1 to 8, which comprises a carbonaceous material and doping elements doped on the surface and in pore channels of the carbonaceous material, wherein the doping elements are one or more of nitrogen, phosphorus, sulfur and boron, and the content of the doping elements in the hard carbon material is 0.5 to 5.5wt%; the interlayer spacing of the 002 surface of the hard carbon material is 0.35-0.42 nm.
10. Use of the hard carbon material according to claim 9 in a negative electrode material for a secondary battery.
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