CN113422008A - Synthesis method of micron-sized silicon monoxide @ carbon nanotube composite lithium ion battery anode material - Google Patents
Synthesis method of micron-sized silicon monoxide @ carbon nanotube composite lithium ion battery anode material Download PDFInfo
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Abstract
The invention relates to a micron silicon monoxide @ carbon nanotube composite lithium ion battery cathode material and a synthesis method thereof. According to the invention, a metal catalysis method is adopted, and nitrogen-doped carbon nanotubes (NCNTs) grow in situ on the surfaces of polydopamine-coated micron SiO particles, so that the SiO @ nitrogen-doped carbon layer-nitrogen-doped carbon nanotube (SiO @ NC-NCNTs) micron composite material is formed. From the results of scanning and transmission electron microscopy, a large number of carbon nanotubes uniformly grow on the surface of the micron SiO @ NC, and the tightly connected carbon nanotubes form a stable three-dimensional structure similar to a sea urchin shape. The unique composite structure can effectively buffer the volume expansion effect in the SiO circulation process, and ensure the stability of the whole structure while improving the conductivity of the electrode material, thereby optimizing the lithium storage performance of the electrode material. The SiO @ NC-NCNTs micron composite material prepared by the method has potential application prospect in the field of new energy such as lithium ion batteries and the like.
Description
Technical Field
The invention relates to a micron silicon monoxide @ carbon nanotube composite lithium ion battery cathode material and a synthesis method thereof.
Background
The lithium ion battery almost occupies the market of portable electronic products by virtue of the advantages of high energy density, long cycle life, environmental friendliness and the like, and becomes a preferred power source of the electric automobile. However, the rapid development of portable electronic devices and electric vehicles puts higher demands on the existing mobile power sources, and it is very important to further improve the energy density and cycle life of lithium ion batteries. Considering that the performance of the lithium ion battery is directly related to the electrode material, the theoretical specific capacity of the current commercial graphite negative electrode material is only 372mAhg-1It has been difficult to meet the requirements of high energy density lithium ion batteries. Therefore, the development of negative electrode materials with high capacity and excellent cycle performance has been an inevitable trend in the development of lithium ion batteries.
Silicon has a high theoretical specific capacity (4200 mAhg)-1) Lower delithiation potential (<0.5v) and abundant reserves, are considered as potential negative electrode materials for next generation high energy density lithium ion batteries. However, the inherently low conductivity and large volume changes of more than 300% severely affect the electrochemical lithium storage properties of the silicon anode material. For nano silicon-based materials, the small particle size can effectively shorten the diffusion distance of electrons and lithium ions and buffer the volume change in the lithiation process, but the characteristics of higher cost, lower tap density and the like seriously limit the large-scale commercial application of the nano silicon-based materials. In contrast, micron-sized silicon-based materials have received much attention due to their high tap density and low manufacturing cost.
Of these micron silicon negative electrode materials, silicon monoxide (SiO) is considered a promising silicon substitute because SiO has much less volume change than Si, and SiO and Li+Reaction-formed Li2O and Li4SiO4Can be used as a buffer medium to relieve the volume change in the first lithiation process. However, poor conductivity hinders Li+The volume change in the long circulation process is not negligible. Therefore, different structural designs and interface management have been used to improve and enhance the lithium storage performance of micron-sized SiO, such as compounding with carbon substrate material such as graphene, amorphous carbon, carbon nanotube, etc. with excellent conductivity, and improving the conductivity of electrode materialAnd the problems of volume expansion and the like can be effectively relieved while the electric property is realized. Compared with the common amorphous carbon layer coating, the one-dimensional Carbon Nanotubes (CNTs) can shorten the transmission path of electrons and ions, improve the transmission dynamics, and the crosslinked network structure can better bear the stress change in the lithium intercalation process. However, most of the research is mainly focused on the simple compounding of SiO and carbon nanotubes, and the bonding force between the SiO and the carbon nanotubes is weak, so that the mechanical stability in the long-cycle process is difficult to ensure. Therefore, the development of the efficient and stable micron-sized SiO @ CNTs composite material has very important research significance and industrial value for the application of the lithium ion battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a micron silicon monoxide @ carbon nanotube composite material and a synthesis method thereof. The method has the advantages of simple operation, controllable reaction conditions, realization of batch production and the like. The micron particles prepared by the method are integrally in a uniform sea urchin-shaped appearance, wherein the particle size of SiO is 2-3 mu m, the intermediate carbon layer is 10-30 nm, and the length of the carbon tube is 200-500 nm.
The micron silicon oxide @ carbon nanotube composite material has integral sea urchin-shaped structure and stable three-dimensional conductive network.
Preferably, a metal catalysis method is adopted, and nitrogen-doped carbon nanotubes grow in situ on the surfaces of the polydopamine-coated micron SiO particles, so that the SiO @ nitrogen-doped carbon layer-nitrogen-doped bamboo joint carbon nanotube micron composite material is obtained. The composite material of the invention shows relatively uniform sea urchin-shaped appearance, and the carbon nano tube grown by in-situ catalysis presents a bamboo joint carbon structure.
Preferably, the particle size of SiO is 2-3 μm, the intermediate carbon layer is 10-30 nm, and the length of the carbon tube is 200-500 nm.
The invention relates to a preparation method of a micron silicon monoxide @ carbon nanotube composite material, which comprises the following steps:
a. ultrasonically dispersing SiO powder in a Tris buffer solution to uniformly disperse the SiO powder, so that the pH value of the solution is not lower than 8.5; wherein the volume ratio parameter range of the SiO mass and the Tris buffer solution is 0.3-0.6 mg/mL;
b. adding dopamine hydrochloride and ferric chloride hexahydrate into the solution obtained in the step a, performing ultrasonic treatment for at least 10min, stirring for at least 24h, and performing centrifugation, washing and drying after the reaction is finished to obtain powder; the ratio parameter range of the mass of the dopamine hydrochloride or ferric chloride hexahydrate to the volume of the Tris buffer solution in the step a is 0.05-0.2 mg/mL;
c. uniformly mixing the powder obtained in the step b with cobalt chloride hexahydrate and melamine through grinding to obtain mixed powder; the mass ratio of the powder obtained in the step b, the cobalt chloride hexahydrate and the melamine is 2 (2.5-5) to 20;
d. putting the powder obtained in the step c in a tube furnace N2Calcining for at least 3h under the atmosphere; calcining at 700-900 ℃ to obtain product powder;
e. dispersing the product powder obtained in the step d in a dilute nitric acid solution, stirring at 40-60 ℃ for at least 12 hours, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron silicon oxide @ carbon nanotube composite material; the concentration of the dilute nitric acid solution is 6-8 mol/L.
Preferably, in the step a, 80-120mg of SiO powder is ultrasonically dispersed in 200mL of Tris buffer solution for at least 20min to ensure that the solution is uniformly dispersed and the pH value of the solution is not lower than 8.5;
preferably, in the step b, 10-20mg of dopamine hydrochloride and 18.4mg of ferric chloride hexahydrate are added into the solution obtained in the step a, ultrasonic treatment is carried out for at least 10min, stirring is carried out for at least 24h, and after the reaction is finished, centrifugation, washing and drying steps are carried out to obtain powder.
Preferably, in the step d, the temperature rise rate is controlled to be not lower than 4 ℃ min-1。
Preferably, in the step e, dispersing the product powder obtained in the step d in a dilute nitric acid solution, stirring at 50-60 ℃ for at least 12 hours, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron-sized silica @ carbon nanotube composite material; the concentration of the dilute nitric acid solution is 6.5-7.0 mol/L.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method has low process cost, can realize batch production and is environment-friendly;
2. the micron particles prepared by the method form a stable conductive network, and have certain application prospect in the field of new energy such as lithium ion batteries and the like.
Drawings
FIG. 1 is an SEM picture of the SiO @ NC-NCNTs micron composite material obtained in the first embodiment of the invention.
FIG. 2 is a TEM image of the SiO @ NC-NCNTs micron composite material obtained in the first embodiment of the present invention.
FIG. 3 is an XRD spectrum of the SiO @ NC-NCNTs micron composite material obtained in the first embodiment of the invention.
FIG. 4 is a graph comparing electrochemical cycle performance of the SiO @ NC-NCNTs nanocomposite obtained in the first example of the present invention and the material obtained in the second comparative example.
Detailed Description
The following examples of the present invention were all operated according to the procedure of the above technical scheme.
The invention is further illustrated by the following examples. For the purpose of better understanding the contents of the present invention.
Example one
A preparation method of a micron silicon oxide @ carbon nanotube composite material comprises the following steps:
a. ultrasonically dispersing 100mg of commercial SiO powder in 200mL of Tris buffer solution for 20min to uniformly disperse the commercial SiO powder, wherein the pH value of the solution is 8.5;
b. adding 20mg of dopamine hydrochloride and 18.4mg of ferric chloride hexahydrate into the solution obtained in the step a, carrying out ultrasonic treatment for 10min, stirring for 24h, and carrying out centrifugation, washing and drying after the reaction is finished to obtain powder;
c. uniformly mixing 80mg of the powder obtained in the step b with 200mg of cobalt chloride hexahydrate and 800mg of melamine by grinding to obtain mixed powder;
d. putting the powder obtained in the step c in a tube furnace N2Calcining for 3 hours in the atmosphere; the calcining temperature is 800 ℃, and the heating rate is 4 ℃ min-1Obtaining product powder;
e. and d, dispersing the product powder obtained in the step d in a dilute nitric acid solution with the concentration of 6.5mol/L, stirring for 12 hours at the temperature of 60 ℃, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron silicon oxide @ carbon nanotube composite material.
This example prepares a uniform SiO @ NC-NCNTs micron composite, and the physical properties of the prepared sample are characterized, some of which are shown in the attached figures 1-3.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
a preparation method of a micron silicon oxide @ carbon nanotube composite material comprises the following steps:
a. ultrasonically dispersing 100mg of commercial SiO powder in 200mL of Tris buffer solution for 20min to uniformly disperse the commercial SiO powder, wherein the pH value of the solution is 8.5;
b. adding 20mg of dopamine hydrochloride and 18.4mg of ferric chloride hexahydrate into the solution obtained in the step a, carrying out ultrasonic treatment for 10min, stirring for 24h, and carrying out centrifugation, washing and drying after the reaction is finished to obtain powder;
c. uniformly mixing 80mg of the powder obtained in the step b with 100mg of cobalt chloride hexahydrate and 800mg of melamine by grinding to obtain mixed powder;
d. putting the powder obtained in the step c in a tube furnace N2Calcining for 3 hours in the atmosphere; the calcining temperature is 800 ℃, and the heating rate is 4 ℃ min-1Obtaining product powder;
e. and d, dispersing the product powder obtained in the step d in a dilute nitric acid solution with the concentration of 7.0mol/L, stirring for 12 hours at the temperature of 50 ℃, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron silicon oxide @ carbon nanotube composite material.
This example prepares a uniform SiO @ NC-NCNTs micron composite. The results obtained are substantially similar to those of the first example, except that the diameter of the carbon nanotubes in the resulting nanocomposite becomes smaller.
EXAMPLE III
This embodiment is substantially the same as the first embodiment, and is characterized in that:
a preparation method of a micron silicon oxide @ carbon nanotube composite material comprises the following steps:
a. ultrasonically dispersing 120mg of commercial SiO powder in 200mL of Tris buffer solution for 20min to uniformly disperse the commercial SiO powder, wherein the pH value of the solution is 8.5;
b. adding 10mg of dopamine hydrochloride and 18.4mg of ferric chloride hexahydrate into the solution obtained in the step a, carrying out ultrasonic treatment for 10min, stirring for 24h, and carrying out centrifugation, washing and drying after the reaction is finished to obtain powder;
c. uniformly mixing 80mg of the powder obtained in the step b with 200mg of cobalt chloride hexahydrate and 800mg of melamine by grinding to obtain mixed powder;
d. putting the powder obtained in the step c in a tube furnace N2Calcining for 3 hours in the atmosphere; the calcining temperature is 800 ℃, and the heating rate is 4 ℃ min-1Obtaining product powder;
e. and d, dispersing the product powder obtained in the step d in a dilute nitric acid solution with the concentration of 6.5mol/L, stirring for 12 hours at the temperature of 60 ℃, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron silicon oxide @ carbon nanotube composite material.
This example prepares a uniform SiO @ NC-NCNTs micron composite. The results obtained are substantially similar to those of the first example, except that the thickness of the intermediate carbon layer of the resulting nanocomposite is significantly reduced.
Comparative example 1
The synthetic method of the micron monox @ carbon composite material comprises the following steps:
(1) ultrasonically dispersing 100mg of commercial SiO powder in 200ml of Tris buffer solution for 20min to uniformly disperse the powder;
(2) 20mg of dopamine hydrochloride and 18.4mg of FeCl3·6H2And (2) adding O into the solution obtained in the step (1), carrying out ultrasonic treatment for 10min, stirring for 24h, and carrying out conventional centrifugation, washing, drying and other steps after the reaction is finished to obtain a brownish black powder product, namely the uniform SiO @ carbon micron composite material.
The comparative preparation process and procedure are different from those of the first embodiment, except that the composite material does not contain carbon nanotubes.
Comparative example No. two
This comparative example is essentially the same as the first example, with the particularity that:
the synthetic method of the micron silicon oxide @ carbon nanotube composite material comprises the following steps:
80mg of commercial SiO powder and 200mg of CoCl2·6H2O and 800mg of melamine were mixed by grinding;
putting the powder obtained in the step I into a tube furnace N2Calcining at 800 deg.C for 3h under atmosphere, and heating rate of 4 deg.C for min-1；
③ dispersing the powder obtained in the step II in 6.5mol/L HNO3Stirring the solution for 12 hours at the temperature of 60 ℃, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, and obtaining the uniform SiO @ NCNTs micron composite material prepared by the embodiment.
The results obtained in this comparative example are substantially similar to those of the first example, except that the resulting nanocomposite is free of intermediate carbon coating and has reduced surface growth of carbon nanotubes.
Experimental test analysis:
referring to the attached drawings, FIG. 1 is a Scanning Electron Microscope (SEM) picture of a SiO @ NC-NCNTs micron composite material obtained in one embodiment of the invention. SEM analysis: and observing the morphology of the material by adopting a ZEISS Gemini 300 type emission scanning electron microscope. From SEM results, a large number of carbon nanotubes uniformly grow on the surface of the micron SiO @ NC, and the tightly connected carbon nanotubes further form a stable three-dimensional structure, so that the conductivity of the composite material is improved, and the mechanical stability of the material can be ensured.
Referring to the attached drawings, FIG. 2 is a Transmission Electron Microscope (TEM) picture of the SiO @ NC-NCNTs micron composite material obtained in the first embodiment of the invention. TEM analysis: the morphology and structure of the material were observed by a JEOL-200CX type transmission electron microscope, Japan Electron Co. The TEM images further demonstrate the close association of SiO @ NC with carbon nanotubes and have a sea urchin-like structure. Through careful observation, the short carbon nanotubes are found to be in a bamboo-like structure, and the length of the short carbon nanotubes is 200-500 nm.
Referring to the attached drawings, FIG. 3 is an XRD spectrum of a SiO @ NC-NCNTs micron composite material obtained in the first embodiment of the invention. XRD analysis: on an X-ray diffractometer model RigaKu D/max-2550, Japan; CuK α diffraction was used, with λ 0.154 nm. As can be seen, the crystal phase structure of the SiO @ NC-NCNTs micron composite material obtained in the first embodiment of the invention is consistent with standard spectrograms (PDF No:41-1487 and PDF No:27-1402), respectively corresponds to the (002) crystal face and the simple substance Si of graphite carbon, and a small amount of simple substance Co which is not completely removed is remained.
According to the micron silicon oxide @ carbon nanotube composite lithium ion battery cathode material disclosed by the embodiment of the invention, the nitrogen-doped carbon nanotubes (NCNTs) are grown in situ on the surfaces of the poly-dopamine-coated micron SiO particles by adopting a metal catalysis method, so that the SiO @ nitrogen-doped carbon layer-nitrogen-doped carbon nanotubes (SiO @ NC-NCNTs) micron composite material is formed. From the results of scanning and transmission electron microscopy, a large number of carbon nanotubes uniformly grow on the surface of the micron SiO @ NC, and the tightly connected carbon nanotubes form a stable three-dimensional structure similar to a sea urchin shape. The unique composite structure can effectively buffer the volume expansion effect in the SiO circulation process, and ensure the stability of the whole structure while improving the conductivity of the electrode material, thereby optimizing the lithium storage performance of the electrode material. The SiO @ NC-NCNTs micron composite material prepared by the method has potential application prospect in the field of new energy such as lithium ion batteries and the like.
Referring to the drawings, FIG. 4 is a graph comparing electrochemical cycling performance of the SiO @ NC-NCNTs nanocomposite obtained in the first example of the present invention and the material obtained in the second comparative example. The method for testing the electrochemical performance comprises the following steps: the prepared SiO @ NC-Adding super-P, sodium alginate and deionized water into the NCNTs micron composite material, fully mixing by grinding, and then drawing and slicing on a copper foil to be used as a negative electrode of the battery; taking metal lithium as a positive electrode and a microporous polypropylene material as a diaphragm; the electrolyte is made of 1.0mol/L LiPF6Dissolving in ethylene carbonate, propylene carbonate and ethyl carbonate (mass ratio of 1:1: 1). The half-cells were assembled in a glove box filled with argon. The voltage range of the battery during charging and discharging test is 0.005-2V, and the current density is 200 mA/g. The test result shows that: the first discharge capacity of the SiO @ NC-NCNTs electrode material obtained in the first example is 1819mAh/g, and the discharge capacity after 100 cycles is 1195 mAh/g. The first discharge capacity of the SiO @ NCNTs product obtained in example two is 1380mAh/g, and the discharge capacity after 100 cycles is 952 mAh/g. The result shows that the coating of the intermediate carbon layer can improve the electrical conductivity of the micron silicon oxide @ carbon nanotube composite electrode material to a certain extent, and enhance the stability of the whole structure, thereby improving the lithium storage performance of the micron silicon oxide @ carbon nanotube composite electrode material.
In summary, in the process of the above embodiment of the present invention, firstly, a layer of Polydopamine (PDA) is uniformly coated on the surface of the micron SiO particle to form a SiO @ PDA core-shell structure; adding CoCl2·6H2O and melamine are respectively used as catalysts and carbon precursors to be mixed with SiO @ PDA, and PDA with abundant hydroxyl groups can absorb Co with positive charge through electrostatic interaction2+And melamine, whereby the cobalt source and melamine are evenly distributed over the surface. Subsequently, the prepared precursor is placed in a tube furnace for heat treatment, so that the PDA is converted into a nitrogen-doped amorphous carbon layer; meanwhile, melamine is pyrolyzed into a gaseous carbon source and adsorbed on the surface of a Co catalyst, and bamboo-shaped nitrogen-doped carbon nanotubes (NCNTs) can well grow on the surface of the intermediate carbon layer in situ according to a Co-catalysis tip growth mechanism. And finally, removing the Co nano particles by adopting an acid etching method to obtain the SiO @ NC-NCNTs micron composite material.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the technical principle and the inventive concept of the present invention are not departed from the application of the technical solution and the inventive concept, which belong to the protection scope of the present invention.
Claims (8)
1. A micron silicon monoxide @ carbon nanotube composite material is characterized in that: the particles are integrally in a uniform sea urchin-shaped morphology structure to form a stable three-dimensional conductive network.
2. The microsilica @ carbon nanotube composite of claim 1, wherein: and (3) growing nitrogen-doped carbon nanotubes on the surfaces of the polydopamine-coated micron SiO particles in situ by adopting a metal catalysis method, so as to obtain the SiO @ nitrogen-doped carbon layer-nitrogen-doped bamboo joint carbon nanotube micron composite material.
3. The microsilica @ carbon nanotube composite of claim 1, wherein: the particle size of SiO is 2-3 μm, the intermediate carbon layer is 10-30 nm, and the length of the carbon tube is 200-500 nm.
4. A method for preparing the micron silica @ carbon nanotube composite material of claim 1, comprising the steps of:
a. ultrasonically dispersing SiO powder in a Tris buffer solution to uniformly disperse the SiO powder, so that the pH value of the solution is not lower than 8.5; wherein the ratio parameter range of the SiO mass to the volume of the Tris buffer solution is 0.3-0.6 mg/mL;
b. adding dopamine hydrochloride and ferric chloride hexahydrate into the solution obtained in the step a, performing ultrasonic treatment for at least 10min, stirring for at least 24h, and performing centrifugation, washing and drying after the reaction is finished to obtain powder; the ratio parameter range of the mass of the dopamine hydrochloride or ferric chloride hexahydrate to the volume of the Tris buffer solution in the step a is 0.05-0.2 mg/mL;
c. uniformly mixing the powder obtained in the step b with cobalt chloride hexahydrate and melamine through grinding to obtain mixed powder; the mass ratio of the powder obtained in the step b, the cobalt chloride hexahydrate and the melamine is 2 (2.5-5) to 20;
d. putting the powder obtained in the step c in a tube furnace N2Calcining for at least 3h under the atmosphere; calcining at 700-900 ℃ to obtain product powder;
e. dispersing the product powder obtained in the step d in a dilute nitric acid solution, stirring at 40-60 ℃ for at least 12 hours, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron silicon oxide @ carbon nanotube composite material; the concentration of the dilute nitric acid solution is 6-8 mol/L.
5. The method for preparing the micron silica @ carbon nanotube composite material as claimed in claim 4, wherein: in the step a, 80-120mg of SiO powder is ultrasonically dispersed in 200mL of Tris buffer solution for at least 20min to ensure that the solution is uniformly dispersed and the pH value of the solution is not lower than 8.5.
6. The method for preparing the micron silica @ carbon nanotube composite material as claimed in claim 4, wherein: in the step b, 10-20mg of dopamine hydrochloride and 18.4mg of ferric chloride hexahydrate are added into the solution obtained in the step a, ultrasonic treatment is carried out for at least 10min, stirring is carried out for at least 24h, and after the reaction is finished, centrifugation, washing and drying are carried out to obtain powder.
7. The method for preparing the micron silica @ carbon nanotube composite material as claimed in claim 4, wherein: in the step d, the temperature rise rate is controlled to be not lower than 4 ℃ min-1。
8. The method for preparing the micron silica @ carbon nanotube composite material as claimed in claim 4, wherein: in the step e, dispersing the product powder obtained in the step d in a dilute nitric acid solution, stirring at 50-60 ℃ for at least 12 hours, naturally cooling, centrifugally collecting, washing and drying to obtain a black powder product, namely the micron silicon oxide @ carbon nanotube composite material; the concentration of the dilute nitric acid solution is 6.5-7.0 mol/L.
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