CN114566637A - Preparation method of heteroatom doped silicon-carbon negative electrode material and material thereof - Google Patents
Preparation method of heteroatom doped silicon-carbon negative electrode 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 41
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 20
- 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 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
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- 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
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
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Images
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 of the heteroatom doped silicon-carbon negative electrode material, ball milling treatment is carried out on the silicon powder to realize nanocrystallization, 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 through granulation, and after calcination and crushing, carbon coating and secondary nitrogen or phosphorus homogeneous phase doping are carried out 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 cathode materials, relates to a preparation method of a heteroatom-doped silicon-carbon cathode material, and also relates to a material prepared by the preparation method.
Background
Under the global great trend of energy conservation and emission reduction, under the drive of a carbon neutralization policy, the new energy industry will meet historical opportunities, the electromotion in the traffic field and the industrial field will be a main emission reduction mode, and the development of an energy storage technology directly influences the electromotion process, so that the lithium ion battery with the energy storage potential is widely applied to various electric drive devices or machines such as mobile phones, new energy automobiles and the like. However, with the development of new technologies and the pursuit of customer experience for satisfaction, a new generation of lithium ion battery with high energy, high rate and high safety performance is urgently developed.
At present, graphite carbon materials such as artificial graphite, natural graphite, mesocarbon microbeads, soft carbon, hard carbon and the like are commonly used as negative electrode materials of lithium ion batteries on the market. However, the discharge of the carbon material is lower than the first reversible capacity, and the requirement of people on the long-endurance lithium ion battery is difficult to meet. Therefore, there is a need for a material having a higher reversible capacity than the first time to replace graphite-based materials. The theoretical reversible capacity of the silicon cathode is 4200mAh/g compared with the first reversible capacity, and the reversible capacity is slightly higher than the voltage platform of the graphite cathode, so that lithium cannot be separated out during charging, the silicon cathode has good safety performance, and becomes the most potential material for replacing the graphite cathode. But the volume change of the battery in different degrees occurs in the charging and discharging process, so that the active substance expands and cracks, even separates from a current collector, the electric contact becomes poor, the electrochemical performance fails, finally the reversible capacity of the battery is reduced for the first time, and the service life is greatly reduced.
In order to solve the problem that the volume change of the silicon cathode is large in the charging and discharging process, the technical personnel in the field buffer the volume change of silicon by preparation technologies such as nanocrystallization, compounding with carbon-based materials and metal materials, and the like, so that the silicon cathode can be commercially applied.
Therefore, the development of a low-expansion, high-rate and long-cycle lithium ion battery cathode material and a preparation method thereof are 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 also provides a cathode material prepared by the preparation method of the heteroatom doped silicon-carbon cathode material.
The first technical scheme adopted by the invention is that the preparation method of the heteroatom doped silicon-carbon cathode material specifically comprises the following steps:
step 1, dispersing silicon powder in an organic solvent, adding a dispersing agent and a carbon material, and performing ball milling and crushing to form a 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 in a carbonization furnace, introducing inert gas, and calcining at high temperature to obtain a precursor II;
and 4, crushing the precursor II prepared in the step 3, doping nitrogen and phosphorus elements for the second time and coating an organic carbon source to obtain a precursor III, and crushing the precursor III to obtain the heteroatom-doped silicon-carbon negative electrode material in a grading manner.
The first technical scheme of the invention is also characterized in that:
In step 1, the organic solvent is at least one of liquid alcohols, ketones, alkanes, lipids, ethers and tetrahydrofuran.
In the step 1, the median particle diameter of the nano-silicon in the nano-silicon suspension is 50-500 nm.
In the step 1, the dispersing agent is an anionic surfactant or a nonionic surfactant, and 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, a carbon nanotube, a carbon nanofiber, a carbon nanocage 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 pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea 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 to adopt a spray dryer for drying treatment, wherein 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 disc 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, a mechanical pulverizer or an airflow pulverizer is adopted for pulverizing the precursor II;
and 4, adopting liquid phase coating or solid phase coating for secondary nitrogen and phosphorus element doping and organic carbon source coating in the step 4.
The second technical scheme adopted by the invention is that the heteroatom doped silicon carbon negative electrode material prepared by the preparation method of the heteroatom doped silicon carbon negative electrode material has the median particle size of 3-15 mu m.
The heteroatom doped silicon-carbon negative electrode material has high reversible capacity, namely the reversible capacity is more than 1300mAh/g, and the silicon powder is subjected to nanocrystallization in the preparation process, so that the expansion problem of the silicon powder in the use process is effectively relieved; 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 nitrogen and phosphorus elements in two steps. The preparation method disclosed by the invention is simple in preparation process, green and environment-friendly, easy to control the industrial process, low in industrial cost and easy to realize large-scale production.
Drawings
FIG. 1 is a SEM image of a scanning electron microscope of a material prepared by the method of the invention for preparing a heteroatom-doped silicon-carbon cathode material in example 2;
FIG. 2 is a charge-discharge curve of the material prepared in example 2 in the method for preparing a heteroatom-doped silicon-carbon anode material according to the present invention;
FIG. 3 is a cycle performance curve of the material prepared in example 2 in the method for preparing a heteroatom-doped silicon-carbon anode material according to the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
The preparation method of the heteroatom doped silicon-carbon cathode material comprises the following steps:
step 1, dispersing silicon powder in an organic solvent, adding a dispersing agent and a carbon material, and performing ball milling and crushing to form a nano silicon suspension;
in the step 1, crushing the nano silicon by a sand mill; the median particle diameter of the nano-silicon in the nano-silicon suspension is 50-500 nm.
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, glycerol 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 the step 1, the carbon material comprises 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 5-15% 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 the 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 the combination of at least two of phytic acid, phosphoric acid, sodium hypophosphite, hydroxyethylidene diphosphate and other phosphorus-containing substances; the nitrogen source or the phosphorus source accounts for 1% -10% of the nano silicon in the nano silicon suspension.
In the step 2, the organic carbon source is 1 or the combination of at least 2 of coal pitch, petroleum pitch, 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 rotating speed of the atomizing disc is 12000-25000 rpm/min
Step 3, placing the precursor I in a carbonization furnace, introducing inert gas, and calcining at high temperature to obtain a precursor II;
step 3, the inert gas is 1 or the 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;
and 4, crushing the precursor II, doping nitrogen and phosphorus elements for the second time and coating an organic carbon source to obtain a precursor III, and crushing the precursor III to obtain the heteroatom-doped silicon-carbon negative electrode material by classification.
And 4, crushing the precursor II by adopting a mechanical crusher or a jet mill.
Step 4, secondary nitrogen and phosphorus element doping and organic carbon source coating adopt liquid phase coating or solid phase coating;
the liquid phase coating 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, then carrying out spray drying, putting the obtained spray-dried product into a carbonization furnace, introducing inert gas, and carrying out high-temperature calcination to obtain a precursor III; the organic solvent is one or more of alcohols, ketones, alkanes, lipids, ethers and tetrahydrofuran; the organic carbon source is 1 or at least 2 of coal pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea-formaldehyde resin, and the nitrogen source is one or at least two of organic amines or inorganic ammonium salts such as melamine, urea, ammonium nitrate, urea-formaldehyde resin, polyacrylamide and the like; the phosphorus source is one or the 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 precursor III; the organic carbon source accounts for 5-30% of the precursor III; spray drying adopts a spray dryer, the inlet temperature is 120-200 ℃, and the outlet temperature is 75-120 ℃; the rotating speed of the atomizing disc is 12000-25000 rpm/min; the inert gas is 1 or the 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) efficiently mixing the crushed precursor II with a nitrogen source or a phosphorus source and an organic carbon source, then placing the mixture into a carbonization furnace, introducing inert gas, and carrying out high-temperature calcination to obtain a precursor III. The organic carbon source is 1 or the combination of at least 2 of coal pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea resin, and accounts for 5-30% of the precursor III; the nitrogen source is one or the 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 the 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 precursor III; the high-efficiency mixing adopts a VC mixer, 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 the 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 particle diameter D50 of the heteroatom doped silicon carbon negative electrode material is 3-15 μm.
Example 1
Dispersing silicon powder in ethanol, and adding a dispersing agent polysorbate which accounts for 1% of the nano silicon; the carbon material is graphene accounting for 5% of the nano silicon, and is ground by a sand mill to obtain a nano silicon suspension with a median particle size of 50 nm; sequentially adding urea and coal pitch into the nano-silicon suspension, wherein the urea and the coal pitch respectively account for 1% and 5% of the nano-silicon, and performing spray drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotating speed of the atomizing disc is 15000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 600 ℃, preserving heat for 0.5h, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding urea which accounts for 1% of the precursor II, adding coal pitch which accounts for 30% of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 120 ℃, and the outlet temperature is set to be 80 ℃; and (3) putting the obtained spray-dried product into a box furnace atmosphere furnace at the rotation speed of 15000rpm/min, heating to 1100 ℃ at the speed of 1 ℃/min under a nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor III, crushing the precursor III, and classifying to obtain the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 microns.
Example 2
Dispersing silicon powder in ethanol, and adding a dispersing agent polysorbate which accounts for 1% of the nano silicon; the carbon material is graphene accounting for 5% of the nano silicon, and the nano silicon suspension with the median particle size of 50nm is obtained by grinding the graphene with a sand mill; adding secondary urea and coal pitch into the nano-silicon suspension in sequence, wherein the secondary urea and the coal pitch respectively account for 1% and 5% of the nano-silicon, and performing spray drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotating speed of the atomizing disc is 15000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 600 ℃, preserving heat for 0.5h, increasing the temperature at the rate of 1 ℃/min, and cooling to obtain a precursor II; pulverizing, and mixing with coal pitch and urea (respectively accounting for 30% and 1% of the precursor II) at VC for 30min at a mixing frequency of 30Hz, calcining at 1100 deg.C for 0.5h and at a heating rate of 1 deg.C/min in a box-type atmosphere furnace, and collecting precursor III; and crushing and grading the precursor III to obtain the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 mu m.
Example 3
Dispersing silicon powder in ethanol, and adding a dispersing agent polysorbate which accounts for 1% of the nano silicon; the carbon material is graphene accounting for 5% of the nano silicon, and the nano silicon suspension with the median particle size of 50nm is obtained by grinding the graphene with a sand mill; sequentially adding sodium hypophosphite and coal pitch which respectively account for 1 percent and 5 percent of the nano silicon into the nano silicon suspension, and spray drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotating speed of the atomizing disc is 15000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 600 ℃, preserving heat for 0.5h, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding sodium hypophosphite accounting for 1 percent of the precursor II, adding coal pitch accounting for 30 percent of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 120 ℃, and the outlet temperature is set to be 80 ℃; and (3) putting the obtained spray-dried product into a box furnace atmosphere furnace at the rotation speed of 15000rpm/min, heating to 1100 ℃ at the speed of 1 ℃/min under a nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor III, crushing the precursor III, and classifying to obtain the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 microns.
Example 4
Dispersing silicon powder in ethanol, and adding a dispersing agent polysorbate which accounts for 1% of the nano silicon; the carbon material is graphene accounting for 5% of the nano silicon, and the nano silicon suspension with the median particle size of 50nm is obtained by grinding the graphene with a sand mill; sequentially adding sodium hypophosphite, melamine and coal pitch into the nano silicon suspension, wherein the sodium hypophosphite, the melamine and the coal pitch respectively account for 1%, 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 rotating speed of the atomizing disc is 15000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 600 ℃, preserving heat for 0.5h, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding sodium hypophosphite and melamine which respectively account for 1 percent and 1 percent of the precursor II, adding coal tar which accounts for 30 percent of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 120 ℃, and the outlet temperature is set to be 80 ℃; and (3) putting the obtained spray-dried product into a box furnace atmosphere furnace at the rotation speed of 15000rpm/min, heating to 1100 ℃ at the speed of 1 ℃/min under a nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor III, crushing the precursor III, and classifying to obtain the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 microns.
Example 5
Dispersing silicon powder in ethanol, and adding a dispersing agent polysorbate accounting for 10% of the nano silicon; the carbon material is graphene accounting for 10% of the nano silicon, and the nano silicon suspension with the median particle size of 50nm is obtained by grinding the graphene with a sand mill; sequentially adding sodium hypophosphite and coal pitch into the nano-silicon suspension, wherein the sodium hypophosphite and the coal pitch respectively account for 5% and 10% of the nano-silicon, and performing spray drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotating speed of the atomizing disc is 15000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 600 ℃, preserving heat for 0.5h, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding sodium hypophosphite accounting for 5% of the precursor II, adding coal pitch accounting for 30% of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 120 ℃, and the outlet temperature is set to be 80 ℃; and (3) putting the obtained spray-dried product into a box furnace atmosphere furnace at the rotation speed of 15000rpm/min, heating to 1100 ℃ at the speed of 1 ℃/min under a nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor III, crushing the precursor III, and classifying to obtain the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 microns.
Example 6
Dispersing silicon powder in ethanol, and adding a dispersing agent glycerol which accounts for 10 percent of the nano silicon; the carbon material is a carbon nano tube, accounts for 10% of the nano silicon, and is ground by a sand mill to obtain nano silicon suspension with the median particle size of 50 nm; sequentially adding phytic acid and petroleum asphalt in the nano-silicon suspension, wherein the phytic acid and the petroleum asphalt respectively account for 5% and 10% of the nano-silicon, and performing spray drying to obtain a precursor I; the inlet temperature of spray drying is 120 ℃, and the outlet temperature is 80 ℃; the rotating speed of the atomizing disc is 15000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 600 ℃, preserving heat for 0.5h, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding phytic acid accounting for 5 percent of the precursor II, adding petroleum asphalt accounting for 30 percent of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 120 ℃, and the outlet temperature is set to be 80 ℃; and (3) putting the obtained spray-dried product into a box furnace atmosphere furnace at the rotation speed of 15000rpm/min, heating to 1100 ℃ at the speed of 1 ℃/min under a nitrogen atmosphere, preserving heat for 0.5h, cooling to obtain a precursor III, crushing the precursor III, and classifying to obtain the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 microns.
Example 7
Dispersing silicon powder in ethanol, and adding a dispersing agent glycerol which accounts for 10% of nano silicon; the carbon material is a carbon nano tube, accounts for 10% of the nano silicon, and is ground by a sand mill to obtain nano silicon suspension with the median particle size of 50 nm; sequentially adding phytic acid and petroleum asphalt in the nano-silicon suspension, wherein the phytic acid and the petroleum asphalt respectively account for 5% and 10% of the nano-silicon, and performing spray drying to obtain a precursor I; the inlet temperature of spray drying is 125 ℃, and the outlet temperature is 85 ℃; the rotating speed of the atomizing disc is 25000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 900 ℃, preserving heat for 2 hours, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding phytic acid accounting for 5 percent of the precursor II, adding petroleum asphalt accounting for 30 percent of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 125 ℃, and the outlet temperature is set to be 85 ℃; the rotation speed of an atomizing disc is 25000rpm/min, the obtained spray drying product is placed into a box furnace atmosphere furnace, the temperature is raised to 900 ℃ at the speed of 1 ℃/min under nitrogen atmosphere, the temperature is preserved for 2h, then the temperature is reduced to obtain a precursor III, the precursor III is crushed, and the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 6 microns is obtained through classification.
Example 8
Dispersing silicon powder in ethanol, and adding a dispersing agent glycerol which accounts for 10 percent of the nano silicon; the carbon material is a carbon nano tube, accounts for 10% of the nano silicon, and is ground by a sand mill to obtain nano silicon suspension with the median particle size of 500 nm; sequentially adding phytic acid and petroleum asphalt in the nano-silicon suspension, wherein the phytic acid and the petroleum asphalt respectively account for 5% and 10% of the nano-silicon, and performing spray drying to obtain a precursor I; the inlet temperature of spray drying is 125 ℃, and the outlet temperature is 85 ℃; the rotating speed of the atomizing disc is 25000 rpm/min; placing the precursor I in a box-type atmosphere furnace, introducing nitrogen, calcining at the high temperature of 900 ℃, preserving heat for 2 hours, and obtaining a precursor II at the heating rate of 1 ℃/min; crushing the precursor II, then carrying out liquid phase coating, dispersing the precursor II into ethanol, adding phytic acid accounting for 5 percent of the precursor II, adding petroleum asphalt accounting for 30 percent of the precursor II, uniformly stirring, and then carrying out spray drying, wherein the inlet temperature is set to be 125 ℃, and the outlet temperature is set to be 85 ℃; the rotation speed of an atomizing disc is 25000rpm/min, the obtained spray drying product is placed into a box furnace atmosphere furnace, the temperature is raised to 900 ℃ at the speed of 1 ℃/min under nitrogen atmosphere, the temperature is preserved for 2h, then the temperature is reduced to obtain a precursor III, the precursor III is crushed, and the heteroatom-doped silicon-carbon negative electrode material with the median particle size of 15 mu m is obtained through classification.
Comparative example 1
Compared with the embodiment 1, the nitrogen doping is carried out without adding urea in the whole preparation process of the material, and the others are kept unchanged.
The button cell is assembled by the samples obtained in the above examples 1-8 and comparative example, and the assembling and testing method is as follows: mixing a negative electrode material, a conductive agent and a binder in a solvent according to the 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 the thickness of 8 mu m, drying and cutting to obtain a negative electrode plate; then, a 2025 button cell was assembled by using metallic lithium as a counter electrode, 1mol/L of LiPF6/EC + DMC + EMC (V/V ═ 1:1) electrolyte and Celgard2400 separator. Adopting a LanD battery test system of Wuhanjinuo electronics Limited to carry out normal-temperature test, wherein the test conditions are as follows: the first charge-discharge I is 0.1C, the cycle I is 0.1C, the voltage range is 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 is better than the solid phase coating effect in example 2, and the first efficiency, capacity retention rate at 150 weeks and rate capability are higher; comparing examples 1 and 3, wherein example 1 is nitrogen doped, and example 2 is phosphorus doped, the performance difference is small; comparing examples 1 and 4, the example 4 is simultaneously carried out with nitrogen doping and phosphorus doping, and the first reversible capacity, the capacity retention rate of 150 weeks and the rate performance of the composite material are all superior to those of the example 1; compared with the examples 3 and 5, when the doping amount of phosphorus and the using amount of the carbon material are increased in the example 5, the capacity and rate capability are obviously improved; comparing the examples 6 and 7, when the calcining temperature of the example 7 is reduced from 1100 ℃ to 900 ℃, the first efficiency, the capacity retention rate of 150 weeks and the rate performance are all reduced; comparing the embodiment 7 and the embodiment 8, when the median particle size of the nano silicon is increased to 500nm and the median particle size of the finished material is increased to 15 μm in the embodiment 8, the product capacity is increased, but the first efficiency, the capacity retention rate of 150 weeks and the rate capability are obviously reduced; .
Compared with the embodiment 1, the nitrogen doping step is omitted, the product capacity, the first efficiency, the capacity retention rate of 150 weeks are obviously reduced, and particularly the rate performance is obviously poor.
The heteroatom doped silicon carbon negative electrode material is characterized in that silicon powder is used as a raw material, ball milling is carried out on the silicon powder to realize nanocrystallization, 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 through granulation, and after calcination and crushing, carbon coating and secondary nitrogen or phosphorus homogeneous phase doping are carried out to finally obtain the heteroatom doped silicon carbon negative electrode material.
Claims (10)
1. The preparation method of the heteroatom doped silicon-carbon anode material is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, dispersing silicon powder in an organic solvent, adding a dispersing agent and a carbon material, and performing ball milling and crushing to form a 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 in a carbonization furnace, introducing inert gas, and calcining at high temperature to obtain a precursor II;
and 4, crushing the precursor II prepared in the step 3, doping nitrogen and phosphorus elements for the second time and coating an organic carbon source to obtain a precursor III, and crushing the precursor III to obtain the heteroatom-doped silicon-carbon negative electrode material in a grading manner.
2. The preparation method of the heteroatom doped silicon carbon anode material of claim 1, characterized in that: in the step 1, the organic solvent is at least one of liquid alcohols, ketones, alkanes, lipids, ethers and tetrahydrofuran.
3. The preparation method of the heteroatom-doped silicon-carbon negative electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 1, the median particle diameter of the nano-silicon in the nano-silicon suspension is 50-500 nm.
4. The preparation method of the heteroatom-doped silicon-carbon negative electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: 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.
5. The preparation method of the heteroatom doped silicon carbon anode material of claim 1, characterized in that: in the step 1, the carbon material is at least one of conductive carbon black, conductive graphite, ketjen black, graphene, a carbon nanotube, a carbon nanofiber, a carbon nanocage and porous carbon; the carbon material accounts for 5% -15% of the mass of the nano silicon in the nano silicon suspension.
6. The preparation method of the heteroatom-doped silicon-carbon negative electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: 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 pitch, petroleum pitch, phenolic resin, furfural resin, epoxy resin and urea resin; the organic carbon source accounts for 5-30% of the mass of the nano silicon in the nano silicon suspension.
7. The preparation method of the heteroatom-doped silicon-carbon negative electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: 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 disc is 12000-25000 rpm/min.
8. The preparation method of the heteroatom doped silicon carbon anode material of claim 1, characterized in that: 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.
9. The preparation method of the heteroatom doped silicon carbon anode material of claim 1, characterized in that: in the step 4, a mechanical crusher or a jet mill is adopted for crushing the precursor II;
and 4, adopting liquid phase coating or solid phase coating for secondary nitrogen and phosphorus element doping and organic carbon source coating in the step 4.
10. The heteroatom-doped silicon-carbon negative electrode material prepared by the preparation method of the heteroatom-doped silicon-carbon negative electrode material according to any one of claims 1 to 9, which is characterized in that: the median particle diameter is 3-15 μm.
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