CN114566637B - Preparation method of heteroatom doped silicon-carbon anode material and material thereof - Google Patents
Preparation method of heteroatom doped silicon-carbon anode material and material thereof Download PDFInfo
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 title claims description 28
- 239000000463 material Substances 0.000 title description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 35
- 238000001694 spray drying Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 107
- 239000005543 nano-size silicon particle Substances 0.000 claims description 79
- 239000000725 suspension Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
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- 238000010438 heat treatment Methods 0.000 claims description 22
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011294 coal tar pitch Substances 0.000 claims description 15
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- 239000007791 liquid phase Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 9
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- 229910021389 graphene Inorganic materials 0.000 claims description 8
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- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 239000011300 coal pitch Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
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- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
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- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical group 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002091 nanocage Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- 229940080350 sodium stearate Drugs 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 12
- 238000007709 nanocrystallization Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010426 asphalt Substances 0.000 description 9
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- 230000002441 reversible effect Effects 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 229910052743 krypton Inorganic materials 0.000 description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052754 neon Inorganic materials 0.000 description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
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- 229910021384 soft carbon Inorganic materials 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
Abstract
The invention discloses a preparation method of a heteroatom doped silicon-carbon negative electrode material, which is characterized in that silicon powder is used as a raw material for ball milling treatment to realize nanocrystallization, then the silicon powder is subjected to homogeneous phase compounding with a nitrogen source or a phosphorus source and a carbon material by a spray drying method, powder particles are obtained by granulation, and after calcination and crushing, carbon coating and secondary nitrogen or phosphorus homogeneous phase doping are performed to finally obtain the heteroatom doped silicon-carbon negative electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, relates to a preparation method of a heteroatom doped silicon-carbon anode material, and also relates to a material prepared by the preparation method.
Background
Under the general trend of global energy conservation and emission reduction, the new energy industry is driven by a carbon neutralization policy to meet historical opportunities, the electric drive in the traffic field and the industrial field is a main emission reduction mode, the development of energy storage technology directly influences the electric drive process, and the new energy industry is widely applied to various electric drive equipment or machines such as mobile phones, new energy automobiles and the like as a lithium ion battery with the current energy storage potential. However, with the development of new technologies and the pursuit of customer experience on satisfaction, a new generation of lithium ion batteries with high energy, high multiplying power and high safety performance is urgently developed.
At present, graphite carbon materials such as artificial graphite, natural graphite, mesophase carbon microspheres, soft carbon, hard carbon and the like are widely used as negative electrode materials of lithium ion batteries in the market. However, the discharge ratio of the carbon material is lower than the first reversible capacity, and the requirement of people on a long-endurance lithium ion battery is difficult to meet. Therefore, a material having a higher reversible capacity than the first is needed to replace the graphite-based material. The theoretical ratio of the silicon negative electrode to the first reversible capacity 4200mAh/g is slightly higher than that of the graphite negative electrode voltage platform, so that lithium can not be separated out during charging, and the silicon negative electrode has good safety performance and becomes the material which has the highest potential of replacing the graphite negative electrode. However, the volume of the battery changes to different degrees in the charge and discharge process, so that the active material is expanded and broken, even separated from a current collector, the electrical contact is poor, the electrochemical performance is invalid, and finally the reversible first reversible capacity of the battery is reduced, and the service life is greatly reduced.
In order to solve the problem of large volume change of the silicon cathode in the charge and discharge process, the volume change of silicon is buffered by the preparation technology of nanocrystallization, compounding with carbon-based materials, metal materials and the like by a person skilled in the art, so that the silicon cathode can be commercially applied.
Therefore, developing a low-expansion, high-rate and long-cycle lithium ion battery anode material and a preparation method thereof are the problems to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a heteroatom doped silicon-carbon anode material, and the anode material prepared by the method has the characteristics of low expansion, high multiplying power and long cycle.
The invention further provides a negative electrode material prepared by the method for preparing the heteroatom doped silicon carbon negative electrode material.
The first technical scheme adopted by the invention is that the preparation method of the heteroatom doped silicon-carbon anode material specifically comprises the following steps:
step 1, silicon powder is dispersed in an organic solvent, a dispersing agent and a carbon material are added, and ball milling and grinding are carried out to form nano silicon suspension;
step 2, adding a nitrogen source or a phosphorus source and an organic carbon source into the nano silicon suspension prepared in the step 1, and drying to obtain a precursor I;
step 3, placing the precursor I prepared in the step 2 into a carbonization furnace, introducing inert gas, and calcining at a high temperature to obtain a precursor II;
and 4, crushing the precursor II prepared in the step 3, carrying out secondary nitrogen and phosphorus element doping and organic carbon source cladding to obtain a precursor III, and then crushing and grading the precursor III to obtain the heteroatom doped silicon carbon anode material.
The first technical scheme of the invention is characterized in that:
in the step 1, the organic solvent is at least one of liquid alcohols, ketones, alkanes, lipids, ethers and tetrahydrofuran.
In the step 1, the median diameter of the nano silicon in the nano silicon suspension is 50-500nm.
In the step 1, the dispersing agent is an anionic surfactant or a nonionic surfactant, and the dispersing agent is at least one of sodium stearate, sodium dodecyl benzene sulfonate, polysorbate, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, glycerol and pentaerythritol; the dispersing agent accounts for 1-50% of the mass of the nano silicon in the nano silicon suspension.
In the step 1, the carbon material is at least one of conductive carbon black, conductive graphite, ketjen black, graphene, carbon nanotubes, carbon nanofibers, carbon nanocages and porous carbon; the carbon material accounts for 5-15% of the mass of the nano silicon in the nano silicon suspension.
In the step 2, the nitrogen source is ammonium salt; the phosphorus source is at least one of phytic acid, phosphoric acid, sodium hypophosphite and hydroxyethylidene diphosphate; the nitrogen source or the phosphorus source accounts for 1-10% of the mass of the nano silicon in the nano silicon suspension;
the organic carbon source is at least one of coal tar pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea formaldehyde resin; the organic carbon source accounts for 5-30% of the mass of the nano silicon in the nano silicon suspension.
In the step 2, the drying process is that a spray dryer is adopted for drying treatment, the inlet temperature of the spray dryer is 120-200 ℃, and the outlet temperature of the spray dryer is 75-120 ℃; the rotation speed of the atomizing disk is 12000-25000 rpm/min.
In the step 3, the inert gas is at least one of nitrogen, helium, neon, argon, krypton or xenon; the carbonization furnace is a box-type atmosphere furnace or a rotary furnace or a roller kiln; the high-temperature calcination temperature is 600-1100 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 0.5-5 h.
In the step 4, the precursor II is crushed by a mechanical crusher or an air flow crusher;
and (4) doping secondary nitrogen and phosphorus elements and coating an organic carbon source in the step (4) by adopting liquid phase coating or solid phase coating.
The second technical scheme adopted by the invention is that the heteroatom doped silicon-carbon anode material prepared by the heteroatom doped silicon-carbon anode material preparation method has a median particle diameter of 3-15 mu m.
The heteroatom doped silicon-carbon anode material has the beneficial effects that the heteroatom doped silicon-carbon anode material has higher reversible capacity, namely the reversible capacity is more than 1300mAh/g, and silicon powder is subjected to nanocrystallization in the preparation process, so that the expansion problem in the use process is effectively relieved; and secondly, a carbon source is added in the sanding process, so that the conductivity between single-particle nano-silicon is further enhanced, the improvement of electrochemical performance and the reduction of expansion are facilitated, the cycle performance of the lithium ion battery is greatly improved, and in addition, the multiplying power performance of the material is enhanced through the doping of two-step nitrogen and phosphorus elements. The preparation method has the advantages of simple preparation process, environment friendliness, easy control of industrial process, low industrial cost and easy realization of large-scale production.
Drawings
FIG. 1 is a SEM image of a material prepared in example 2 of the method for preparing a heteroatom-doped silicon-carbon negative electrode material of the present invention;
FIG. 2 is a charge-discharge curve of the material prepared in example 2 in the method for preparing a heteroatom-doped silicon-carbon negative electrode material of the present invention;
FIG. 3 is a graph showing the cycle performance of the material prepared in example 2 in the method for preparing a heteroatom-doped silicon-carbon negative electrode material of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The preparation method of the heteroatom doped silicon carbon anode material comprises the following steps:
step 1, silicon powder is dispersed in an organic solvent, a dispersing agent and a carbon material are added, and ball milling and grinding are carried out to form nano silicon suspension;
in the step 1, nano silicon is crushed by a sand mill; the median diameter of the nano silicon in the nano silicon suspension is 50-500nm.
In the step 1, the organic solvent is one or more of liquid alcohols, ketones, alkanes, lipids, ethers and tetrahydrofuran.
In the step 1, the dispersing agent is an anionic surfactant or a nonionic surfactant, including but not limited to sodium stearate, sodium dodecyl benzene sulfonate, polysorbate, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, glycerin and pentaerythritol, or a combination of at least two of the above; the dispersing agent accounts for 1-50% of the mass of the nano silicon in the nano silicon suspension.
In step 1, the carbon material includes, but is not limited to, one or a mixture of at least two of conductive carbon black, conductive graphite, ketjen black, graphene, carbon nanotubes, carbon nanofibers, carbon nanocages, and porous carbon; the carbon material accounts for 5 to 15 percent of the mass of the nano silicon in the nano silicon suspension.
Step 2, adding a nitrogen source or a phosphorus source and an organic carbon source into the nano silicon suspension, and drying to obtain a precursor I;
in the step 2, the nitrogen source is one or a combination of at least two of organic amine or inorganic ammonium salts such as melamine, urea, ammonium nitrate, urea-formaldehyde resin, polyacrylamide and the like; the phosphorus source is one or a combination of at least two of phosphorus-containing substances such as phytic acid, phosphoric acid, sodium hypophosphite, hydroxyethylidene diphosphate and the like; the nitrogen source or the phosphorus source accounts for 1 to 10 percent of the nano silicon in the nano silicon suspension.
In the step 2, the organic carbon source is coal pitch, petroleum pitch, 1 or at least 2 of phenolic resin, furfural resin, epoxy resin and urea resin; the organic carbon source accounts for 5 to 30 percent of the nano silicon in the nano silicon suspension
In the step 2, a spray dryer is adopted for drying treatment, the inlet temperature is 120-200 ℃, and the outlet temperature is 75-120 ℃; the rotation speed of the atomizing disk is 12000-25000 rpm/min
Step 3, placing the precursor I in a carbonization furnace, introducing inert gas, and calcining at a high temperature to obtain a precursor II;
step 3, the inert gas is 1 or at least 2 of nitrogen, helium, neon, argon, krypton or xenon; the carbonization furnace is a box-type atmosphere furnace or a rotary furnace or a roller kiln; the high-temperature calcination temperature is 600-1100 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 0.5-5 h;
and 4, after the precursor II is crushed, secondary nitrogen and phosphorus element doping and organic carbon source cladding are carried out to obtain a precursor III, and then the precursor III is crushed and graded to obtain the heteroatom doped silicon-carbon anode material.
And 4, crushing the precursor II by adopting a mechanical crusher or an air flow crusher.
Step 4, secondary nitrogen and phosphorus element doping and organic carbon source coating are carried out by adopting liquid phase coating or solid phase coating;
the liquid phase cladding is carried out in the following way: dispersing the crushed precursor II into an organic solution, adding a nitrogen source or a phosphorus source and an organic carbon source, uniformly stirring, performing spray drying, placing the obtained spray dried product into a carbonization furnace, introducing inert gas, and performing high-temperature calcination to obtain a precursor III; the organic solution is one or more of alcohols, ketones, alkanes, lipids, ethers and tetrahydrofuran; the organic carbon source is coal pitch, petroleum pitch, 1 or a combination of at least 2 of phenolic resin, furfural resin, epoxy resin and urea-formaldehyde resin, and the nitrogen source is one or a combination of at least two of organic amine or inorganic ammonium salt such as melamine, urea, ammonium nitrate, urea-formaldehyde resin and polyacrylamide; the phosphorus source is one or a combination of at least two of phosphorus-containing substances such as phytic acid, phosphoric acid, sodium hypophosphite, hydroxyethylidene diphosphate and the like; the nitrogen source or the phosphorus source accounts for 1% -10% of the precursor III; the organic carbon source accounts for 5% -30% of the precursor III; spray drying is carried out by adopting a spray dryer, wherein the inlet temperature is 120-200 ℃, and the outlet temperature is 75-120 ℃; the rotating speed of the atomizing disk is 12000-25000 rpm/min; the inert gas is 1 or a combination of at least 2 of nitrogen, helium, neon, argon, krypton or xenon; the carbonization furnace is a box-type atmosphere furnace or a rotary furnace or a roller kiln; the high-temperature calcination temperature is 600-1100 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 0.5-5 h.
The solid phase coating is carried out in the following way: and (3) mixing the crushed precursor II with a nitrogen source or a phosphorus source and an organic carbon source efficiently, then placing the mixture into a carbonization furnace, introducing inert gas, and calcining at a high temperature to obtain a precursor III. The organic carbon source is coal pitch, petroleum pitch, 1 or a combination of at least 2 of phenolic resin, furfural resin, epoxy resin and urea resin, and the organic carbon source accounts for 5-30% of the precursor III; the nitrogen source is one or a combination of at least two of organic amine or inorganic ammonium salt such as melamine, urea, ammonium nitrate, urea formaldehyde resin, polyacrylamide and the like; the phosphorus source is one or a combination of at least two of phosphorus-containing substances such as phytic acid, phosphoric acid, sodium hypophosphite, hydroxyethylidene diphosphate and the like; the nitrogen source or the phosphorus source accounts for 1% -10% of the precursor III; a VC mixer is adopted for efficient mixing, the mixing frequency is 15-40Hz, and the mixing time is 10-60 minutes; the carbonization furnace is a box-type atmosphere furnace or a rotary furnace or a roller kiln; the inert gas is 1 or a combination of at least 2 of nitrogen, helium, neon, argon, krypton or xenon; the high-temperature calcination temperature is 600-1100 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 0.5-5 h.
In the step 4, the median diameter D50 of the heteroatom doped silicon carbon anode material is 3-15 mu m.
Example 1
Silicon powder is dispersed in ethanol, and a dispersing agent polysorbate is added to account for 1% of nano silicon; the carbon material is graphene accounting for 5% of nano silicon, and grinding treatment is carried out by a sand mill to obtain nano silicon suspension with the median particle diameter of 50 nm; sequentially adding urea and coal tar pitch into the nano silicon suspension, wherein the urea and the coal tar pitch respectively account for 1% and 5% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotation speed of the atomizing disk is 15000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 600 ℃, preserving heat for 0.5h, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding urea accounting for 1% of the precursor II, adding coal pitch accounting for 30% of the precursor II, uniformly stirring, then spray-drying, and setting the inlet temperature to 120 ℃ and the outlet temperature to 80 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace, heating to 1100 ℃ at 1 ℃/min under nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor, obtaining a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 2
Silicon powder is dispersed in ethanol, and a dispersing agent polysorbate is added to account for 1% of nano silicon; the carbon material is graphene accounting for 5% of nano silicon, and grinding treatment is carried out by a sand mill to obtain nano silicon suspension with the median particle diameter of 50 nm; adding urea and coal tar pitch into the nano silicon suspension in sequence, wherein the urea and the coal tar pitch respectively account for 1% and 5% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotation speed of the atomizing disk is 15000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 600 ℃, preserving heat for 0.5h, heating at a rate of 1 ℃/min, and cooling to obtain a precursor II; pulverizing, mixing with coal tar pitch and urea (30% and 1% of precursor II) respectively, mixing at a frequency of 30Hz for 30min, calcining at 1100deg.C for 0.5 hr under nitrogen in a box-type atmosphere furnace, and heating at a rate of 1deg.C/min to obtain precursor III; and (3) crushing and grading the precursor III to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 3
Silicon powder is dispersed in ethanol, and a dispersing agent polysorbate is added to account for 1% of nano silicon; the carbon material is graphene accounting for 5% of nano silicon, and grinding treatment is carried out by a sand mill to obtain nano silicon suspension with the median particle diameter of 50 nm; sequentially adding sodium hypophosphite and coal tar pitch into the nano silicon suspension, wherein the sodium hypophosphite and the coal tar pitch respectively account for 1% and 5% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotation speed of the atomizing disk is 15000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 600 ℃, preserving heat for 0.5h, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding sodium hypophosphite accounting for 1% of the precursor II, adding coal tar pitch accounting for 30% of the precursor II, uniformly stirring, and then spray-drying, wherein the inlet temperature is 120 ℃, and the outlet temperature is 80 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace, heating to 1100 ℃ at 1 ℃/min under nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor, obtaining a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 4
Silicon powder is dispersed in ethanol, and a dispersing agent polysorbate is added to account for 1% of nano silicon; the carbon material is graphene accounting for 5% of nano silicon, and grinding treatment is carried out by a sand mill to obtain nano silicon suspension with the median particle diameter of 50 nm; sequentially adding sodium hypophosphite, melamine and coal tar pitch into the nano silicon suspension, wherein the sodium hypophosphite, the melamine and the coal tar pitch respectively account for 1 percent, 1 percent and 5 percent of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotation speed of the atomizing disk is 15000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 600 ℃, preserving heat for 0.5h, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding sodium hypophosphite and melamine which respectively account for 1% and 1% of the precursor II, adding coal pitch which accounts for 30% of the precursor II, uniformly stirring, then spray-drying, and setting the inlet temperature to 120 ℃ and the outlet temperature to 80 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace, heating to 1100 ℃ at 1 ℃/min under nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor, obtaining a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 5
Silicon powder is dispersed in ethanol, and a dispersing agent polysorbate is added to account for 10% of nano silicon; the carbon material is graphene accounting for 10% of nano silicon, and grinding treatment is carried out by a sand mill to obtain nano silicon suspension with the median particle diameter of 50 nm; sequentially adding sodium hypophosphite and coal tar pitch into the nano silicon suspension, wherein the sodium hypophosphite and the coal tar pitch respectively account for 5% and 10% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotation speed of the atomizing disk is 15000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 600 ℃, preserving heat for 0.5h, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding sodium hypophosphite accounting for 5% of the precursor II, adding coal tar pitch accounting for 30% of the precursor II, uniformly stirring, and then spray-drying, wherein the inlet temperature is 120 ℃, and the outlet temperature is 80 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace, heating to 1100 ℃ at 1 ℃/min under nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor, obtaining a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 6
Silicon powder is dispersed in ethanol, and dispersant glycerol accounting for 10% of nano silicon is added; the carbon material is carbon nano tube, accounting for 10% of nano silicon, grinding treatment is carried out by using a sand mill, and nano silicon suspension with the median particle diameter of 50nm is obtained; sequentially adding sub-phytic acid and petroleum asphalt into the nano silicon suspension, wherein the sub-phytic acid and the petroleum asphalt respectively account for 5% and 10% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotation speed of the atomizing disk is 15000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 600 ℃, preserving heat for 0.5h, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding phytic acid accounting for 5% of the precursor II, adding petroleum asphalt accounting for 30% of the precursor II, uniformly stirring, and then spray-drying, wherein the inlet temperature is 120 ℃, and the outlet temperature is 80 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace, heating to 1100 ℃ at 1 ℃/min under nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor, obtaining a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 7
Silicon powder is dispersed in ethanol, and dispersant glycerol accounting for 10% of nano silicon is added; the carbon material is carbon nano tube, accounting for 10% of nano silicon, grinding treatment is carried out by using a sand mill, and nano silicon suspension with the median particle diameter of 50nm is obtained; sequentially adding sub-phytic acid and petroleum asphalt into the nano silicon suspension, wherein the sub-phytic acid and the petroleum asphalt respectively account for 5% and 10% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 125 ℃, and the outlet temperature is 85 ℃; the rotation speed of the atomizing disk is 25000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 900 ℃, preserving heat for 2 hours, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding phytic acid accounting for 5% of the precursor II, adding petroleum asphalt accounting for 30% of the precursor II, uniformly stirring, and then spray-drying, wherein the inlet temperature is set to be 125 ℃, and the outlet temperature is set to be 85 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace at the speed of 25000rpm/min, heating to 900 ℃ at the speed of 1 ℃/min under nitrogen atmosphere, preserving heat for 2 hours, cooling to obtain a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 6 mu m.
Example 8
Silicon powder is dispersed in ethanol, and dispersant glycerol accounting for 10% of nano silicon is added; the carbon material is carbon nano tube, accounting for 10% of nano silicon, grinding treatment is carried out by using a sand mill, and nano silicon suspension with the median particle diameter of 500nm is obtained; sequentially adding sub-phytic acid and petroleum asphalt into the nano silicon suspension, wherein the sub-phytic acid and the petroleum asphalt respectively account for 5% and 10% of the nano silicon, and spray-drying to obtain a precursor I; the inlet temperature of spray drying is 125 ℃, and the outlet temperature is 85 ℃; the rotation speed of the atomizing disk is 25000rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at a high temperature of 900 ℃, preserving heat for 2 hours, and heating at a rate of 1 ℃/min to obtain a precursor II; crushing a precursor II, then coating a liquid phase, dispersing the precursor II into ethanol, adding phytic acid accounting for 5% of the precursor II, adding petroleum asphalt accounting for 30% of the precursor II, uniformly stirring, and then spray-drying, wherein the inlet temperature is set to be 125 ℃, and the outlet temperature is set to be 85 ℃; placing the obtained spray-dried product into a box furnace atmosphere furnace at the speed of 25000rpm/min, heating to 900 ℃ at the speed of 1 ℃/min under nitrogen atmosphere, preserving heat for 2 hours, cooling to obtain a precursor III, then crushing the precursor III, and grading to obtain the heteroatom doped silicon-carbon anode material with the median particle diameter of 15 mu m.
Comparative example 1
Compared with example 1, urea is not added for nitrogen doping during the whole preparation process of the material, and the others are kept unchanged.
The samples obtained in examples 1 to 8 and comparative example were assembled into button cells, and the assembly test method was as follows: mixing a negative electrode material, a conductive agent and a binder in a solvent according to a mass percentage of 93:1.5:5.5, controlling the solid content of slurry to be 48%, coating the slurry on a copper foil current collector with a thickness of 8 mu m, drying, and cutting to obtain a negative electrode plate; then, a 2025 button cell was assembled with lithium metal as a counter electrode, 1mol/L LiPF6/ec+dmc+emc (V/v=1:1:1) electrolyte, celgard2400 separator. The method adopts a LAND battery test system of the Wuhan Jinno electronics limited company to test at normal temperature, and the test conditions are as follows: first charge and discharge i=0.1C, cycle i=0.1C, voltage range 0.005-2.0Vvs Li/li+. The test results are shown in table 1;
TABLE 1
As can be seen from table 1 above, in comparative examples 1 and 2, the liquid phase coating effect in example 1 was better than the solid phase coating effect in example 2, and the initial efficiency, 150-week capacity retention rate and rate capability were higher; comparative examples 1,3, example 1 was nitrogen doped and example 2 was phosphorus doped, the performance difference was not great compared to the two; comparing examples 1 and 4, example 4 is simultaneously doped with nitrogen and phosphorus, and the first reversible capacity, 150-week capacity retention rate and rate capability are superior to those of example 1; comparing examples 3 and 5, when the doping amount of phosphorus and the amount of carbon material are increased in example 5, the capacity and the rate performance are obviously improved; comparing examples 6 and 7, when example 7 was conducted to lower the calcination temperature from 1100 ℃ to 900 ℃, the first efficiency, 150-week capacity retention, and rate performance were all lowered; comparing examples 7 and 8, when the median particle diameter of the nano silicon is increased to 500nm in example 8, the median particle diameter of the finished product material is increased to 15 mu m, but the first efficiency, the 150-week capacity retention rate and the multiplying power performance are obviously reduced; .
Comparative example 1 compared with example 1, the nitrogen doping step was omitted, the product capacity, the first efficiency, the 150-week capacity retention rate, the rate performance degradation was remarkable, and particularly the rate performance was remarkably deteriorated.
The preparation method of the heteroatom doped silicon-carbon negative electrode material is characterized in that silicon powder is used as a raw material, ball milling treatment is carried out on the silicon powder to realize nanocrystallization, then the silicon powder, a nitrogen source or a phosphorus source and a carbon material are subjected to homogeneous phase compounding through a spray drying method, powder particles are obtained through granulation, and after calcination and crushing, carbon cladding and secondary nitrogen or phosphorus homogeneous phase doping are carried out, finally the heteroatom doped silicon-carbon negative electrode material is obtained, and the heteroatom doped silicon-carbon negative electrode material has high first reversible capacity, excellent multiplying power charge and discharge performance, low expansion and long cycle life, and in addition, the preparation process is simple, the industrial cost is low, and the large-scale production is easy to realize.
Claims (2)
1. The preparation method of the heteroatom doped silicon carbon anode material is characterized by comprising the following steps of: the method specifically comprises the following steps:
step 1, silicon powder is dispersed in an organic solvent, a dispersing agent and a carbon material are added, and ball milling and grinding are carried out to form nano silicon suspension;
in the step 1, the organic solvent is liquid alcohol;
in the step 1, the median particle diameter of the nano silicon in the nano silicon suspension is 50-500nm;
in the step 1, the dispersing agent is at least one of sodium stearate, sodium dodecyl benzene sulfonate, polysorbate, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, glycerin and pentaerythritol; the dispersing agent accounts for 1-10% of the mass of the nano silicon in the nano silicon suspension;
in the step 1, the carbon material is at least one of conductive carbon black, conductive graphite, ketjen black, graphene, carbon nanotubes, carbon nanofibers, carbon nanocages and porous carbon; the carbon material accounts for 5-10% of the mass of the nano silicon in the nano silicon suspension;
step 2, adding an organic carbon source and a nitrogen source or a phosphorus source into the nano-silicon suspension prepared in the step 1, and drying to obtain a precursor I;
in the step 2, the nitrogen source is ammonium salt; the phosphorus source is at least one of phytic acid, phosphoric acid, sodium hypophosphite and hydroxyethylidene diphosphate; the nitrogen source or the phosphorus source accounts for 1-5% of the mass of the nano silicon in the nano silicon suspension;
the organic carbon source is at least one of coal tar pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea formaldehyde resin; the organic carbon source accounts for 5-10% of the mass of the nano silicon in the nano silicon suspension;
in the step 2, the drying process is that a spray dryer is adopted for drying treatment, the inlet temperature of the spray dryer is 120-125 ℃, and the outlet temperature of the spray dryer is 80-85 ℃; the rotating speed of the atomizing disk is 15000-25000 rpm/min;
step 3, placing the precursor I prepared in the step 2 into a carbonization furnace, introducing nitrogen, and calcining at a high temperature to obtain a precursor II;
in the step 3, the carbonization furnace is a box-type atmosphere furnace or a rotary furnace or a roller kiln; the high-temperature calcination temperature is 600-900 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 0.5-2 h;
step 4, after the precursor II prepared in the step 3 is crushed, secondary nitrogen and phosphorus element doping and organic carbon source cladding are carried out to obtain a precursor III, and then the precursor III is crushed and graded to obtain the heteroatom doped silicon carbon anode material;
in the step 4, the precursor II is crushed by a mechanical crusher or an air flow crusher;
the secondary nitrogen and phosphorus element doping and the organic carbon source coating in the step 4 adopt liquid phase coating;
the liquid phase cladding is carried out in the following manner: dispersing the crushed precursor II into an organic solvent, adding an organic carbon source and a nitrogen source or a phosphorus source, uniformly stirring, performing spray drying, placing the obtained spray dried product into a carbonization furnace, introducing nitrogen, and performing high-temperature calcination to obtain a precursor III; the organic solvent is alcohols; the organic carbon source is at least one of coal pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea-formaldehyde resin, and the nitrogen source is at least one of melamine, urea, ammonium nitrate, urea-formaldehyde resin and polyacrylamide; the phosphorus source is at least one of phytic acid, phosphoric acid, sodium hypophosphite and hydroxyethylidene diphosphate; the nitrogen source or the phosphorus source accounts for 1% -5% of the precursor III; the organic carbon source accounts for 30% of the precursor III; spray drying is carried out by adopting a spray dryer, wherein the inlet temperature is 120-125 ℃, and the outlet temperature is 80-85 ℃; the rotating speed of the atomizing disk is 15000-25000 rpm/min; the carbonization furnace is a box-type atmosphere furnace or a rotary furnace or a roller kiln; the high-temperature calcination temperature is 900-1100 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 0.5-2 h.
2. The heteroatom-doped silicon-carbon anode material prepared by the method for preparing the heteroatom-doped silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: the median particle diameter is 3-15 μm.
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