CN113860288B - Silicon-carbon nanotube composite negative electrode material and preparation method and application thereof - Google Patents

Silicon-carbon nanotube composite negative electrode material and preparation method and application thereof Download PDF

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CN113860288B
CN113860288B CN202111308277.7A CN202111308277A CN113860288B CN 113860288 B CN113860288 B CN 113860288B CN 202111308277 A CN202111308277 A CN 202111308277A CN 113860288 B CN113860288 B CN 113860288B
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carbon nanotube
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CN113860288A (en
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刘双科
许静
郝紫勋
李宇杰
孙巍巍
郑春满
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National University of Defense Technology
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Abstract

The invention discloses a silicon-carbon nanotube composite negative electrode material and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly, taking nano silicon powder, resorcinol, formaldehyde and the like as raw materials, reacting under heating and stirring to generate phenolic resin, and coating the phenolic resin on the surface of a nano silicon; then grinding or ball-milling and mixing the phenolic aldehyde coated silicon particles with high-boiling-point mineral oil, melamine, cobalt salt solution and the like to form a muddy mixture, placing the muddy mixture in an inert atmosphere for heat treatment, carbonizing the phenolic resin, the melamine and the high-boiling-point mineral oil at high temperature, heating cobalt ions in the inert atmosphere to reduce the cobalt ions into metal cobalt, and growing carbon nanotubes in situ under the catalysis of the metal cobalt; and finally, removing the nano metal cobalt by acid washing to obtain the silicon-carbon nanotube composite material. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process and capability of realizing mass preparation. When the cathode material is used as a cathode material of a lithium ion battery, the electrochemical activity and the cycling stability can be effectively improved.

Description

Silicon-carbon nanotube composite negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of battery materials, in particular to a silicon-carbon nanotube composite negative electrode material and a preparation method and application thereof.
Background
Silicon as the negative electrode material of the lithium ion battery has the highest theoretical specific capacity of 4200mAh/g, and the silicon has low lithium intercalation potential (< 0.5V vs Li) and abundant reserves, so the silicon is considered as the most ideal negative electrode material of the next generation of lithium ion batteries. However, silicon itself has very low electronic conductivity and poor electrochemical activity. And the volume expansion of the silicon negative electrode after lithium insertion can reach 300%, and a large stress can be generated by a large volume expansion effect, so that the silicon negative electrode material is pulverized, the contact between active materials is poor, the active materials are separated from a current collector, and the capacity is rapidly attenuated. In addition, the volume expansion effect of the silicon negative electrode also causes that a stable solid electrolyte interface (SEI film) is difficult to form on the surface of the silicon negative electrode, and the specific capacity, the stability, the coulombic efficiency and the like of the silicon negative electrode are seriously influenced.
Disclosure of Invention
The invention provides a silicon-carbon nanotube composite negative electrode material, and a preparation method and application thereof, which are used for overcoming the defects of low electrochemical activity, volume expansion effect and the like of a silicon negative electrode in the prior art.
In order to achieve the purpose, the invention provides a preparation method of a silicon-carbon nanotube composite negative electrode material, which comprises the following steps:
s1: adding nano silicon powder into a mixed solution containing a surfactant, stirring, performing ultrasonic treatment, sequentially adding resorcinol and formaldehyde solution, heating, stirring, filtering, washing and drying to obtain precursor powder of phenolic aldehyde coated silicon; the mixed solution consists of water, alcohol and ammonia water;
s2: mixing the precursor powder with mineral oil and melamine, then adding a cobalt salt solution, grinding or ball-milling and uniformly mixing to form a muddy mixture, and placing the muddy mixture in an inert atmosphere for heat treatment to obtain sintered powder;
s3: and (3) placing the sintered powder in an acidic aqueous solution for washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
In order to achieve the purpose, the invention also provides a silicon-carbon nanotube composite anode material which is prepared by the preparation method; the cathode material consists of carbon-coated nano silicon and in-situ grown carbon nanotubes and is in a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; the carbon-coated nano silicon is dispersed in the three-dimensional network structure.
In order to achieve the purpose, the invention also provides an application of the silicon-carbon nanotube composite negative electrode material, and the negative electrode material prepared by the preparation method or the negative electrode material is applied to a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the silicon-carbon nanotube composite cathode material comprises the steps of firstly, taking nano silicon powder, resorcinol, formaldehyde and the like as raw materials, reacting the resorcinol and the formaldehyde under heating and stirring to generate phenolic resin, and coating the phenolic resin on the surface of the nano silicon to form phenolic coated silicon; then grinding or ball-milling and mixing the phenolic aldehyde coated silicon particles with high-boiling-point mineral oil, melamine, cobalt salt solution and the like to form a muddy mixture, placing the muddy mixture in an inert atmosphere for heat treatment, cracking and carbonizing the phenolic resin, the melamine and the high-boiling-point mineral oil at high temperature, heating the muddy mixture in the inert atmosphere, reducing cobalt ions into metal cobalt, and growing carbon nanotubes in situ under the catalysis of the metal cobalt; and finally, removing the nano metal cobalt by acid washing to obtain the silicon-carbon nanotube composite material. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process and capability of realizing mass preparation.
2. The silicon-carbon nanotube composite cathode material provided by the invention consists of carbon-coated nano silicon and in-situ grown carbon nanotubes, and is in a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; the carbon-coated nano silicon is dispersed in the carbon nano tube three-dimensional network structure. The carbon layer is coated on the surface of the active silicon nano particle, so that the electronic conductivity of the silicon cathode can be improved, and the structural damage caused by volume expansion is inhibited, so that the electrochemical activity and the stability of the silicon cathode are improved; the carbon nano tube has good conductivity and mechanical property, and forms a three-dimensional conductive network structure by compounding with the silicon particles, so that on one hand, the conductivity among the silicon particles is improved, the rate capability is improved, and on the other hand, the volume expansion and contraction effects of the silicon negative electrode material can be effectively inhibited, thereby improving the stability of a solid electrolyte interface (SEI film). When the cathode material is used as a cathode material of a lithium ion battery, the electrochemical activity and the cycling stability can be effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a silicon-carbon nanotube composite material in example 1 of the present invention;
fig. 2 is a cycle performance curve diagram of a lithium ion battery assembled by the silicon-carbon nanotube composite material and the silicon-superconducting carbon and silicon-carbon nanotubes in example 1 of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific indication.
The invention provides a preparation method of a silicon-carbon nanotube composite negative electrode material, which is characterized by comprising the following steps of:
s1: adding nano silicon powder into a mixed solution containing a surfactant, stirring, performing ultrasonic treatment, sequentially adding resorcinol and formaldehyde solution, heating, stirring, filtering, washing and drying to obtain precursor powder of phenolic aldehyde coated silicon; the mixed solution is composed of water, alcohol and ammonia water.
The surfactant is added to disperse the nano-silicon more uniformly, so that the phenolic resin is coated more uniformly.
The mixed solution consists of water, alcohol and ammonia water, and the resorcinol and the formaldehyde can react to generate the phenolic resin in the environment and slowly and uniformly coat the surface of the nanometer silicon.
Preferably, the molar ratio of the resorcinol to the formaldehyde is 1 (1-2), and the reaction is more uniform under the condition of the ratio; the mass ratio of the nano silicon powder to the resorcinol is (0.2-20): 1, and the carbon content coated on the surface of the nano silicon is controlled by controlling the ratio; the ratio of the nano silicon powder to the mixed solution is (0.01-0.5) g:100ml, and the nano silicon is dispersed more uniformly under the condition of the ratio; the mass ratio of the surfactant to the mixed solution is (0.1-2) to 100, so that the nano silicon is dispersed more uniformly; the volume ratio of the alcohol to the water in the mixed solution is (50-1): 1, and the volume ratio of the ammonia water to the water is 1: (1-20).
Preferably, the surfactant is at least one of dodecyltrimethyl ammonium bromide, dodecyltrimethyl ammonium bromide and polyvinylpyrrolidone.
Preferably, the particle size of the nano silicon powder is 30-300 nm, and the electrochemical performance of the negative electrode material under the particle size is more excellent.
Preferably, the heating and stirring temperature is 20-80 ℃, and the time is 12-36 h.
S2: and mixing the precursor powder with mineral oil and melamine, then adding a cobalt salt solution, grinding or ball-milling and uniformly mixing to form a muddy mixture, and placing the muddy mixture in an inert atmosphere for heat treatment to obtain sintered powder.
Besides carbonization, the mineral oil has certain fluidity, so that the cobalt salt can be dispersed more uniformly.
Preferably, the mass ratio of the precursor powder to the mineral oil is (0.02-0.2): 1, which is favorable for forming a uniform semi-solid pasty mixture; the mass ratio of the precursor powder to the melamine is (0.01-0.2): 1, and the content of the carbon nano tube is controlled by controlling the proportional relation.
Preferably, the mineral oil is at least one of paraffin oil, kerosene, diesel oil, lubricating oil and liquid asphalt; the cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; the inert atmosphere is Ar gas and N 2 Gas and Ar/H 2 At least one of the mixed gas of (1).
Preferably, the temperature of the heat treatment is 500-1000 ℃ and the time is 1-5 h.
S3: and (3) placing the sintered powder in an acidic aqueous solution for washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
Preferably, the acid in the acidic aqueous solution is at least one of hydrochloric acid, sulfuric acid and nitric acid, and the mass fraction of the acid in the acidic aqueous solution is 10-30 wt%.
The invention also provides a silicon-carbon nanotube composite cathode material which is prepared by the preparation method; the cathode material consists of carbon-coated nano silicon and in-situ grown carbon nanotubes and has a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; the carbon-coated nano silicon is dispersed in the three-dimensional network structure.
Preferably, the particle size of the nano-silicon is 30-300 nm, the diameter of the in-situ grown carbon nano-tube is 10-200 nm, and the length of the in-situ grown carbon nano-tube is 0.5-20 mu m.
The invention also provides an application of the silicon-carbon nanotube composite negative electrode material, and the negative electrode material prepared by the preparation method or the negative electrode material is applied to a lithium ion battery.
The silicon-carbon nanotube composite material is used as the lithium ion battery cathode, and the mass fraction of silicon in the silicon-carbon nanotube composite cathode material is 40-90 wt%.
Example 1
The embodiment provides a silicon-carbon nanotube composite negative electrode material, which consists of carbon-coated nano silicon and in-situ grown carbon nanotubes and has a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; carbon-coated nano-silicon is dispersed within the three-dimensional network structure. The grain diameter of the nano-silicon is 30-80 nm, the pipe diameter of the in-situ grown carbon nano-tube is 10-50 nm, and the length is 1-10 mu m.
The embodiment also provides a preparation method of the silicon-carbon nanotube composite anode material, which comprises the following steps:
(1) Adding 0.50g of nano silicon powder (with the particle size of 30-80 nm) into a mixed solution of 40ml of water containing 0.1g of dodecyl trimethyl ammonium bromide, 360ml of ethanol and 4ml of ammonia water, stirring, ultrasonically dispersing uniformly, then adding 0.6g of resorcinol until the resorcinol is dissolved, finally adding 0.8g of formaldehyde solution, stirring and reacting at 30 ℃ for 24 hours, filtering, washing and drying to obtain precursor powder of phenolic aldehyde coated silicon;
(2) Grinding and mixing 0.15g of precursor powder, 2g of paraffin oil and 3g of melamine uniformly, then adding 5ml of ethanol solution containing 0.15g of cobalt nitrate, continuously grinding uniformly to form a pasty mixture, keeping the temperature of the mixture at 900 ℃ for 2 hours in a high-purity Ar atmosphere, and naturally cooling to obtain black powder;
(3) And (3) placing the obtained black sintered powder in 100ml of 10% hydrochloric acid water solution for washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
As shown in fig. 1, which is an SEM image of the silicon-carbon nanotube composite negative electrode material prepared in this embodiment, it can be seen from the figure that the silicon-carbon nanotube composite negative electrode material prepared in this embodiment is formed by compounding carbon-coated nano-silicon with a carbon nanotube three-dimensional network, the particle size of the carbon-coated nano-silicon is 50 to 100nm, the tube diameter of the in-situ grown carbon nanotube is 10 to 50nm, and the length is 1 to 10 μm.
The silicon-carbon nanotube composite negative electrode material prepared in the embodiment can be used as a negative electrode material of a lithium ion battery, and the silicon-carbon nanotube composite material and the superconducting material are usedCarbon and a binder LA133 according to a mass ratio of 8:1:1, dispersing the mixture in an aqueous solution (solid content is 20 percent), stirring the mixture for 12 hours to obtain uniform silicon negative electrode slurry, coating the slurry on a copper foil by using a wire bar coater, drying the slurry, and cutting the slurry into pole pieces with the diameter of 12mm, wherein the silicon loading capacity on the pole pieces is 1.5mg/cm to 1.5mg/cm 2 The pole piece, the lithium cathode and the diaphragm are assembled into a lithium ion battery in a glove box to carry out charge-discharge and cycle performance tests.
Fig. 2 is a graph showing cycle performance curves of the silicon-carbon nanotube composite negative electrode prepared in the present example, the silicon-carbon nanotube composite negative electrode prepared in the comparative example 1, and the silicon-superconducting carbon composite negative electrode prepared in the comparative example 2, where the first discharge capacity of the silicon-carbon nanotube composite negative electrode is 1667mAh/g, the first discharge capacity of the silicon-carbon nanotube composite negative electrode is 1069mAh/g after 50 cycles, and the capacity retention rate is 64.1% at a rate of 0.1C. Compared with the silicon-carbon nanotube composite cathode prepared in the comparative example 1 (the first discharge capacity is 1334.7mAh/g, 39.1mAh/g after 50 times of circulation, and the capacity retention rate is 3%) and the silicon-superconducting carbon composite cathode prepared in the comparative example 2 (the first discharge capacity is 2246mAh/g, 1.6mAh/g after 50 times of circulation, and the capacity retention rate is 0.07%), the cycle performance is obviously improved.
Example 2
The embodiment provides a silicon-carbon nanotube composite negative electrode material, which consists of carbon-coated nano silicon and in-situ grown carbon nanotubes and has a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; carbon-coated nano-silicon is dispersed within the three-dimensional network structure. The grain diameter of the nano-silicon is 100-150 nm, the pipe diameter of the in-situ grown carbon nano-tube is 50-200 nm, and the length is 1-10 mu m.
The embodiment also provides a preparation method of the silicon-carbon nanotube composite anode material, which comprises the following steps:
(1) Adding 0.50g of nano silicon powder (with the particle size of 100-150 nm) into a mixed solution of 80ml of water containing 0.02g of dodecyl trimethyl ammonium bromide, 320ml of ethanol and 4ml of ammonia water, stirring, ultrasonically dispersing uniformly, then adding 0.6g of resorcinol until the resorcinol is dissolved, finally adding 0.8g of formaldehyde solution, stirring and reacting for 24 hours at 50 ℃, filtering, washing and drying to obtain precursor powder of the phenolic coated silicon;
(2) Grinding and uniformly mixing 0.15g of precursor powder, 2g of diesel oil and 2g of melamine, then adding 5ml of ethanol solution containing 0.10g of cobalt chloride, continuously grinding uniformly to form a pasty mixture, keeping the temperature of the mixture at 700 ℃ for 2h in a high-purity Ar atmosphere, and naturally cooling to obtain black powder;
(3) And (3) placing the obtained black sintered powder in 100ml of 10% hydrochloric acid water solution for washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
Example 3
The embodiment provides a silicon-carbon nanotube composite negative electrode material, which consists of carbon-coated nano silicon and in-situ grown carbon nanotubes and has a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; carbon-coated nano-silicon is dispersed within the three-dimensional network structure. The grain diameter of the nano-silicon is 100-150 nm, the pipe diameter of the in-situ grown carbon nano-tube is 10-100 nm, and the length is 10-20 mu m.
The embodiment also provides a preparation method of the silicon-carbon nanotube composite anode material, which comprises the following steps:
(1) Adding 0.50g of nano silicon powder (with the particle size of 100-150 nm) into a mixed solution of 80ml of water containing 0.02g of polyvinylpyrrolidone, 320ml of ethanol and 4ml of ammonia water, stirring, ultrasonically dispersing uniformly, then adding 1.0g of resorcinol until the resorcinol is dissolved, finally adding 1.3g of formaldehyde solution, stirring and reacting for 24 hours at 30 ℃, filtering, washing and drying to obtain precursor powder of the phenolic coated silicon;
(2) Grinding and uniformly mixing 0.15g of precursor powder, 1g of paraffin oil and 3g of melamine, then adding 5ml of ethanol solution containing 0.15g of cobalt acetate, continuously grinding uniformly to form a pasty mixture, keeping the temperature at 800 ℃ for 5 hours in a high-purity Ar atmosphere, and naturally cooling to obtain black powder;
(3) And (3) placing the obtained black sintered powder in 100ml of hydrochloric acid water solution containing 30 percent, washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
Comparative example 1
The comparative example provides a preparation method of a silicon-carbon nanotube composite negative electrode material, which comprises the following steps:
(1) Grinding and mixing 0.15g of nano silicon powder (with the particle size of 30-80 nm), 2g of paraffin oil and 3g of melamine uniformly, then adding 5ml of ethanol solution containing 0.15g of cobalt acetate, continuously grinding uniformly to form a pasty mixture, keeping the temperature of 900 ℃ for 2 hours in a high-purity Ar atmosphere, and naturally cooling to obtain black powder;
(2) And (3) placing the obtained black sintered powder in 100ml of 10% hydrochloric acid water solution for washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
Comparative example 2
The comparative example provides a preparation method of a silicon-superconducting carbon composite negative electrode material, which comprises the following steps: and (3) grinding or ball-milling 0.15g of nano silicon powder (with the particle size of 30-80 nm) and 0.04g of superconducting carbon for 1 hour to obtain the silicon-superconducting carbon composite cathode material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (9)

1. A preparation method of a silicon-carbon nanotube composite anode material is characterized by comprising the following steps:
s1: adding the nano silicon powder into a mixed solution containing a surfactant, stirring, performing ultrasonic treatment, then sequentially adding resorcinol and formaldehyde solution, heating, stirring, filtering, washing and drying to obtain precursor powder of phenolic aldehyde coated silicon; the mixed solution consists of water, alcohol and ammonia water;
s2: mixing the precursor powder with mineral oil and melamine, then adding a cobalt salt solution, grinding or ball-milling and uniformly mixing to form a muddy mixture, and placing the muddy mixture in an inert atmosphere for heat treatment to obtain sintered powder; the mass ratio of the precursor powder to the mineral oil is (0.02-0.2): 1; the mass ratio of the precursor powder to the melamine is (0.01-0.2) to 1;
s3: and (3) placing the sintered powder in an acidic aqueous solution for washing, filtering and drying to obtain the silicon-carbon nanotube composite negative electrode material.
2. The method according to claim 1, wherein in the step S1, the molar ratio of resorcinol to formaldehyde is 1 (1-2); the mass ratio of the nano silicon powder to the resorcinol is (0.2-20) to 1; the proportion of the nano silicon powder to the mixed solution is (0.01-0.5) g:100ml; the mass ratio of the surfactant to the mixed solution is (0.1-2) to 100; the volume ratio of alcohol to water in the mixed solution is (50-1) to 1, and the volume ratio of ammonia water to water is 1 (1-20).
3. The method according to claim 1, wherein in step S1, the surfactant is at least one of dodecyltrimethylammonium bromide, and polyvinylpyrrolidone.
4. The preparation method according to any one of claims 1 to 3, wherein the nano silicon powder has a particle size of 30 to 300nm.
5. The process according to any one of claims 1 to 3, wherein the heating and stirring are carried out at a temperature of 20 to 80 ℃ for 12 to 36 hours.
6. The method of claim 1, wherein in step S2, the mineral oil is at least one of paraffin oil, kerosene, diesel oil, lubricating oil, and liquid asphalt; the cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; the inert atmosphere is Ar gas and N 2 Gas and Ar/H 2 At least one of the mixed gas of (1).
7. The method of claim 1, wherein the heat treatment is performed at 500 to 1000 ℃ for 1 to 5 hours in step S2.
8. A silicon-carbon nanotube composite negative electrode material, which is characterized by being prepared by the preparation method of any one of claims 1 to 7; the cathode material consists of carbon-coated nano silicon and in-situ grown carbon nanotubes and is in a three-dimensional network structure; the three-dimensional network structure is built by in-situ grown carbon nano tubes; the carbon-coated nano silicon is dispersed in the three-dimensional network structure.
9. An application of a silicon-carbon nanotube composite negative electrode material is characterized in that the negative electrode material prepared by the preparation method of any one of claims 1 to 7 or the negative electrode material of claim 8 is applied to a lithium ion battery.
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