CN106410167B - A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material and preparation method thereof - Google Patents
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to material technologies, and in particular to a kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material and preparation method thereof, wherein method includes the following steps: to prepare nano-silicon ethanol solution；Prepare multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material；Mechanical stirring mixes nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material, and enters part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore；Centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore, generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material；Magneto separate separates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material with extra nano-silicon ethanol solution.Composite material prepared by the present invention has good use value on electrode material, energy storage material.
Description
Technical field
The invention belongs to material technologies, and in particular to a kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nano-silicon
Composite material and preparation method, the composite material have good use value on electrode material, energy storage material.
Background technique
The lithium ion battery negative material commercially produced mainly includes natural graphite, artificial graphite, hard carbon and soft carbon etc.,
But their capacity needs to be further improved.Become recently since silicon materials have the theoretical lithium storage content of 4200mAh/g
Research hotspot, to it, further research is expected to become the lithium ion battery negative material of next-generation high capacity, long circulation life.Mesh
Preceding silicon is that volume change is big in charge and discharge process as main problem existing for cathode, and chemical property is easy to cause to decay,
Active material is easy to fall off from conductive network, and silicon particle is caused to crack dusting, to seriously affect silica-base material
Chemical property.Nanosizing, Composite are carried out to silicon and prepare porous structure as main research direction.Nanosizing is conducive to
The diffusion path for shortening lithium ion improves the cycle performance of material, and reducing silicon particle volume change bring influences.Composite is just
It is the expansion issues for introducing " cushioning frame " in silicon based anode material and being effectively improved material.Porous structure can be silicon
Volume expansion provides certain space, to reduce bulk effect.At present mainly using carbon nanotubes and multi-layer graphene and silicon
Formed it is compound, to obtain the distribution of uniform silicon and providing silicon expansion space, through frequently with complicated technique.It is really necessary to be ground
Study carefully, to develop a kind of simple, effective, low cost, and the method that can effectively buffer the volume expansion of silicon.
Summary of the invention
For in background technique, there are problems, and the technical problem to be solved in the present invention is to provide a kind of multi-layer graphene nanometers
Carbon pipe three-dimensional carbon material fills nanometer silicon composite material and preparation method thereof.The Multi-layer graphite that the present invention utilizes applicant to invent
Alkene-multiple-wall carbon nanotube three-dimensional carbon material is template, using nano particle and the collision of multi-layer graphene-multiple-wall carbon nanotube,
So that silicon nanoparticle is packed into the gap between carbon nanotubes, and use magnetic separation technique, not entering into Multi-layer graphite
The extra nano-silicon of alkene-multiple-wall carbon nanotube three-dimensional carbon material is separated.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
A kind of preparation of multi-layer graphene of the invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material
Method includes the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution；
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material；
S30, addition multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material in nano-silicon ethanol solution, mechanical stirring,
Nano-silicon is set uniformly to mix with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material, and part nano-silicon is made to enter multilayer stone
In black alkene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore；
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material；
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.
Preferably, in S10, the quality of nano-silicon is 0.1-2.0mg/mL, ultrasound relative to the ratio between alcohol solvent volume
0.5-2h。
Preferably, S20 is specifically included:
S201 measures DMF and distilled water that volume ratio is 8:2-9:1, mixed solvent, the two volume and work is used as after mixing
It is mixed solvent volume for calculating；
S202 is added expanded graphite, sonic oscillation 2-7 hours, obtains multi-layer graphene；
Four hydration cobalt acetates and four hydration manganese acetates are added in mixed solution, stirs 5-10 minutes, solution is fallen by S203
Enter hydrothermal reaction kettle, compactedness is 20%-50% to solution in a kettle, after keeping the temperature 1-3 hours at a temperature of 100 DEG C -130 DEG C
It is cooled to room temperature；
S204, takes out reactant alcohol and water carries out eccentric cleaning each 3 times, 60 DEG C of dryings 24 in drying box after cleaning
Hour, obtain dry supported catalyst multi-layer graphene；
Quartz ampoule is heated to 500-650 DEG C of set temperature, and uses N by S2052Emptying, then by supported catalyst multilayer
Graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, it is kept for 5-20 minutes,
Middle N2Air-flow 50-200mL/min, C2H2Air-flow 20-60mL/min；
S206, in N2Protection under be cooled to room temperature after take out, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon materials
Material.
Preferably, in S30, the mass ratio of multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 1:
1-5:1, mechanical stirring 2-5 hours at room temperature.
Preferably, S40 is kept under 4500-5500r/min revolving speed specifically, the solution after stirring is poured into centrifuge tube
5-15 minutes, clear liquid is retained after centrifugation, deposit is scatter again with glass bar, re-starts centrifugal treating, by with
Upper step is centrifuged repeatedly 4~6 times.
Preferably, magnet is placed on the bottom of beaker, passed through specifically, the mixed solution after centrifugation is poured into beaker by S50
The composite material of multi-layer graphene-multiple-wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on bottom of the beaker by the magnetic action of magnet
Portion outwells the extra nano-silicon for not entering into nano-pore with ethanol solution, dry at 50-70 DEG C repeatedly after Magneto separate 3-5 times
Dry 24-48h, obtains multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon composite material in dry case.
Preferably, expanded graphite is 1.3-2.5mg/mL relative to mixed solvent.
Preferably, volume the ratio between of the weight of four hydration cobalt acetates relative to mixed solvent is 14-25mg/mL, and is added
When four hydration manganese acetates, Mn and Co atomic ratio are 5%-20%.
Preferably, the number of plies of multi-layer graphene is at 100 layers or less.
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material, is made up of the above method,
The diameter of carbon nanotubes is in 50-80cm, and the diameter grain of nano-silicon is in 60nm hereinafter, carbon nanotubes is close vertical on multi-layer graphene surface
Growing straight is long, and uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, absorption
In carbon nanotubes surface.
Using the present invention have it is following the utility model has the advantages that
1, nano-silicon prepared by the present invention enters multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore
Nano-silicon can be effectively isolated in the carbon nanotubes of gap, the distribution of multi-layer graphene surface high density, to reduce the group of nano-silicon
It is poly-.
2, gap of the nano-silicon between carbon nanotubes, gap can provide space for the volume change of nano-silicon.
3, multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material forms three-dimensional conductive network, can provide for electronics good
Good electron channel, can improve the transfer velocity of electronics, to improve the high rate performance of material.
4, multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon are prepared respectively, not by another material
Performance influence, therefore, method of the invention be multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material fill other nanometers of materials
Material method provides conventional method.
5, multilayer multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nanometer are prepared by the method for stirring, being centrifuged
The preparation method of silicon is easy, convenient for preparing composite material in batches.
Detailed description of the invention
Fig. 1 is that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention fills nano-silicon composite wood
The step flow chart of the preparation method of material；
Fig. 2 is multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material structural schematic diagram of the embodiment of the present invention；
Fig. 3 is multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material low power scanning electron microscope (SEM) photograph of the embodiment of the present invention；
Fig. 4 is multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material transmission electron microscope picture of the embodiment of the present invention；
Fig. 5 is that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention fills nano-silicon composite wood
The high power electron microscope of material；
Fig. 6 is that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention fills nano-silicon composite wood
The low power electron microscope of material；
Fig. 7 is that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention 3 fills nano-silicon composite wood
The XRD diagram of material；
Fig. 8 is that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention 3 fills nano-silicon composite wood
The charging and discharging curve figure of material.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Referring to Fig. 1, it show multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer of the embodiment of the present invention
The step flow chart of the preparation method of silicon composite comprising following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 0.1-2.0mg/mL, ultrasonic 0.5-2h relative to the ratio between alcohol solvent volume.
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measuring volume ratio is 8:
The DMF and distilled water of 2-9:1, as mixed solvent, the two volume and as mixed solvent volume for calculating after mixing；
S202 is added expanded graphite, sonic oscillation 2-7 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene at 100 layers hereinafter,
Expanded graphite is 1.3-2.5mg/mL relative to mixed solvent；Four hydration cobalt acetates and four water are added in S203 in mixed solution
Manganese acetate is closed, is stirred 5-10 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 20%-50% to solution in a kettle,
It is cooled to room temperature after keeping the temperature 1 hour at a temperature of 100 DEG C -130 DEG C, volume of the weight of four hydration cobalt acetates relative to mixed solvent
The ratio between be 14-25mg/mL, and when four hydration manganese acetates is added, Mn and Co atomic ratio are 5%-20%；S204 takes out reactant
Carried out eccentric cleaning each 3 times with alcohol and water, after cleaning in drying box 60 DEG C drying 24 hours, obtain dry supported catalyst
Agent multi-layer graphene；Quartz ampoule is heated to 500-650 DEG C of set temperature, and uses N by S2052Emptying, then by supported catalyst
Multi-layer graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, kept for 5-20 points
Clock, wherein N2Air-flow 50-200mL/min, C2H2Air-flow 20-60mL/min；S206, in N2Protection under be cooled to room temperature after take
Out, multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material is obtained.
S30, addition multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material in nano-silicon ethanol solution, mechanical stirring,
Nano-silicon is set uniformly to mix with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material, and part nano-silicon is made to enter multilayer stone
In black alkene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon materials
Expect to be 1:1-5:1 with the mass ratio of nano-silicon, mechanical stirring 2-5 hours at room temperature.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Centrifuge tube is poured into, is kept for 5-15 minutes under 4500-5500r/min revolving speed, clear liquid is retained after centrifugation, with glass bar heavy
Product object scatter again, re-starts centrifugal treating, is centrifuged repeatedly 4~6 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, and repeatedly after Magneto separate 3-5 times, dry 24-48h, obtains multilayer stone in 50-70 DEG C of drying box
Black alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon composite material.
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material as made from the above method,
The diameter of carbon nanotubes is in 50-80cm, and the diameter grain of nano-silicon is in 60nm hereinafter, carbon nanotubes is close vertical on multi-layer graphene surface
Growing straight is long, and uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, absorption
In carbon nanotubes surface, structural schematic diagram is shown in Figure 2.
Illustrate implementation process of the invention below by way of several concrete application embodiments.
Embodiment 1
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material system
Preparation Method, comprising the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 2mg, and the volume of ethanol solution is 10mL, and the quality of nano-silicon is 0.2mg/mL relative to the ratio between alcohol solvent volume, is surpassed
Sound 1h.
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measurement volume ratio is 8:2
DMF and distilled water, be used as mixed solvent after mixing, the two volume and as mixed solvent volume for calculating；S202 is added
20mg expanded graphite sonic oscillation 3 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene is at 100 layers hereinafter, expansion stone
Ink is 2mg/mL relative to mixed solvent；Four hydration cobalt acetates and four hydration manganese acetates, stirring is added in S203 in mixed solution
7 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 30% to solution in a kettle, keeps the temperature 2 hours at a temperature of 120 DEG C
After be cooled to room temperature, the weight of four hydration cobalt acetates are 200mg, body of the weight of four hydration cobalt acetates relative to mixed solvent
The ratio between product is 20mg/mL, and it is 10% that the quality of four hydration manganese acetates, which is 19.7mg, Mn and Co atomic ratio,；S204 takes out reactant
Carried out eccentric cleaning each 3 times with alcohol and water, after cleaning in drying box 60 DEG C drying 24 hours, obtain dry supported catalyst
Agent multi-layer graphene；Quartz ampoule is heated to 650 DEG C of set temperature, and uses N by S2052Emptying, then by supported catalyst multilayer
Graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, it is kept for 10 minutes, wherein
N2Air-flow 200mL/min, C2H2Air-flow 40mL/min；S206, in N2Protection under be cooled to room temperature after take out, obtain multilayer stone
Black alkene-multiple-wall carbon nanotube three-dimensional carbon material.
Multi-layer graphene-multi wall nanometer that 10mg is prepared by the method for S20 is added in S30 in nano-silicon ethanol solution
Carbon pipe three-dimensional carbon material, mechanical stirring mix nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material,
And enter part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, Multi-layer graphite
The mass ratio of alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 5:1, at room temperature mechanical stirring 2 hours.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Pour into centrifuge tube, kept for 5 minutes under 5000r/min revolving speed, clear liquid is retained after centrifugation, with glass bar deposit again
It scatter, re-starts centrifugal treating, be centrifuged repeatedly 6 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, and repeatedly after Magneto separate 5 times, dry 48h, it is more to obtain multi-layer graphene-in 60 DEG C of drying boxes
The composite material of wall carbon nanotube three-dimensional carbon material and nano-silicon.
Referring to Fig. 3 and Fig. 4, Fig. 3 is that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention is low
Times scanning electron microscope (SEM) photograph, Fig. 4 are multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material transmission electron microscope of the embodiment of the present invention
Figure, a kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material, nanometer as made from the above method
The diameter of carbon pipe is in 50cm, and the diameter grain of nano-silicon is in 60nm, and carbon nanotubes is on multi-layer graphene surface close to vertical-growth, diameter
Uniformly, it is evenly distributed, there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, is adsorbed in carbon nanotubes
Surface.
Embodiment 2
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material system
Preparation Method, comprising the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 3.3mg, and the volume of ethanol solution is 10mL, and the quality of nano-silicon is 0.33mg/mL relative to the ratio between alcohol solvent volume,
Ultrasonic 0.8h.
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measuring volume ratio is
The DMF and distilled water of 8.5:1.5, as mixed solvent, the two volume and as mixed solvent volume for calculating after mixing；
S202 is added 15mg expanded graphite, sonic oscillation 2 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene 100 layers with
Under, expanded graphite is 1.5mg/mL relative to mixed solvent；Four hydration cobalt acetates and four hydrations are added in S203 in mixed solution
Manganese acetate stirs 8 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 30% to solution in a kettle, in 100 DEG C of temperature
Lower heat preservation is cooled to room temperature after 2 hours, and the weight of four hydration cobalt acetates is 140mg, the weight of four hydration cobalt acetates relative to
The ratio between volume of mixed solvent is 14mg/mL, and it is 15% that the quality of four hydration manganese acetates, which is 20.7mg, Mn and Co atomic ratio,；
S204 takes out reactant alcohol and water and carries out eccentric cleaning each 3 times, after cleaning in drying box 70 DEG C drying 30 hours, obtain
To dry supported catalyst multi-layer graphene；Quartz ampoule is heated to 600 DEG C of set temperature, and uses N by S2052Emptying, then
Supported catalyst multi-layer graphene is placed in quartz ampoule, set temperature is risen to again to quartz ampoule temperature, is passed through N2With
C2H2, kept for 5 minutes, wherein N2Air-flow 100mL/min, C2H2Air-flow 30mL/min；S206, in N2Protection under be cooled to room temperature
After take out, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.
Multi-layer graphene-multi wall nanometer that 10mg is prepared by the method for S20 is added in S30 in nano-silicon ethanol solution
Carbon pipe three-dimensional carbon material, mechanical stirring mix nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material,
And enter part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, Multi-layer graphite
The mass ratio of alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 3:1, at room temperature mechanical stirring 4 hours.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Centrifuge tube is poured into, is kept for 15 minutes under 4500r/min revolving speed, clear liquid is retained after centrifugation, with glass bar deposit weight
It newly scatter, re-starts centrifugal treating, be centrifuged repeatedly 5 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, and repeatedly after Magneto separate 4 times, dry 40h, it is more to obtain multi-layer graphene-in 50 DEG C of drying boxes
The composite material of wall carbon nanotube three-dimensional carbon material and nano-silicon.
Referring to figs. 5 and 6, Fig. 5 is multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling of the embodiment of the present invention
The high power electron microscope of nanometer silicon composite material, Fig. 6 are multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon materials of the embodiment of the present invention
The low power electron microscope of material filling nanometer silicon composite material, a kind of multi-layer graphene carbon nanotubes as made from the above method are three-dimensional
Carbon material fills nanometer silicon composite material, and the diameter of carbon nanotubes is in 80cm, and the diameter grain of nano-silicon is in 59nm, and carbon nanotubes is more
Layer graphene surface is close to vertical-growth, and uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is equal
It is even to be filled in the gap, it is adsorbed in carbon nanotubes surface.
Embodiment 3
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material system
Preparation Method, comprising the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 5mg, and the volume of ethanol solution is 10mL, and the quality of nano-silicon is 0.5mg/mL relative to the ratio between alcohol solvent volume, is surpassed
Sound 2h.
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measurement volume ratio is 9:1
DMF and distilled water, be used as mixed solvent after mixing, the two volume and as mixed solvent volume for calculating；S202 is added
13mg expanded graphite sonic oscillation 2 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene is at 100 layers hereinafter, expansion stone
Ink is 1.3mg/mL relative to mixed solvent；Four hydration cobalt acetates and four hydration manganese acetates are added in mixed solution, stir by S203
It mixes 6 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 25% to solution in a kettle, and it is small that 3 are kept the temperature at a temperature of 100 DEG C
When after be cooled to room temperature, the weight of four hydration cobalt acetates are 140mg, and the weight of four hydration cobalt acetates is relative to mixed solvent
The ratio between volume is 14mg/mL, and it is 20% that the quality of four hydration manganese acetates, which is 27.6mg, Mn and Co atomic ratio,；S204 takes out reaction
Object alcohol and water carry out eccentric cleaning each 3 times, and 50 DEG C drying 36 hours, the load for obtaining drying are urged in drying box after cleaning
Agent multi-layer graphene；Quartz ampoule is heated to 500 DEG C of set temperature, and uses N by S2052Emptying, it is then that supported catalyst is more
Layer graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, it is kept for 5 minutes,
Middle N2Air-flow 50mL/min, C2H2Air-flow 20mL/min；S206, in N2Protection under be cooled to room temperature after take out, obtain multilayer stone
Black alkene-multiple-wall carbon nanotube three-dimensional carbon material.
Multi-layer graphene-multi wall nanometer that 10mg is prepared by the method for S20 is added in S30 in nano-silicon ethanol solution
Carbon pipe three-dimensional carbon material, mechanical stirring mix nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material,
And enter part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, Multi-layer graphite
The mass ratio of alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 2:1, at room temperature mechanical stirring 5 hours.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Centrifuge tube is poured into, is kept for 10 minutes under 5500r/min revolving speed, clear liquid is retained after centrifugation, with glass bar deposit weight
It newly scatter, re-starts centrifugal treating, be centrifuged repeatedly 5 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, and repeatedly after Magneto separate 3 times, dry 30h, it is more to obtain multi-layer graphene-in 52 DEG C of drying boxes
The composite material of wall carbon nanotube three-dimensional carbon material and nano-silicon.
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material as made from the above method,
The diameter of carbon nanotubes in 60cm, the diameter grain of nano-silicon in 55nm, carbon nanotubes on multi-layer graphene surface close to vertical-growth,
Uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, is adsorbed in nanometer
Carbon pipe surface, Fig. 7 are that multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material of the embodiment of the present invention fills nano-silicon composite wood
The XRD diagram of material, incidence angle obtain peak value when being 13.5 °, Fig. 8 is multi-layer graphene-multiple-wall carbon nanotube of the embodiment of the present invention
The charging and discharging curve figure of three-dimensional carbon material filling nanometer silicon composite material, first time charge and discharge known to charging and discharging curve three times before comparison
There are biggish irreversible capacity losses in electric process, and it is related mainly to form SEI film with electrode surface；In process of intercalation,
There is voltage platform in 0.2V or so, this voltage potential is the intercalation potential of silicon.During de- lithium, occurs one near 0.4V
Apparent voltage platform, this voltage potential are the de- lithium current potential of silicon.
Embodiment 4
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material system
Preparation Method, comprising the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 6.7mg, and the volume of ethanol solution is 10mL, and the quality of nano-silicon is 0.67mg/mL relative to the ratio between alcohol solvent volume,
Ultrasonic 1.5h.
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measurement volume ratio is 8:2
DMF and distilled water, be used as mixed solvent after mixing, the two volume and as mixed solvent volume for calculating；S202 is added
25mg expanded graphite sonic oscillation 7 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene is at 100 layers hereinafter, expansion stone
Ink is 2.5mg/mL relative to mixed solvent；Four hydration cobalt acetates and four hydration manganese acetates are added in mixed solution, stir by S203
It mixes 10 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 50% to solution in a kettle, and it is small that 2 are kept the temperature at a temperature of 120 DEG C
When after be cooled to room temperature, the weight of four hydration cobalt acetates are 250mg, and the weight of four hydration cobalt acetates is relative to mixed solvent
The ratio between volume is 25mg/mL, and it is 20% that the quality of four hydration manganese acetates, which is 49.2mg, Mn and Co atomic ratio,；S204 takes out reaction
Object alcohol and water carry out eccentric cleaning each 5 times, and 55 DEG C drying 24 hours, the load for obtaining drying are urged in drying box after cleaning
Agent multi-layer graphene；Quartz ampoule is heated to 650 DEG C of set temperature, and uses N by S2052Emptying, it is then that supported catalyst is more
Layer graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, it is kept for 20 minutes,
Middle N2Air-flow 200mL/min, C2H2Air-flow 40mL/min；S206, in N2Protection under be cooled to room temperature after take out, obtain multilayer
Graphene-multiple-wall carbon nanotube three-dimensional carbon material.
Multi-layer graphene-multi wall nanometer that 20mg is prepared by the method for S20 is added in S30 in nano-silicon ethanol solution
Carbon pipe three-dimensional carbon material, mechanical stirring mix nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material,
And enter part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, Multi-layer graphite
The mass ratio of alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 3:1, at room temperature mechanical stirring 3 hours.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Pour into centrifuge tube, kept for 8 minutes under 4750r/min revolving speed, clear liquid is retained after centrifugation, with glass bar deposit again
It scatter, re-starts centrifugal treating, be centrifuged repeatedly 4 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 5 times, in 54 DEG C of drying boxes it is dry for 24 hours, it is more to obtain multi-layer graphene-
The composite material of wall carbon nanotube three-dimensional carbon material and nano-silicon.
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material as made from the above method,
The diameter of carbon nanotubes in 70cm, the diameter grain of nano-silicon in 54nm, carbon nanotubes on multi-layer graphene surface close to vertical-growth,
Uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, is adsorbed in nanometer
Carbon pipe surface.
Embodiment 5
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material system
Preparation Method, comprising the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 10mg, and the volume of ethanol solution is 10mL, and the quality of nano-silicon is 1mg/mL, ultrasound relative to the ratio between alcohol solvent volume
1.1h。
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measuring volume ratio is
The DMF and distilled water of 8.3:1.7, as mixed solvent, the two volume and as mixed solvent volume for calculating after mixing；
S202 is added 15mg expanded graphite, sonic oscillation 5 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene 100 layers with
Under, expanded graphite is 1.5mg/mL relative to mixed solvent；Four hydration cobalt acetates and four hydrations are added in S203 in mixed solution
Manganese acetate stirs 5 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 40% to solution in a kettle, in 130 DEG C of temperature
Lower heat preservation is cooled to room temperature after 1 hour, and the weight of four hydration cobalt acetates is 180mg, the weight of four hydration cobalt acetates relative to
The ratio between volume of mixed solvent is 18mg/mL, and it is 5% that the quality of four hydration manganese acetates, which is 8.9mg, Mn and Co atomic ratio,；S204,
Reactant alcohol and water is taken out to carry out eccentric cleaning each 3 times, after cleaning in drying box 60 DEG C drying 36 hours, obtain drying
Supported catalyst multi-layer graphene；Quartz ampoule is heated to 550 DEG C of set temperature, and uses N by S2052Emptying, then will load
Catalyst multi-layer graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, keep
20 minutes, wherein N2Air-flow 200mL/min, C2H2Air-flow 60mL/min；S206, in N2Protection under be cooled to room temperature after take out,
Obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.
Multi-layer graphene-multi wall nanometer that 10mg is prepared by the method for S20 is added in S30 in nano-silicon ethanol solution
Carbon pipe three-dimensional carbon material, mechanical stirring mix nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material,
And enter part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, Multi-layer graphite
The mass ratio of alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 1:1, at room temperature mechanical stirring 5 hours.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Centrifuge tube is poured into, is kept for 13 minutes under 5250r/min revolving speed, clear liquid is retained after centrifugation, with glass bar deposit weight
It newly scatter, re-starts centrifugal treating, be centrifuged repeatedly 6 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, and repeatedly after Magneto separate 4 times, dry 36h, it is more to obtain multi-layer graphene-in 56 DEG C of drying boxes
The composite material of wall carbon nanotube three-dimensional carbon material and nano-silicon.
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material as made from the above method,
The diameter of carbon nanotubes in 65cm, the diameter grain of nano-silicon in 55nm, carbon nanotubes on multi-layer graphene surface close to vertical-growth,
Uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, is adsorbed in nanometer
Carbon pipe surface.
Embodiment 6
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material system
Preparation Method, comprising the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 20mg, and the volume of ethanol solution is 10mL, and the quality of nano-silicon is 2mg/mL, ultrasound relative to the ratio between alcohol solvent volume
2h。
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.Specifically, S201, measurement volume ratio is 8:2
DMF and distilled water, be used as mixed solvent after mixing, the two volume and as mixed solvent volume for calculating；S202 is added
13mg expanded graphite sonic oscillation 4 hours, obtains multi-layer graphene, the number of plies of multi-layer graphene is at 100 layers hereinafter, expansion stone
Ink is 1.3mg/mL relative to mixed solvent；Four hydration cobalt acetates and four hydration manganese acetates are added in mixed solution, stir by S203
It mixes 9 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 40% to solution in a kettle, and it is small that 3 are kept the temperature at a temperature of 110 DEG C
When after be cooled to room temperature, the weight of four hydration cobalt acetates are 180mg, and the weight of four hydration cobalt acetates is relative to mixed solvent
The ratio between volume is 18mg/mL, and it is 5% that the quality of four hydration manganese acetates, which is 8.9mg, Mn and Co atomic ratio,；S204 takes out reactant
Carried out eccentric cleaning each 4 times with alcohol and water, after cleaning in drying box 60 DEG C drying 48 hours, obtain dry supported catalyst
Agent multi-layer graphene；Quartz ampoule is heated to 575 DEG C of set temperature, and uses N by S2052Emptying, then by supported catalyst multilayer
Graphene is placed in quartz ampoule, is risen to set temperature again to quartz ampoule temperature, is passed through N2And C2H2, it is kept for 15 minutes, wherein
N2Air-flow 125mL/min, C2H2Air-flow 50mL/min；S206, in N2Protection under be cooled to room temperature after take out, obtain multilayer stone
Black alkene-multiple-wall carbon nanotube three-dimensional carbon material.
Multi-layer graphene-multi wall nanometer that 80mg is prepared by the method for S20 is added in S30 in nano-silicon ethanol solution
Carbon pipe three-dimensional carbon material, mechanical stirring mix nano-silicon uniformly with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material,
And enter part nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore.Specifically, Multi-layer graphite
The mass ratio of alkene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is 4:1, at room temperature mechanical stirring 3 hours.
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore,
It generates multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and fills nanometer silicon composite material.Specifically, by the solution after stirring
Centrifuge tube is poured into, is kept for 11 minutes under 5400r/min revolving speed, clear liquid is retained after centrifugation, with glass bar deposit weight
It newly scatter, re-starts centrifugal treating, be centrifuged repeatedly 6 times by above step.
S50, Magneto separate make multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and extra nano-silicon ethanol solution
It is dry after separation, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours into beaker, and magnet is placed on to the bottom of beaker, by the magnetic action of magnet that multi-layer graphene-is more
The composite material of wall carbon nanotube nano-carbon material and nano-silicon is adsorbed on beaker bottom, will not enter into the extra of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 3 times, in 58 DEG C of drying boxes it is dry for 24 hours, it is more to obtain multi-layer graphene-
The composite material of wall carbon nanotube three-dimensional carbon material and nano-silicon.
A kind of multi-layer graphene carbon nanotubes three-dimensional carbon material filling nanometer silicon composite material as made from the above method,
The diameter of carbon nanotubes in 55cm, the diameter grain of nano-silicon in 57nm, carbon nanotubes on multi-layer graphene surface close to vertical-growth,
Uniform diameter is evenly distributed, and there are gap between carbon nanotubes, silicon nanoparticle is uniformly filled in the gap, is adsorbed in nanometer
Carbon pipe surface.
It should be appreciated that exemplary embodiment as described herein is illustrative and be not restrictive.Although being retouched in conjunction with attached drawing
One or more embodiments of the invention is stated, it should be understood by one skilled in the art that not departing from through appended right
In the case where the spirit and scope of the present invention defined by it is required that, the change of various forms and details can be made.
Claims (10)
1. a kind of multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material preparation method, special
Sign is, includes the following steps:
Nano-silicon is added in S10 in ethanol solution, and ultrasound prepares nano-silicon ethanol solution；
S20 prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material；
S30, is added multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material in nano-silicon ethanol solution, and mechanical stirring makes to receive
Rice silicon uniformly mixes with multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material, and part nano-silicon is made to enter multi-layer graphene-
In the nano-pore of multiple-wall carbon nanotube three-dimensional carbon material；
S40, centrifugation, is sputtered nano-silicon in multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material nano-pore, generates
Multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material；
S50, Magneto separate separate multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material with extra nano-silicon ethanol solution
Afterwards, dry, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material filling nanometer silicon composite material.
2. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that in S10, the quality of the nano-silicon is 0.1mg/mL- relative to the ratio between alcohol solvent volume
2.0mg/mL, ultrasonic 0.5-2h.
3. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that S20 is specifically included:
S201 measures DMF and distilled water that volume ratio is 8:2-9:1, as mixed solvent, the two volume and as mixed after mixing
Bonding solvent volume is for calculating；
S202 is added expanded graphite, sonic oscillation 2-7 hours, obtains multi-layer graphene；
Four hydration cobalt acetates and four hydration manganese acetates are added in mixed solution, stirs 5-10 minutes, solution is poured into water by S203
Thermal response kettle, compactedness is 20%-50% to solution in a kettle, cooling after keeping the temperature 1-3 hours at a temperature of 100 DEG C -130 DEG C
To room temperature；
S204, takes out reactant alcohol and water carries out eccentric cleaning each 3 times, and 60 DEG C of dryings 24 are small in drying box after cleaning
When, obtain dry supported catalyst multi-layer graphene；
Quartz ampoule is heated to 500-650 DEG C of set temperature, and uses N by S2052Emptying, then by supported catalyst multi-layer graphene
It is placed in quartz ampoule, rises to set temperature again to quartz ampoule temperature, be passed through N2And C2H2, kept for 5-20 minutes, wherein N2Gas
Flow 50-200mL/min, C2H2Air-flow 20-60mL/min；
S206, in N2Protection under be cooled to room temperature after take out, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material.
4. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that in S30, the quality of multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon it
Than for 1:1-5:1, mechanical stirring 2-5 hours at room temperature.
5. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that S40 is specifically, pour into centrifuge tube for the solution after stirring, in 4500-5500r/min revolving speed
Lower holding 5-15 minutes, retains clear liquid after centrifugation, deposit is scatter again with glass bar, is re-started at centrifugation
Reason, is centrifuged repeatedly 4~6 times by above step.
6. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that magnet is placed on the bottom of beaker specifically, the mixed solution after centrifugation is poured into beaker by S50
The composite material of multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon is adsorbed by the magnetic action of magnet in portion
In beaker bottom, the extra nano-silicon for not entering into nano-pore is outwelled with ethanol solution, repeatedly after Magneto separate 3-5 times,
Dry 24-48h in 50-70 DEG C of drying box obtains the compound of multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon material and nano-silicon
Material.
7. multi-layer graphene according to claim 3-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that expanded graphite relative to mixed solvent be 1.3-2.5mg/mL.
8. multi-layer graphene according to claim 3-multiple-wall carbon nanotube three-dimensional carbon material fills nanometer silicon composite material
Preparation method, which is characterized in that the ratio between volume relative to mixed solvent of weight of four hydration cobalt acetates is 14-25mg/mL,
And when four hydration manganese acetates is added, Mn and Co atomic ratio are 5%-20%.
9. multi-layer graphene described according to claim 1 or 3 or 7 or 8-multiple-wall carbon nanotube three-dimensional carbon material fills nano-silicon
The preparation method of composite material, which is characterized in that the number of plies of multi-layer graphene is at 100 layers or less.
10. a kind of multi-layer graphene carbon nanotubes three-dimensional carbon material fills nanometer silicon composite material, which is characterized in that by such as weighing
Benefit requires any preparation method of 1-9 to be made, and in 50-80cm, the diameter grain of nano-silicon exists the diameter of the carbon nanotubes
60nm hereinafter, carbon nanotubes on multi-layer graphene surface close to vertical-growth, uniform diameter is evenly distributed, between carbon nanotubes
There are gap, silicon nanoparticle is uniformly filled in the gap, is adsorbed in carbon nanotubes surface.
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| CN105036117A (en) * | 2015-09-08 | 2015-11-11 | 杭州电子科技大学 | Multilayer graphene and multi-walled carbon nanotube three-dimensional carbon material and preparation method thereof |
| CN105576194A (en) * | 2014-10-10 | 2016-05-11 | 南京工业大学 | Preparation method of graphene-carbon nanotube aerogel supported nano-silicon composite electrode material |
| CN105762337A (en) * | 2016-01-22 | 2016-07-13 | 三峡大学 | Silicon/graphene/carbon fiber composite cathode material and preparation method thereof |
| CN105958071A (en) * | 2016-07-11 | 2016-09-21 | 杭州电子科技大学 | Three-dimensional porous carbon material with carbon nanotubes vertically grown on multilayer graphene surface, preparation method and lithium ion battery applying material |
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| CN104993109A (en) * | 2015-06-02 | 2015-10-21 | 北京航空航天大学 | Method for preparation of graphene/nano-silicon lithium ion battery cathode material by liquid phase physical technique |
| CN105036117A (en) * | 2015-09-08 | 2015-11-11 | 杭州电子科技大学 | Multilayer graphene and multi-walled carbon nanotube three-dimensional carbon material and preparation method thereof |
| CN105762337A (en) * | 2016-01-22 | 2016-07-13 | 三峡大学 | Silicon/graphene/carbon fiber composite cathode material and preparation method thereof |
| CN105958071A (en) * | 2016-07-11 | 2016-09-21 | 杭州电子科技大学 | Three-dimensional porous carbon material with carbon nanotubes vertically grown on multilayer graphene surface, preparation method and lithium ion battery applying material |
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