CN111403744A - Nitrogen-containing silicon oxygen carbon compound composite negative electrode material of lithium ion secondary battery and preparation method - Google Patents
Nitrogen-containing silicon oxygen carbon compound composite negative electrode material of lithium ion secondary battery and preparation method Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-containing silicon oxygen carbon compound composite negative electrode material of a lithium ion secondary battery, which comprises the following steps: stirring and mixing a silica precursor, a carbon source and a nitrogen source in an acidic aqueous solution to form slurry; drying the slurry, roasting at high temperature under protective gas, cooling, crushing and scattering to obtain a carbonized nitrogen-containing porous silicon oxygen carbon compound prepolymer; and blending the obtained nitrogen-containing porous silicon-oxygen carbide precursor and a carbon coating material, and carrying out high-temperature carbonization, cooling, crushing and scattering under protective gas to obtain the uniform and stable coating structure of the nitrogen-containing silicon-oxygen carbide composite negative electrode material of the lithium ion secondary battery. The composite negative electrode material containing the nitrogen-silicon oxygen carbon compound of the lithium ion secondary battery prepared by the preparation method has good negative electrode material conductivity and cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of a lithium ion secondary battery and a preparation method thereof.
Background
Compared with the traditional lithium ion negative electrode material carbon-based negative electrode material (maximum theoretical specific capacity 372mAh/g), the lithium ion secondary battery silicon-based negative electrode material has higher theoretical specific capacity, wherein the maximum theoretical specific capacity of the silicon simple substance negative electrode material reaches 4200mAh/g, the maximum theoretical specific capacity of the silicon-oxygen negative electrode material also reaches 2100mAh/g, the specific capacity is far greater than that of the carbon-based negative electrode material, and the lithium ion secondary battery silicon-based negative electrode material has higher commercial value and development prospect.
Although the silicon-based material has a huge capacity advantage compared with a carbon-based material, the defects are very obvious, and the main defects of the silicon-based material are represented by large cyclic expansion and poor conductivity, wherein the expansion rate of the silicon single substance negative electrode material can reach more than 300%, and the expansion rate of the silicon-oxygen negative electrode material is close to 200%, so that the silicon-based material is very easy to pulverize and fall off, the capacity is reduced, the service life is shortened, and the commercialization of the silicon-based negative electrode material is seriously influenced when the silicon-based material is used as the negative electrode material of the lithium ion secondary battery in the cyclic use process.
Compared with a silicon simple substance material, the silicon-oxygen material used as the lithium ion battery cathode material has a relatively small expansion rate, and the main reason is that oxygen in the silicon-oxygen cathode material is easy to react with lithium ions to generate a stable lithium silicate compound (L i)2O，Li4SiO4) The expansion of the silicon-oxygen cathode material can be effectively controlled and relieved, and the cycle performance of the silicon-oxygen cathode material is improved to a certain extent. Therefore, silicon oxide materials have been widely studied as negative electrode materials for lithium ion secondary batteries.
Therefore, the composite negative electrode material containing the nitrogen-containing silicon-oxygen-carbon compound of the lithium ion secondary battery and the preparation method are provided.
Disclosure of Invention
The invention mainly aims to provide a nitrogen-containing silicon oxygen carbon compound composite negative electrode material of a lithium ion secondary battery and a preparation method thereof, and the composite negative electrode material has the advantages of improving the conductivity and the cycle performance of the negative electrode material.
In order to realize the purpose, the invention provides a preparation method of a nitrogen-containing silicon oxygen carbon compound composite negative electrode material of a lithium ion secondary battery, which comprises the following steps:
stirring and mixing a silica precursor, a carbon source and a nitrogen source in an acidic aqueous solution to form slurry;
and (2) drying the slurry obtained in the step (1), roasting at high temperature under protective gas, cooling, crushing and scattering to obtain the carbonized nitrogen-containing porous silicon-oxygen-carbon compound prepolymer. Wherein, the cooling is naturally cooling to room temperature; the material is crushed and scattered, and the median particle size of the material D50 is 1-20 μm.
And (3) blending the nitrogen-containing porous silicon-oxygen carbide precursor obtained in the step (2) with a carbon coating material, carbonizing at high temperature under protective gas, cooling, crushing and scattering to obtain the uniform and stable coating structure-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery, wherein the particle size median diameter D50 of the obtained nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery is 1-80 mu m. Wherein, the high-temperature baking, cooling, crushing and scattering in the step (3) are the same as those in the step (2).
Preferably, the silicon oxide precursor in step (1) is one or more hydrolyzable silicon oxides such as silicon tetrachloride, ethyl orthosilicate, trimethylhydroxysilane, trimethylmethoxysilane, aminopropyltriethoxysilane, silane coupling agents and the like.
Preferably, the carbon source in step (1) is one or more carbon-based polymers or compounds with functional groups, such as citric acid, polyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyquaternium, and the like.
Preferably, the nitrogen source in step (1) is one or more compounds or polymers containing nitrogen and having functional groups, such as melamine, polyacrylamide, polyethyleneimine, polyvinylamine, acetamide, formamide, p-aminobenzoic acid, amino acid, acrylamide, urea, isocyanate, carbamate, and the like.
Preferably, the pH value of the acidic aqueous solution in the step (1) is controlled to be 1-6, and the acidic aqueous solution is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the hydrolysis and reaction speed of the raw materials are controlled by adjusting the pH value of the acidic aqueous solution.
Preferably, the stirring in the step (1) is magnetic stirring, mechanical stirring, ultrasonic mixing or heating stirring, the reaction temperature is controlled to be 20-120 ℃, and the hydrolysis and reaction speed are adjusted by adjusting the reaction temperature.
Preferably, the slurry drying in the step (2) is to wash the materials with pure water and then dry the materials at the temperature of 80-120 ℃, and the drying equipment is a vacuum oven or a blast air box; the protective gas is one or more of nitrogen, argon, helium, neon and xenon; the high-temperature roasting device is a box furnace, a roller kiln, a rotary kiln or a heating kettle, the temperature is set to be 600-1500 ℃, and the roasting time is 5-48 hours. Preferably, the temperature is set to be 800-1200 ℃, and the roasting time is 6-24 h. The heating rate is 0.1-20 ℃/min, preferably 0.5-15 ℃/min.
Preferably, the carbon-coated material in step (3) is obtained by mixing one or more of coal tar pitch, petroleum pitch, starch, polyvinyl chloride, glucose, epoxy resin, polystyrene, phenolic resin, urea resin, polyurethane, polythiophene, polyhydric alcohols and the like and performing high-temperature treatment. Preferably, the coal tar pitch, the petroleum pitch, the starch, the glucose and the like are obtained by mixing one or more of coal tar pitch, petroleum pitch, starch and glucose and performing high-temperature treatment, and the coal tar pitch, the petroleum pitch, the starch, the glucose and the like are powdery, and the particle size is 10-1000 μm, preferably 100-500 μm.
Preferably, the addition mass ratio of the nitrogen-containing porous silicon oxycarbide prepolymer to the carbon coating material is 1: 0.05-1: 1; more preferably 1:0.1 to 1: 0.8.
The composite negative electrode material of the lithium ion secondary battery prepared by the preparation method comprises a nitrogen-containing silicon-oxygen-carbon compound, wherein the structure of the nitrogen-containing silicon-oxygen-carbon compound is a core-shell structure with a carbon-nitrogen compound as a shell and a silicon-oxygen compound as a core, the carbon shell is uniformly coated on the surface of the silicon-oxygen compound, and nitrogen elements are uniformly dispersed in the middle or inside of the carbon shell.
Preferably, the particle size median diameter D50 of the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery is 1-80 μm, the first reversible capacity is not lower than 1580mAh/g, the first coulombic efficiency is greater than 76%, the capacity retention rate is greater than 90% after 50 weeks of circulation, the expansion rate is less than 45%, and the conductivity is greater than 3.5S/m.
Compared with the prior art, the invention has the following beneficial effects:
1. the structure of the material prepared by the invention is a core-shell structure taking a carbon nitride compound as a shell and silicon oxide as a core; the carbon-based material and the silica precursor are uniformly dispersed in the aqueous solvent by utilizing the action of hydrogen bonds or chemical bonds, and a foundation is laid for generating a stable coating layer uniformly in situ; the composite negative electrode material containing the nitrogen silicon oxygen carbon compound and being uniformly and stably coated is generated by an in-situ method, and is modified by a carbon-based coating material to generate the composite negative electrode material with a stable and uniform core-shell structure, so that the conductivity and the cycle performance of the composite negative electrode material are greatly improved;
2. by utilizing the action of hydrogen bonds or chemical bonds, when nitrogen is introduced, nitrogen-containing compounds can be uniformly dispersed in the material, and a foundation is laid for uniformly improving the conductivity of the material; the carbon coating material is adopted, so that the surface performance of the material can be obviously improved, the specific surface of the material is reduced, and meanwhile, a double-layer carbon coating layer is formed, so that the conductivity and the cycle performance of the material are obviously improved;
3. and the preparation method is simple, low in cost and pollution-free.
Drawings
Fig. 1 is a scanning electron microscope atlas of the nitrogen-containing silicon oxygen carbon compound composite negative electrode material of the lithium ion secondary battery prepared in example 1.
Fig. 2 is a graph of conductivity data for example 1, example 2, and comparative example 1 at different compaction densities.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
Dissolving tetraethyl orthosilicate in an aqueous solution, wherein the mass ratio of the tetraethyl orthosilicate to water is 1:5, adding hydrochloric acid to adjust the pH to 2, heating in a water bath and mechanically stirring, setting the temperature to be 60 ℃, the stirring speed to be 200rpm, stirring for 30min, then adding citric acid, keeping the molar ratio of the tetraethyl orthosilicate to the citric acid at 1:0.5, the temperature and the stirring speed unchanged, stirring for 120min, adding melamine, keeping the molar ratio of the tetraethyl orthosilicate to the melamine at 1:0.2, keeping the temperature and the stirring speed unchanged, stirring for 120min, and after the reaction is finished, drying in an oven at the drying temperature of 80 ℃. Placing the dried material into a box-type furnace for roasting at the roasting temperature of 1000 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a semi-finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing, demagnetizing and sieving the material to obtain a material with the median particle size (D50) of 1-80 mu m, mixing the material and phenolic resin in a VC manner, wherein the mixing speed is 1000rpm, the time is 3h, the mass ratio of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material to the phenolic resin is 1:0.02, placing the mixed material into the box-type furnace for roasting, the roasting temperature is 800 ℃, the protection of nitrogen atmosphere, the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing the material, and (3) demagnetizing and sieving to obtain a material with the particle size median diameter (D50) of 1-80 mu m, namely the nitrogen-silicon-oxygen-carbon containing composite negative electrode material of the lithium ion secondary battery.
Example 2
Dissolving tetraethyl orthosilicate in an aqueous solution, wherein the mass ratio of the tetraethyl orthosilicate to water is 1:5, adding hydrochloric acid to adjust the pH to 2, heating in a water bath and mechanically stirring, setting the temperature to be 60 ℃, the stirring speed to be 200rpm, stirring for 30min, then adding citric acid, keeping the molar ratio of the tetraethyl orthosilicate to the citric acid at 1:0.8, the temperature and the stirring speed unchanged, stirring for 120min, adding melamine, keeping the molar ratio of the tetraethyl orthosilicate to the melamine at 1:0.4, keeping the temperature and the stirring speed unchanged, stirring for 120min, and after the reaction is finished, drying in an oven at the drying temperature of 80 ℃. Placing the dried material into a box-type furnace for roasting at the roasting temperature of 1000 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a semi-finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing, demagnetizing and sieving the material to obtain a material with the median particle size (D50) of 1-80 mu m, mixing the material and phenolic resin in a VC manner, wherein the mixing speed is 1000rpm, the time is 3h, the mass ratio of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material to the phenolic resin is 1:0.02, placing the mixed material into the box-type furnace for roasting, the roasting temperature is 800 ℃, the protection of nitrogen atmosphere, the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing the material, and (3) demagnetizing and sieving to obtain a material with the particle size median diameter (D50) of 1-80 mu m, namely the nitrogen-silicon-oxygen-carbon containing composite negative electrode material of the lithium ion secondary battery.
Example 3
Dissolving tetraethyl orthosilicate in an aqueous solution, wherein the mass ratio of the tetraethyl orthosilicate to water is 1:5, adding hydrochloric acid to adjust the pH to 2, heating in a water bath and mechanically stirring, setting the temperature to be 60 ℃, the stirring speed to be 200rpm, the stirring time to be 30min, then adding citric acid, keeping the molar ratio of the tetraethyl orthosilicate to the citric acid to be 1:1, the temperature and the stirring speed unchanged, stirring for 120min, adding melamine, keeping the molar ratio of the tetraethyl orthosilicate to the melamine to be 1:0.6, keeping the temperature and the stirring speed unchanged, stirring for 120min, and after the reaction is finished, drying in an oven at the drying temperature of 80 ℃. Placing the dried material into a box-type furnace for roasting at the roasting temperature of 1000 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a semi-finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing, demagnetizing and sieving the material to obtain a material with the median particle size (D50) of 1-80 mu m, mixing the material and phenolic resin in a VC manner, wherein the mixing speed is 1000rpm, the time is 3h, the mass ratio of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material to the phenolic resin is 1:0.02, placing the mixed material into the box-type furnace for roasting, the roasting temperature is 800 ℃, the protection of nitrogen atmosphere, the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing the material, and (3) demagnetizing and sieving to obtain a material with the particle size median diameter (D50) of 1-80 mu m, namely the nitrogen-silicon-oxygen-carbon containing composite negative electrode material of the lithium ion secondary battery.
Example 4
Dissolving silicon tetrachloride in an aqueous solution, wherein the mass ratio of the silicon tetrachloride to water is 1:5, adding hydrochloric acid to adjust the pH to 2, heating in a water bath, mechanically stirring in a water bath manner at the temperature of 60 ℃, at the stirring speed of 200rpm for 30min, then adding polyacrylic acid, wherein the molar ratio of the silicon tetrachloride to the polyacrylic acid is 1:0.5, the temperature and the stirring speed are unchanged, stirring for 120min, adding polyacrylamide, keeping the molar ratio of the silicon tetrachloride to the polyacrylamide at the temperature of 1:0.2, stirring for 120min, and after the reaction is finished, drying in an oven at the drying temperature of 80 ℃. Placing the dried material into a box-type furnace for roasting at the roasting temperature of 1000 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a semi-finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing, demagnetizing and sieving the material to obtain a material with the median particle size (D50) of 1-80 mu m, mixing the material and phenolic resin in a VC manner, wherein the mixing speed is 1000rpm, the time is 3h, the mass ratio of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material to the phenolic resin is 1:0.02, placing the mixed material into the box-type furnace for roasting, the roasting temperature is 800 ℃, the protection of nitrogen atmosphere, the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing the material, and (3) demagnetizing and sieving to obtain a material with the particle size median diameter (D50) of 1-80 mu m, namely the nitrogen-silicon-oxygen-carbon containing composite negative electrode material of the lithium ion secondary battery.
Example 5
Dissolving trimethyl methoxy silane in an aqueous solution, wherein the mass ratio of trimethyl methoxy silane to water is 1:5, adding hydrochloric acid to adjust the pH value to 2, heating in a water bath and mechanically stirring, setting the temperature at 60 ℃, stirring at 200rpm for 30min, then adding polyacrylic acid, wherein the molar ratio of trimethyl methoxy silane to polyacrylic acid is 1:0.8, the temperature and the stirring speed are unchanged, stirring for 120min, then adding p-aminobenzoic acid, wherein the molar ratio of trimethyl methoxy silane to p-aminobenzoic acid is 1:0.4, keeping the temperature and the stirring speed unchanged, stirring for 120min, and after the reaction is finished, drying in an oven at 80 ℃. Placing the dried material into a box-type furnace for roasting at the roasting temperature of 1000 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a semi-finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing, demagnetizing and sieving the material to obtain a material with the median particle size (D50) of 1-80 mu m, mixing the material and phenolic resin in a VC manner, wherein the mixing speed is 1000rpm, the time is 3h, the mass ratio of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material to the phenolic resin is 1:0.02, placing the mixed material into the box-type furnace for roasting, the roasting temperature is 800 ℃, the protection of nitrogen atmosphere, the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing the material, and (3) demagnetizing and sieving to obtain a material with the particle size median diameter (D50) of 1-80 mu m, namely the nitrogen-silicon-oxygen-carbon containing composite negative electrode material of the lithium ion secondary battery.
Example 6
Dissolving aminopropyltriethoxysilane in an aqueous solution, wherein the mass ratio of the aminopropyltriethoxysilane to water is 1:5, adding hydrochloric acid to adjust the pH to 2, heating in a water bath and mechanically stirring, setting the temperature to 60 ℃, stirring at the speed of 200rpm for 30min, adding polyacrylic acid, keeping the molar ratio of the aminopropyltriethoxysilane to the polyacrylic acid at 1:1, the temperature and the stirring speed unchanged, stirring for 120min, adding amino acid, keeping the molar ratio of the aminopropyltriethoxysilane to the amino acid at 1:0.6, keeping the temperature and the stirring speed unchanged, stirring for 120min, and after the reaction is finished, drying in an oven at the drying temperature of 80 ℃. Placing the dried material into a box-type furnace for roasting at the roasting temperature of 1000 ℃ under the protection of nitrogen atmosphere, wherein the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a semi-finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing, demagnetizing and sieving the material to obtain a material with the median particle size (D50) of 1-80 mu m, mixing the material and phenolic resin in a VC manner, wherein the mixing speed is 1000rpm, the time is 3h, the mass ratio of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material to the phenolic resin is 1:0.02, placing the mixed material into the box-type furnace for roasting, the roasting temperature is 800 ℃, the protection of nitrogen atmosphere, the heating rate is 3 ℃/min, preserving heat for 6h, cooling to obtain a finished product of the nitrogen-containing silicon-oxygen-carbon composite negative electrode material, crushing the material, and (3) demagnetizing and sieving to obtain a material with the particle size median diameter (D50) of 1-80 mu m, namely the nitrogen-silicon-oxygen-carbon containing composite negative electrode material of the lithium ion secondary battery.
Comparative example 1
VC mixing is carried out on silicon monoxide and phenolic resin according to the mass ratio of 1:0.04, the mixing rotating speed is 1000rpm, the time is 4 hours, the mixed material is placed into a box-type furnace for roasting, the roasting temperature is 800 ℃, the nitrogen atmosphere is protected, the heating rate is 3 ℃/min, the temperature is kept for 6 hours, the silicon-oxygen-carbon composite negative electrode material is obtained after cooling, the material is crushed, demagnetized and sieved, and the material with the median particle size (D50) of 1-80 mu m is obtained, namely the silicon-oxygen-carbon composite negative electrode material for the lithium ion secondary battery.
Comparative example 2
Performing VC mixing on silicon monoxide, phenolic resin and melamine according to the mass ratio of 1:0.04:0.02, wherein the mixing rotation speed is 1000rpm, the time is 4 hours, placing the mixed material into a box-type furnace for roasting, the roasting temperature is 800 ℃, the nitrogen atmosphere is protected, the heating rate is 3 ℃/min, keeping the temperature for 6 hours, cooling to obtain a silicon-oxygen-carbon composite negative electrode material, and crushing, demagnetizing and sieving the material to obtain the silicon-oxygen-carbon composite negative electrode material of the lithium ion secondary battery, wherein the particle size median particle diameter (D50) of the material is 1-80 mu m.
The negative electrode materials of examples 1-6 and comparative examples 1-2 were tested, and the particle size range and distribution of the materials were tested using a Malvern laser particle size tester MS 3000; the specific surface area of the material is tested by adopting Tristar3000 full-automatic specific surface area and porosity analysis of American Michel instruments; the material structure was tested using an X-ray diffractometer X' Pert Pro, PANALYTICAL.
Observing the appearance, the particle size and the like of a sample by adopting a scanning electron microscope of Hitachi S4800; the particle size and surface condition of the material are clearly reflected in fig. 1, indicating the modified morphology of the material.
Testing the conductivity of the material by adopting MCP-PD51 powder conductivity testing equipment of Mitsubishi chemical company of Japan; the variation in conductivity of different materials and the conductivity of different materials at the same compaction density is clearly reflected in fig. 2.
The electrochemical cycle performance is tested by the following method, a negative electrode material, a conductive agent and a binder are mixed in a solvent according to a mass ratio of 92:2:6, the solid content is controlled to be 55%, the mixture is coated on a copper foil current collector and dried to obtain a negative electrode plate, then a conventional positive electrode plate, L iPF6/EC + DMC (V/V is 1:1) electrolyte of 1 mol/L and a Ce L gard2400 diaphragm are utilized, a 18650 cylindrical battery is assembled by a shell through a conventional production process, constant-current charging and discharging are carried out under the multiplying power of 1C, and the charging and discharging voltage is limited to 2.75-4.2V.
The electrochemical test results and the expansion ratio test results of the negative electrode materials prepared in examples 1 to 6 and comparative examples 1 and 2 are shown in table 1:
by combining the electrochemical test results and the expansion rate test in examples 1 to 6, as can be seen from table 1, the particle size median diameter D50 of the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary batteries obtained in examples 1 to 6 is 1 to 80 μm, the first reversible capacity is not lower than 1580mAh/g, the first coulombic efficiency is greater than 76%, the capacity retention rate after 50 weeks of circulation is greater than 90%, the expansion rate is lower than 45%, and the conductivity is greater than 3.5S/m.
In contrast, comparative example 1 and comparative example 2 are insufficient in capacity, cycle performance, expansion rate, conductivity, and the like, respectively. Compared with comparative examples 1 and 2, the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery prepared by the preparation method disclosed by the invention has the advantages that the expansion rate is low and the guiding performance is excellent under the condition that the high capacity is ensured to be unchanged.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a nitrogen-containing silicon oxygen carbon compound composite negative electrode material of a lithium ion secondary battery is characterized by comprising the following steps:
stirring and mixing a silica precursor, a carbon source and a nitrogen source in an acidic aqueous solution to form slurry;
drying the slurry obtained in the step (1), roasting at high temperature under protective gas, cooling, crushing and scattering to obtain a carbonized nitrogen-containing porous silicon-oxygen-carbon compound prepolymer;
and (3) blending the nitrogen-containing porous silicon-oxygen carbide precursor obtained in the step (2) with a carbon coating material, and carrying out high-temperature carbonization, cooling, crushing and scattering under protective gas to obtain the uniform and stable coating structure of the nitrogen-containing silicon-oxygen carbide compound composite negative electrode material of the lithium ion secondary battery.
2. The method for preparing the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery as claimed in claim 1, wherein the silicon-oxygen precursor in the step (1) is one or more hydrolyzable silicon oxides such as silicon tetrachloride, ethyl orthosilicate, trimethylhydroxysilane, trimethylmethoxysilane, aminopropyltriethoxysilane, silane coupling agent, and the like.
3. The method for preparing the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery according to claim 1, wherein the carbon source in the step (1) is one or more carbon-based polymers or compounds with functional groups, such as citric acid, polyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyquaternary ammonium salt and the like.
4. The method for preparing the nitrogen-containing silicon oxycarbide compound composite anode material for the lithium ion secondary battery according to claim 1, wherein the nitrogen source in the step (1) is one or more compounds or polymers containing nitrogen elements and having functional groups, such as melamine, polyacrylamide, polyethyleneimine, polyvinylamine, acetamide, formamide, p-aminobenzoic acid, amino acid, acrylamide, urea, isocyanate and carbamate.
5. The preparation method of the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery according to claim 1, wherein the pH value of the acidic aqueous solution in the step (1) is controlled to be 1-6, and the acidic aqueous solution is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the hydrolysis and reaction speed of the raw materials are controlled by adjusting the pH value of the acidic aqueous solution; in the step (1), the stirring is magnetic stirring, mechanical stirring, ultrasonic mixing or heating stirring, and the reaction temperature is controlled to be 20-120 ℃.
6. The preparation method of the nitrogen-containing silicon oxygen carbon compound composite anode material for the lithium ion secondary battery according to claim 1, wherein the step (2) of drying the slurry is to dry the material at 80-120 ℃ after washing the material with pure water, and the drying equipment is a vacuum oven or a blast air box; the protective gas is one or more of nitrogen, argon, helium, neon and xenon; the high-temperature roasting device is a box furnace, a roller kiln, a rotary kiln or a heating kettle, the temperature is set to be 600-1500 ℃, and the roasting time is 5-48 hours.
7. The method for preparing the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery according to claim 1, wherein the carbon coating material in the step (3) is obtained by mixing one or more of coal tar pitch, petroleum pitch, starch, polyvinyl chloride, glucose, epoxy resin, polystyrene, phenolic resin, urea resin, polyurethane, polythiophene, polyhydric alcohols and the like and performing high-temperature treatment.
8. The method for preparing the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material of the lithium ion secondary battery according to claim 1, wherein the addition mass ratio of the nitrogen-containing porous silicon-oxygen-carbon compound prepolymer to the carbon coating material is 1: 0.05-1: 1.
9. The composite negative electrode material of the nitrogen-containing silicon-oxygen-carbon compound for the lithium ion secondary battery prepared by the preparation method of any one of claims 1 to 8 is characterized by comprising the nitrogen-containing silicon-oxygen-carbon compound, wherein the structure of the nitrogen-containing silicon-oxygen-carbon compound is a core-shell structure with a carbon-nitrogen compound as a shell and a silicon-oxygen compound as a core, the carbon shell is uniformly coated on the surface of the silicon-oxygen compound, and nitrogen elements are uniformly dispersed in the middle or inside of the carbon shell.
10. The nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material for the lithium ion secondary battery as claimed in claim 9, wherein the particle size median diameter D50 of the nitrogen-containing silicon-oxygen-carbon compound composite negative electrode material for the lithium ion secondary battery is 1-80 μm, the first reversible capacity is not less than 1580mAh/g, the first coulombic efficiency is greater than 76%, the capacity retention rate after 50 weeks of circulation is greater than 90%, the expansion rate is less than 45%, and the conductivity is greater than 3.5S/m.
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