CN111732092A - Graphene/carbon nanotube/porous silicon composite material and preparation method and application thereof - Google Patents
Graphene/carbon nanotube/porous silicon composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium batteries, and discloses a graphene/carbon nanotube/porous silicon composite material and a preparation method and application thereof. Adding an acidified carbon nano tube into a graphene oxide aqueous solution, performing ultrasonic treatment I to obtain a graphene oxide/carbon nano tube solution, adding an aluminum-silicon alloy into the graphene oxide/carbon nano tube solution, performing ultrasonic treatment II, adding a graphene oxide reducing agent into the obtained suspension solution, performing ultrasonic treatment III, standing, filtering or centrifuging, washing to be neutral, and performing vacuum drying to obtain a graphene/carbon nano tube/aluminum-silicon alloy composite material; and finally, adding the graphene/carbon nano tube/aluminum-silicon alloy composite material into an inorganic acid solution, mixing and stirring, filtering or centrifuging to be neutral, and performing vacuum drying to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material. The composite material has excellent high reversible capacity, cycling stability and rate capability. The method has the advantages of low equipment requirement, low energy consumption, simple steps, high controllability and easy industrial production, and can be applied to the field of lithium batteries.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a graphene/carbon nanotube/porous silicon composite material and a preparation method and application thereof.
Background
With the wide application of portable consumer electronics, medical electronics, new energy automobiles and the like, consumers have made higher requirements on the energy density of lithium batteries. At present, the anode material is difficult to break through to improve the energy density of the lithium battery, the development of the cathode material is imminent, and the research shows that the silicon cathode is an ideal material of the lithium ion battery, and the anode material has the following advantages: silicon forming Li with lithium15Si4The theoretical specific capacity of lithium storage of the alloy is up to 4200mAh/g, which is ten times of that of a graphite cathode; the lithium intercalation potential of silicon is about 0.5V and is slightly higher than that of a graphite material, so that lithium dendrite is more difficult to form in the charging process; the reaction activity of silicon and electrolyte is low, and the co-intercalation phenomenon of organic solvent can not occur.
However, the silicon-based material still has many problems as the negative electrode of the lithium ion battery, such as volume expansion, low first efficiency, electrolyte consumption caused by repeated growth of SEI film, low electron ion transmission efficiency, poor conductivity and the like. In the process of charging and discharging, because of obvious volume expansion effect (more than 360%), huge stress is generated, the active material is easy to peel off from the current collector, and even the active material is crushed and pulverized seriously, so that the conductivity of the active material is reduced, and the impedance is increased. In the conventional method, a carbon layer is coated on a bare silicon outer layer, and due to the existence of the carbon layer, the transmission rate of lithium ions is reduced, and larger interface impedance is caused. And the above process is easy to cause the structure collapse, the rapid capacity attenuation, the impedance increase and the like of the cathode material. In order to effectively solve the problems occurring as described above, improvement of conductivity and maintenance of structural stability may be respectively achieved by adding graphene and a carbon material.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a graphene/carbon nanotube/porous silicon composite material which has excellent high reversible capacity, excellent cycling stability and excellent rate capability.
Another object of the present invention is to provide a method for preparing the graphene/carbon nanotube/porous silicon composite material. The method has the advantages of low equipment requirement, low energy consumption, simple steps, high controllability and easy industrial production.
The invention further aims to provide application of the graphene/carbon nanotube/porous silicon composite material.
The purpose of the invention is realized by the following technical scheme:
a graphene/carbon nanotube/porous silicon composite material is prepared by adding an acidified carbon nanotube into a graphene oxide aqueous solution, performing ultrasonic treatment I to obtain a graphene oxide/carbon nanotube solution, adding an aluminum-silicon alloy into the graphene oxide/carbon nanotube solution, performing ultrasonic treatment II to obtain a suspension solution, adding a graphene oxide reducing agent into the suspension solution, performing ultrasonic treatment III, standing, filtering or centrifuging, washing to be neutral, and performing vacuum drying to obtain the graphene/carbon nanotube/aluminum-silicon alloy composite material; and finally, adding the graphene/carbon nano tube/aluminum-silicon alloy composite material into an inorganic acid solution, mixing and stirring, filtering or centrifuging to be neutral, and performing vacuum drying to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material.
Preferably, the acidified carbon nanotube is one or more of a single-walled carbon nanotube and a multi-walled carbon nanotube acidified by an inorganic acid, the inorganic acid is one or more of hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the inorganic acid is 0.5-1.5 mol/L.
Preferably, the mass ratio of the acidified carbon nanotube to the graphene oxide in the graphene oxide aqueous solution is 1: (2-4).
Preferably, the average particle size of the aluminum-silicon alloy is 1-5 μm, and the mass ratio of aluminum to silicon in the aluminum-silicon alloy is (4-9): 1.
preferably, the mass ratio of the graphene oxide to the aluminum-silicon alloy in the graphene oxide/carbon nanotube solution is 1: (3-5).
Preferably, the graphene oxide reducing agent is more than one of hydrazine, sodium borohydride, ascorbic acid, sodium citrate or tea polyphenol.
Preferably, the time of the ultrasonic I is 0.5-1.5 h; the time of the ultrasonic II is 0.5-1.5 h; the time of the ultrasonic III is 1-3 h; the standing time is 12-24 h.
Preferably, the temperature of the vacuum drying is 50-70 ℃.
The preparation method of the graphene/carbon nanotube/porous silicon composite material comprises the following specific steps:
s1, adding a carbon nano tube into inorganic acid for ultrasonic treatment, washing with deionized water, and drying in vacuum to obtain an acidified carbon nano tube;
s2, adding graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide aqueous solution;
s3, adding the acidified carbon nano tube into a graphene oxide aqueous solution for ultrasonic treatment to obtain a graphene oxide/carbon nano tube composite solution;
s4, adding aluminum-silicon alloy into the graphene oxide/carbon nano tube composite solution, and performing ultrasonic treatment to obtain a suspension solution;
s5, adding a reducing agent into the suspension solution for ultrasonic treatment, and then standing, washing and vacuum drying to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material;
and S6, adding the graphene/carbon nano tube/aluminum-silicon alloy composite material into an inorganic acid solution, stirring, filtering or centrifuging, and drying in vacuum to obtain the graphene/carbon nano tube/porous silicon composite material.
The graphene/carbon nanotube/porous silicon composite material is applied to the field of lithium batteries.
The principle of the invention mainly comprises the following points:
(1) the graphene and the carbon nano tube are combined together due to the action of pi-pi bonds. (2) The aluminum-silicon alloy and the graphene/carbon nanotube composite material are positively charged, carbon nanotubes in the graphene/carbon nanotube composite material are acidified and negatively charged due to positive and negative opposite charges, and the acidified carbon nanotubes play a middle bridge role. (3) After acid washing, the aluminum-silicon alloy is tightly wound on the porous silicon outer layer by the acidified carbon nano tube; simultaneously, due to the action of the pi-pi bond, the graphene and the acidified carbon nanotube are combined together; and loading porous silicon on the graphene so as to obtain the graphene/carbon nanotube/porous silicon composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. the graphene/carbon nanotube/porous silicon composite material has excellent high reversible capacity, cycling stability and rate capability. The porous silicon structure is prepared by utilizing the aluminum-silicon alloy, the porous silicon ball is composed of a plurality of ordered silicon strips, and the space between the silicon strips can greatly relieve the volume expansion problem caused by the silicon-carbon cathode in the circulation process.
2. According to the graphene/carbon nanotube/porous silicon composite material, the carbon nanotube is used as a bridge between graphene and silicon; the graphene and the carbon nano tube are combined together under the action of pi-pi bonds; meanwhile, the aluminum is positively charged, the treated carbon nano tube is negatively charged, and the positive charges and the negative charges are mutually attracted, so that the graphene/carbon nano tube can be tightly combined with the aluminum-silicon alloy; and finally, acid washing is carried out, so that the porous silicon and the graphene/carbon nano tube can be effectively and tightly compounded together, and the carbon nano tube is tightly wound on the outer layer of the porous silicon, so that the problem of volume expansion of the porous silicon is greatly relieved.
3. The graphene in the graphene/carbon nanotube/porous silicon composite material can well improve the conductivity problem of silicon in the charging and discharging processes.
4. The aluminum-silicon alloy in the graphene/carbon nanotube/porous silicon composite material is prepared by melting aluminum-silicon alloy ingots serving as raw materials and atomizing nitrogen into powder, and the aluminum-silicon alloy is easy to prepare on a large scale and is commercialized.
5. The preparation method disclosed by the invention is low in equipment requirement, low in energy consumption, simple in steps, high in controllability and easy for industrial production.
Drawings
Fig. 1 is a scanning electron micrograph of the graphene/carbon nanotube material obtained in example 1.
Fig. 2 is a transmission electron micrograph of the graphene/carbon nanotube material obtained in example 1.
FIG. 3 is a scanning electron micrograph of the aluminum-silicon alloy obtained in example 1.
Fig. 4 is a scanning electron microscope image of the graphene/carbon nanotube/porous silicon composite material obtained in example 1.
Fig. 5 is a transmission electron microscope image of the graphene/carbon nanotube/porous silicon composite material obtained in example 1.
Fig. 6 is a graph of the first charge-discharge specific capacity of a battery electrode plate prepared from the graphene/carbon nanotube/porous silicon composite material of example 1.
Fig. 7 is a cycle performance test chart of a battery electrode plate prepared from the graphene/carbon nanotube/porous silicon composite material of example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. 0.2314g of multi-walled carbon nano-tube is uniformly added into 6mLHCl (1mol/L) for ultrasonic treatment for 2h, the mixture is washed by deionized water and absolute ethyl alcohol for a plurality of times, and the obtained sample is placed in a vacuum drying oven to be dried for 10h at 50 ℃ to prepare the acidified carbon nano-tube.
2. And (3) slowly adding 0.15g of graphene oxide into 200mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain a graphene oxide aqueous solution.
3. 0.05g of multi-walled carbon nano tube is added into the graphene oxide solution for ultrasonic treatment for 1 hour, and then the mixture is stirred for 2 hours to prepare graphene oxide/carbon nano tube.
4. Adding 0.6g of aluminum-silicon alloy (the average diameter is 1 mu m, the mass ratio of aluminum to silicon is 4: 1) into the graphene oxide/carbon nano tube mixed solution, carrying out ultrasonic treatment for 1h, then respectively adding 1.5g of ascorbic acid and 0.75g of sodium citrate, carrying out ultrasonic treatment for 2h, standing for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, placing the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material.
5. Adding the graphene/carbon nanotube/aluminum-silicon alloy composite material into 0.5mol/LHCl, magnetically stirring for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nanotube/porous silicon composite material.
Fig. 1 and 2 are a scanning electron microscope image and a transmission electron microscope image of the graphene/carbon nanotube obtained in example 1, respectively, and it can be seen from fig. 1 and 2 that the carbon nanotube and the graphene are well compounded with each other. FIG. 3 is a scanning electron microscope image of the Al-Si alloy obtained in example 1, which shows that the Al-Si alloy is spherical, has uniform size and has a diameter of 1-2 μm. Fig. 4 and 5 are a scanning electron microscope image and a transmission electron microscope image of the graphene/carbon nanotube/porous silicon composite material obtained in example 1, respectively, and it can be seen from the images that the carbon nanotubes are bonded to the graphene due to pi-pi bonds, and the aluminum-silicon alloy and the carbon nanotubes are tightly bonded to the porous silicon due to positive and negative electrical properties; thereby enabling the porous silicon to be tightly loaded on the graphene.
Mixing a graphene/carbon nanotube/porous silicon composite material, a conductive agent (SP) and a binding agent (sodium alginate) according to a mass ratio of 3: 1: 1, mixing the slurry to be proper, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The obtained pole pieces were assembled into a 2032R type button cell, and the used silicon-carbon electrolyte (purchased from Koledo Co., Ltd.) was subjected to electrochemical performance test, the test results are shown in FIG. 6 and FIG. 7.
The graphene/carbon nanotube/porous silicon composite material in the example is used as a negative electrode material to prepare a lithium ion battery, and a cycle performance test is performed on the lithium ion battery, and fig. 6 is a graph of the first charge-discharge specific capacity of the battery pole piece prepared in example 1. As seen from FIG. 6, the first discharge specific capacity of the material is 2224.5mAh/g, the first charge specific capacity is 1780.3mAh/g, and the first coulombic efficiency is 80%. FIG. 7 is a graph of cycle performance testing of battery pole pieces prepared in example 1. As can be seen from FIG. 7, under the condition of the current density of 1A/g, after 100 cycles, the charging specific capacity is still 1244.5 mAh/g. The prepared graphene/carbon nanotube/porous silicon composite material has excellent high reversible capacity, cycle stability and rate capability when being used as a negative electrode material. The aluminum-silicon alloy has a porous structure after being subjected to acid washing, so that the volume expansion of silicon in the circulation process can be effectively relieved, and the acidified carbon nano tube is wound on the outer layer of the porous silicon, so that the effect of inhibiting the volume expansion of the porous silicon is achieved; the acidified carbon nano tube is used as a bridge, and the graphene at the other end is arranged on the outer layer of the porous silicon, so that the conductivity of the porous silicon can be greatly improved.
Example 2
1. 0.2314g of multi-walled carbon nano-tube is uniformly added into 6mLHCl (1mol/L) for ultrasonic treatment for 2h, the mixture is washed by deionized water and absolute ethyl alcohol for a plurality of times, and the obtained sample is placed in a vacuum drying oven and dried for 10h at 50 ℃ to prepare the acidified carbon nano-tube.
2. And (3) slowly adding 0.1g of graphene oxide into 200mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain a graphene oxide aqueous solution.
3. And adding 0.05g of acidified carbon nano tube into the graphene oxide aqueous solution, performing ultrasonic treatment for 1h, and stirring for 2h to obtain the graphene oxide/carbon nano tube solution.
4. Adding 0.6g of aluminum-silicon alloy (the average diameter is 1 mu m, the mass ratio of aluminum to silicon is 4: 1) into the graphene oxide/carbon nanotube solution, carrying out ultrasonic treatment for 1h, then respectively adding 1.5g of ascorbic acid and 0.75g of sodium citrate, carrying out ultrasonic treatment for 2h, standing for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nanotube/aluminum-silicon alloy composite material.
5. Adding the graphene/carbon nanotube/aluminum-silicon alloy composite material into 0.5mol/LHCl, magnetically stirring for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nanotube/porous silicon composite material.
Mixing the obtained graphene/carbon nanotube/porous silicon composite material, a conductive agent (SP) and a binding agent (sodium alginate) according to a mass ratio of 3: 1: 1, mixing the slurry to be proper, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The obtained pole pieces are assembled into a 2032R type button cell battery, and silicon-carbon electrolyte (purchased from Koledo Co., Ltd.) is used.
Example 3
1. 0.2314g of multi-walled carbon nano-tube is uniformly added into 6mLHCl (1mol/L), ultrasonic treatment is carried out for 2h, the obtained sample is washed by deionized water and absolute ethyl alcohol for multiple times, and the obtained sample is placed in a vacuum drying oven and dried for 10h at 50 ℃ to prepare an acidified carbon nano-tube;
2. and (3) taking 0.15g of graphene oxide, slowly adding the graphene oxide into 200mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain a graphene oxide aqueous solution.
3. 0.05g of multi-walled carbon nano tube is added into the graphene oxide solution for ultrasonic treatment for 1 hour, and then the mixture is stirred for 2 hours to prepare graphene oxide/carbon nano tube.
4. Adding 0.75g of aluminum-silicon alloy (the average diameter is 1 mu m, the mass ratio of aluminum to silicon is 4: 1) into the graphene oxide/carbon nano tube mixed solution, carrying out ultrasonic treatment for 1h, then respectively adding 1.5g of ascorbic acid and 0.75g of sodium citrate, carrying out ultrasonic treatment for 2h, standing for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, placing the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material.
5. Adding the graphene/carbon nanotube/aluminum-silicon alloy composite material into 0.5mol/LHCl, magnetically stirring for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nanotube/porous silicon composite material.
Mixing the obtained graphene/carbon nanotube/porous silicon composite material, a conductive agent (SP) and a binding agent (sodium alginate) according to a mass ratio of 3: 1: 1, mixing the slurry to be proper, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The obtained pole pieces are assembled into a 2032R type button cell battery, and silicon-carbon electrolyte (purchased from Koledo Co., Ltd.) is used.
Example 4
1. 0.2314g of multi-walled carbon nano-tube is uniformly added into 6mLHCl (1mol/L) for ultrasonic treatment for 2h, the multi-time washing is carried out by deionized water and absolute ethyl alcohol, the obtained sample is placed in a vacuum drying oven and dried for 10h at 50 ℃, and the acidified carbon nano-tube is prepared;
2. and (3) taking 0.15g of graphene oxide, slowly adding the graphene oxide into 200mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain a graphene oxide aqueous solution.
3. 0.05g of multi-walled carbon nano tube is added into the graphene oxide solution for ultrasonic treatment for 1 hour, and then the mixture is stirred for 2 hours to prepare graphene oxide/carbon nano tube.
4. Adding 0.75g of aluminum-silicon alloy (the average diameter is 1 mu m, the mass ratio of aluminum to silicon is 4: 1) into the graphene oxide/carbon nano tube mixed solution, carrying out ultrasonic treatment for 1h, then respectively adding 0.75g of ascorbic acid and 0.75g of sodium citrate, carrying out ultrasonic treatment for 2h, standing for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material.
5. Adding the graphene/carbon nanotube/aluminum-silicon alloy composite material into 0.5mol/LHCl, magnetically stirring for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nanotube/porous silicon composite material.
Mixing a graphene/carbon nanotube/porous silicon composite material, a conductive agent (SP) and a binding agent (sodium alginate) according to a mass ratio of 3: 1: 1, mixing the slurry to be proper, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The obtained pole pieces are assembled into a 2032R type button cell battery, and silicon-carbon electrolyte (purchased from Koledo Co., Ltd.) is used.
Example 5
1. 0.2314g of multi-walled carbon nano-tube is uniformly added into 6mLHCl (1mol/L), ultrasonic treatment is carried out for 2h, the multi-time washing is carried out through deionized water and absolute ethyl alcohol, the obtained sample is placed in a vacuum drying oven and dried for 10h under the condition of 50 ℃, and the acidified carbon nano-tube is prepared;
2. and (3) slowly adding 0.15g of graphene oxide into 200mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain a graphene oxide aqueous solution.
3. 0.05g of multi-walled carbon nano tube is added into the graphene oxide solution for ultrasonic treatment for 1 hour, and then the mixture is stirred for 2 hours to prepare graphene oxide/carbon nano tube.
4. Adding 0.75g of aluminum-silicon alloy (the average diameter is 1 mu m, the mass ratio of aluminum to silicon is 4: 1) into the graphene oxide/carbon nano tube mixed solution, carrying out ultrasonic treatment for 1h, then respectively adding 1.5g of ascorbic acid and 1.5g of sodium citrate, carrying out ultrasonic treatment for 2h, standing for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, placing the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material.
5. Adding the graphene/carbon nanotube/aluminum-silicon alloy composite material into 0.5mol/LHCl, magnetically stirring for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying at 50 ℃ for 10h to obtain the graphene/carbon nanotube/porous silicon composite material.
Mixing the obtained graphene/carbon nanotube/porous silicon composite material, a conductive agent (SP) and a binding agent (sodium alginate) according to a mass ratio of 3: 1: 1, mixing the slurry to be proper, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The obtained pole pieces are assembled into a 2032R type button cell battery, and silicon-carbon electrolyte (purchased from Koledo Co., Ltd.) is used.
Electrochemical performance tests are carried out on the embodiments 2 to 5, and the results also show that the prepared graphene/carbon nanotube/porous silicon composite material has excellent high reversible capacity, cycle stability and rate capability as a negative electrode material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The graphene/carbon nanotube/porous silicon composite material is characterized in that an acidified carbon nanotube is added into a graphene oxide aqueous solution for ultrasonic treatment I to obtain a graphene oxide/carbon nanotube solution, an aluminum-silicon alloy is added into the graphene oxide/carbon nanotube solution for ultrasonic treatment II, a graphene oxide reducing agent is added into an obtained suspension solution for ultrasonic treatment III, then the suspension solution is stood, filtered or centrifuged, washed to be neutral, and dried in vacuum to obtain the graphene/carbon nanotube/aluminum-silicon alloy composite material; and finally, adding the graphene/carbon nano tube/aluminum-silicon alloy composite material into an inorganic acid solution, mixing and stirring, filtering or centrifuging to be neutral, and performing vacuum drying to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material.
2. The graphene/carbon nanotube/porous silicon composite material according to claim 1, wherein the acidified carbon nanotubes are one or more of single-walled carbon nanotubes and multi-walled carbon nanotubes acidified by an inorganic acid, the inorganic acid is one or more of hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the inorganic acid is 0.5-1.5 mol/L.
3. The graphene/carbon nanotube/porous silicon composite material according to claim 1, wherein the mass ratio of the acidified carbon nanotube to the graphene oxide in the graphene oxide aqueous solution is 1: (2-4).
4. The graphene/carbon nanotube/porous silicon composite material according to claim 1, wherein the aluminum-silicon alloy has an average particle size of 1 to 5 μm, and a mass ratio of aluminum to silicon in the aluminum-silicon alloy is (4 to 9): 1.
5. the graphene/carbon nanotube/porous silicon composite material according to claim 1, wherein the mass ratio of graphene oxide to aluminum-silicon alloy in the graphene oxide/carbon nanotube solution is 1: (3-5).
6. The graphene/carbon nanotube/porous silicon composite material according to claim 1, wherein the graphene oxide reducing agent is one or more of hydrazines, sodium borohydride, ascorbic acid, sodium citrate, or tea polyphenols.
7. The graphene/carbon nanotube/porous silicon composite material as claimed in claim 1, wherein the time of the ultrasonic I is 0.5-1.5 h; the time of the ultrasonic II is 0.5-1.5 h; the time of the ultrasonic III is 1-3 h; the standing time is 12-24 h.
8. The graphene/carbon nanotube/porous silicon composite material according to claim 1, wherein the temperature of the vacuum drying is 50-70 ℃.
9. The preparation method of the graphene/carbon nanotube/porous silicon composite material according to any one of claims 1 to 8, comprising the following specific steps:
s1, adding a carbon nano tube into inorganic acid for ultrasonic treatment, washing with deionized water, and drying in vacuum to obtain an acidified carbon nano tube;
s2, adding graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide aqueous solution;
s3, adding the acidified carbon nano tube into a graphene oxide aqueous solution for ultrasonic treatment to obtain a graphene oxide/carbon nano tube composite solution;
s4, adding aluminum-silicon alloy into the graphene oxide/carbon nano tube composite solution, and performing ultrasonic treatment to obtain a suspension solution;
s5, adding a reducing agent into the suspension solution for ultrasonic treatment, and then standing, washing and vacuum drying to obtain the graphene/carbon nano tube/aluminum-silicon alloy composite material;
and S6, adding the graphene/carbon nano tube/aluminum-silicon alloy composite material into an inorganic acid solution, stirring, filtering or centrifuging, and drying in vacuum to obtain the graphene/carbon nano tube/porous silicon composite material.
10. Use of the graphene/carbon nanotube/porous silicon composite material of any one of claims 1 to 8 in the field of lithium batteries.
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