CN112110436B - Preparation method of nitrogen-doped carbon-silicon negative electrode material of lithium ion battery - Google Patents
Preparation method of nitrogen-doped carbon-silicon negative electrode material of lithium ion battery Download PDFInfo
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- CN112110436B CN112110436B CN202010983395.7A CN202010983395A CN112110436B CN 112110436 B CN112110436 B CN 112110436B CN 202010983395 A CN202010983395 A CN 202010983395A CN 112110436 B CN112110436 B CN 112110436B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a nitrogen-doped carbon-silicon negative electrode material of a lithium ion battery, which comprises the steps of carrying out enzymolysis pore-forming on starch by using amylase to prepare porous starch, and carbonizing the porous starch at high temperature to obtain porous carbon; mixing porous carbon, silicon powder and a nitrogen source compound to prepare a silicon/porous carbon @ nitrogen source precursor; the high-capacity Si/C @ NC cathode material is obtained by carrying out a certain synthesis method on the silicon/porous carbon @ nitrogen source precursor, nitrogen doping provides more active sites, diffusion and transfer dynamics of lithium are enhanced, and cycle and rate performance of the cathode material are effectively improved; the preparation method has the advantages of green and environment-friendly raw materials, simple process, easily-controlled process, low energy consumption, no toxicity and no pollution in the production process, belongs to an environment-friendly green process, and is easy for large-scale production and popularization.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a method for preparing a lithium ion battery cathode material by using starch as a raw material and nitrogen-doped carbon silicon.
Background
The high-speed development of new energy automobiles puts higher requirements on the energy density of battery materials; the carbon-silicon cathode material is considered to be one of the lithium ion battery cathode materials leading the future due to the advantages of high specific capacity, abundant resources, low price and the like; however, the silicon material itself has significant disadvantages, such as poor conductivity and poor cyclability due to high expansion rate; and the problems of uniformity problem, fast capacity attenuation, poor conductivity, poor rate performance, complex and time-consuming synthesis process, high material cost, easy environmental pollution and the like of silicon-carbon compounding are not overcome.
Disclosure of Invention
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a nitrogen-doped carbon-silicon negative electrode material of a lithium ion battery comprises the following steps:
(1) placing starch into a container, adding a buffer solution and an amylase solution with proper pH, placing the container on a constant-temperature magnetic stirrer, performing enzymolysis for 8-24 hours at room temperature-60 ℃ to obtain starch milk, filtering and washing the starch milk to obtain a precipitate, drying the precipitate, and grinding to obtain porous starch; placing porous starch in an inert atmosphere, carbonizing at a high temperature in vacuum, preserving heat, and cooling to room temperature to obtain porous carbon;
(2) simultaneously putting porous carbon, silicon powder and a nitrogen source compound into a dispersing agent at the temperature of 50-100 ℃, uniformly mixing for 8-24 h to obtain a mixed solution, and after the solution is evaporated for half, putting the mixed solution into an oven for drying to obtain a silicon/porous carbon @ nitrogen source precursor;
(3) and (3) carrying out a certain synthesis method on the silicon/porous carbon @ nitrogen source precursor to obtain the high-capacity Si/C @ NC negative electrode material.
The starch is one or more of wheat flour, corn flour, potato flour, bean flour and tapioca flour.
The buffer solution is disodium hydrogen phosphate-citric acid buffer solution; the pH value is 4.6-5.8.
The amylase in the amylase liquid is one or more of alpha-amylase, beta-amylase, gamma-amylase and isoamylase in any ratio, and the mass ratio of starch to amylase is 100-10: 1.
The inert gas is argon or nitrogen, the carbonization vacuum degree is 1-50 Pa, the carbonization temperature rise rate is 0.1-5 ℃/min, the carbonization temperature is 500-900 ℃, and the heat preservation time is 1-4 h.
The silicon powder is nano silicon powder or micron silicon powder, and the diameter is 2 nm-5 mu m; the mass ratio of the porous carbon to the silicon powder is 10: 1-10, and the mass ratio of the porous carbon to the nitrogen source compound is 10: 1-10.
The nitrogen source is 2,4, 6-trichlorotriazine, 2,4, 6-triazotriazine, melamine, cyanamide, dicyandiamide, amino compound, benzylamine, N-containing heterocyclic compound, such as polyacrylonitrile, polypyrrole and other polymers, and N-containing precursor (such as NH3, acetonitrile, urea and other nitrogen-containing compounds).
The dispersing agent is one or a mixture of anhydrous ethanol, deionized water, propylene glycol, polyethylene glycol, glycerol, methyl acetate, ethyl acetate, propyl acetate and the like, and the dispersing agent is prepared by mixing the anhydrous ethanol, the deionized water, the propylene glycol, the polyethylene glycol, the glycerol, the methyl acetate, the ethyl acetate, the propyl acetate and the like in a volume ratio of 10-1: 1.
The uniformly mixing method comprises an ultrasonic method, a mechanical stirring method, a vibration method and a magnetic stirring method; the drying temperature of the oven is a constant temperature oven of 40 ℃ to 100 ℃.
The synthesis method comprises different methods such as a template method, a Chemical Vapor Deposition (CVD) method, a hydrothermal method, a solvothermal method, a solid polycondensation reaction and the like.
Compared with the prior art, the method has the advantages that:
according to the invention, nitrogen is successfully doped into the silicon-carbon cathode material, so that the conductivity of the material is effectively improved; meanwhile, porous carbon prepared by starch through enzymolysis pore-forming and carbonization can perfectly encapsulate silicon particles, and the starch frameworks can greatly buffer the volume expansion of silicon in the electrochemical circulation process and effectively inhibit the pulverization of the material. In addition, the preparation method has the advantages of green and environment-friendly raw materials, simple process, easily-controlled process, low energy consumption, no toxicity and no pollution in the production process, belongs to an environment-friendly green process, and is easy for large-scale production and popularization.
Drawings
FIG. 1 is a scanning electron micrograph of a composite prepared in example 1 of the present invention;
FIG. 2 is a graph of the cycle performance of the composite material prepared in example 2 of the present invention
FIG. 3 is a graph showing the first charge and discharge curves of the composite material prepared in example 3 of the present invention;
Detailed Description
The invention provides a preparation method of a nitrogen-doped carbon-silicon cathode material of a lithium ion battery, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
Example 1
(1) Placing 5g of corn starch in a triangular flask, adding 20mL of disodium hydrogen phosphate-citric acid buffer solution with the pH value of 5.2, uniformly stirring and mixing in the triangular flask, placing the triangular flask in a constant-temperature water bath oscillator, adjusting to 55 ℃, uniformly stirring and pretreating for 30min to obtain raw starch slurry; adding 0.3mL (the mass ratio of the alpha-amylase to the beta-amylase is 3:1) of mixed enzyme liquid containing the alpha-amylase and the beta-amylase into raw starch slurry, wherein the mass ratio of starch to the amylase is 100: 1; placing the reaction bottle on a constant-temperature magnetic stirrer with the rotation speed of 180r/min and the temperature of 45 ℃ for enzymolysis reaction for 24 hours, filtering and washing to obtain a precipitate, finally placing the washed precipitate in a constant-temperature drying oven with the temperature of 80 ℃ for about 3 hours, drying and grinding to obtain porous starch; placing porous starch in argon atmosphere, heating to 800 ℃ at the speed of 1 ℃/min, carbonizing at high temperature under the vacuum of 10Pa for 4 hours, and cooling to room temperature to obtain porous carbon;
(2) putting porous carbon, nano silicon powder and urea into a beaker, adding deionized water and absolute ethyl alcohol, wherein the mass ratio of the porous carbon to the nano silicon powder to the urea is 5:1:1, the volume mass ratio of the deionized water to the porous carbon is mL: g is 100:1.5, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, the size of the nano silicon is 20nm, stirring and mixing the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ to obtain a mixed solution, stirring the mixed solution for 8 hours at the stirring speed of 500r/min, and drying the mixed solution in a drying box at the temperature of 80 ℃ to obtain a silicon/porous carbon nitrogen source @ precursor;
(3) and (3) placing the dried silicon/porous carbon @ nitrogen source precursor in an argon atmosphere, carbonizing at the high temperature of 800 ℃ and preserving heat for 4 hours, and cooling to room temperature to obtain the high-capacity Si/C @ NC negative electrode material. The scanning electron micrograph of the composite material is shown in figure 1.
Example 2
(1) Placing 5g of corn starch in a triangular flask, adding 20mL of disodium hydrogen phosphate-citric acid buffer solution with the pH value of 4.5, uniformly stirring and mixing in the triangular flask, placing the triangular flask in a constant-temperature water bath oscillator, adjusting to 55 ℃, uniformly stirring and pretreating for 30min to obtain raw starch slurry; adding 0.3mL (the mass ratio of the alpha-amylase to the beta-amylase is 1:1) of mixed enzyme solution containing the alpha-amylase and the beta-amylase into raw starch slurry, wherein the mass ratio of starch to the amylase is 100: 1; placing the reaction bottle on a constant-temperature magnetic stirrer with the rotation speed of 180r/min and the temperature of 45 ℃ for enzymolysis reaction for 24 hours, filtering and washing to obtain a precipitate, finally placing the washed precipitate in a constant-temperature drying oven with the temperature of 40 ℃ for about 3 hours, drying and grinding to obtain porous starch; placing porous starch in argon atmosphere, heating to 700 ℃ at the speed of 1 ℃/min, carbonizing at high temperature under the vacuum of 10Pa for 4 hours, and cooling to room temperature to obtain porous carbon;
(2) putting porous carbon, nano silicon powder and melamine into a beaker, adding deionized water and absolute ethyl alcohol, wherein the mass ratio of the porous carbon, the nano silicon powder and the melamine is 5:1:1, the volume mass ratio of the deionized water to the porous carbon is mL: g is 100:1.5, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, the size of the nano silicon is 20nm, stirring and mixing the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ to obtain a mixed solution, stirring the mixed solution for 8 hours at the stirring speed of 500r/min, and drying the mixed solution in a drying box at the temperature of 80 ℃ to obtain a silicon/porous carbon nitrogen source @ precursor;
(3) and (3) placing the dried silicon/porous carbon @ nitrogen source precursor in an argon atmosphere, carbonizing at the high temperature of 700 ℃ and preserving heat for 4h, and cooling to room temperature to obtain the high-capacity Si/C @ NC negative electrode material. The cycle performance of the composite material is shown in figure 2.
Example 3
(1) Placing 5g of corn starch in a triangular flask, adding 20mL of disodium hydrogen phosphate-citric acid buffer solution with the pH value of 5, uniformly stirring and mixing in the triangular flask, placing the triangular flask in a constant-temperature water bath oscillator, adjusting to 45 ℃, uniformly stirring and pretreating for 30min to obtain raw starch slurry; adding 0.3mL of alpha-amylase-containing liquid into raw starch slurry, wherein the mass ratio of starch to amylase is 100: 1; placing the reaction bottle on a constant-temperature magnetic stirrer with the rotation speed of 200r/min and the temperature of 45 ℃ for enzymolysis reaction for 24 hours, filtering and washing to obtain a precipitate, finally placing the washed precipitate in a constant-temperature drying oven with the temperature of 40 ℃ for about 3 hours, drying and grinding to obtain porous starch; placing porous starch in argon atmosphere, heating to 650 ℃ at the speed of 1 ℃/min, carbonizing at high temperature under the vacuum of 10Pa for 4 hours, and cooling to room temperature to obtain porous carbon;
(2) putting porous carbon, nano silicon powder and 2,4, 6-trichlorotriazine into a beaker, adding deionized water and absolute ethyl alcohol, wherein the mass ratio of the porous carbon, the nano silicon powder and the 2,4, 6-trichlorotriazine is 5:1:1, the volume mass ratio of the deionized water to the porous carbon is mL: g is 100:1.5, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, the size of nano silicon is 500nm, stirring and mixing the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃ to obtain a mixed solution, stirring for 8 hours at the stirring speed of 500r/min, and drying the mixed solution in a drying box at the temperature of 80 ℃ to obtain a silicon/porous carbon @ nitrogen source precursor;
(3) and (3) placing the dried silicon/porous carbon @ nitrogen source precursor in an argon atmosphere, carbonizing at a high temperature of 650 ℃ and preserving heat for 4 hours, and cooling to room temperature to obtain the high-capacity Si/C @ NC negative electrode material. The first charge-discharge curve of the composite material is shown in figure 3.
Claims (4)
1. A preparation method of a nitrogen-doped carbon-silicon negative electrode material of a lithium ion battery is characterized by comprising the following steps:
(1) placing starch into a container, adding a buffer solution with the pH value of 4.6-5.8 and an amylase solution, placing the container on a constant-temperature magnetic stirrer, performing enzymolysis for 8-24 hours at room temperature-60 ℃ to obtain starch milk, filtering and washing the starch milk to obtain a precipitate, drying the precipitate, and grinding to obtain porous starch; placing porous starch in an inert atmosphere, carbonizing at a high temperature in vacuum, preserving heat, and cooling to room temperature to obtain porous carbon;
(2) simultaneously putting porous carbon, silicon powder and a nitrogen source compound into a dispersing agent at the temperature of 50-100 ℃, uniformly mixing for 8-24 h to obtain a mixed solution, and after the solution is evaporated for half, putting the mixed solution into an oven for drying to obtain a silicon/porous carbon @ nitrogen source precursor;
(3) the high-capacity Si/C @ NC negative electrode material is obtained by carrying out a certain synthesis method on a silicon/porous carbon @ nitrogen source precursor;
the amylase in the amylase liquid in the step (1) is one or more of alpha-amylase, beta-amylase and gamma-amylase, and the mass ratio of starch to amylase is 100-10: 1;
the silicon powder in the step (2) is nano silicon powder or micron silicon powder, and the diameter is 2 nm-5 mu m; the mass ratio of the porous carbon to the silicon powder is 10: 1-10, and the mass ratio of the porous carbon to the nitrogen source compound is 10: 1-10; the nitrogen source is 2,4, 6-trichlorotriazine, 2,4, 6-triazotriazine, melamine, cyanamide, dicyandiamide, phenylmethylamine, the N-containing heterocyclic compound is polyacrylonitrile or polypyrrole, and the N-containing precursor is NH3Acetonitrile and urea;
the synthesis method in the step (3) comprises a template method, a chemical vapor deposition method, a hydrothermal method, a solvothermal method and a solid polycondensation reaction method.
2. The preparation method of the nitrogen-doped carbon-silicon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the starch in the step (1) is one or more of wheat flour, corn flour, potato flour, bean flour and cassava flour; the buffer solution is disodium hydrogen phosphate-citric acid buffer solution.
3. The preparation method of the nitrogen-doped carbon-silicon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the inert gas is argon or nitrogen, the carbonization vacuum degree is 1-50 Pa, the carbonization temperature rise rate is 0.1-5 ℃/min, the carbonization temperature is 500-900 ℃, and the heat preservation time is 1-4 h.
4. The preparation method of the nitrogen-doped carbon-silicon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the dispersing agent is one or a mixture of more of absolute ethyl alcohol, deionized water, propylene glycol, polyethylene glycol, glycerol, methyl acetate, ethyl acetate and propyl acetate, and the dispersing agent is prepared by mixing the absolute ethyl alcohol, the deionized water, the propylene glycol, the polyethylene glycol, the glycerol, the methyl acetate, the ethyl acetate and the propyl acetate in a volume ratio of 10-1: 1; the mixing method comprises an ultrasonic method, a mechanical stirring method and a magnetic stirring method; the drying temperature of the oven is a constant temperature oven of 40 ℃ to 100 ℃.
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