CN106410167A - Multi-layer graphene carbon nanotube three-dimensional carbon material-filled nanometer silicon composite material and preparation method thereof - Google Patents
Multi-layer graphene carbon nanotube three-dimensional carbon material-filled nanometer silicon composite material and preparation method thereof Download PDFInfo
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- CN106410167A CN106410167A CN201611112238.9A CN201611112238A CN106410167A CN 106410167 A CN106410167 A CN 106410167A CN 201611112238 A CN201611112238 A CN 201611112238A CN 106410167 A CN106410167 A CN 106410167A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention belongs to a material technique, and particularly relates to a multi-layer graphene carbon nanotube three-dimensional carbon material-filled nanometer silicon composite material and a preparation method thereof. The preparation method comprises the following steps of preparing a nanometer silicon ethanol solution; preparing a multi-layer graphene-multi-wall carbon nanotube three-dimensional carbon material; mechanically stirring, thus uniformly mixing nanometer silicon and the multi-layer graphene-multi-wall carbon nanotube three-dimensional carbon material, and enabling one part of the nanometer silicon to enter nanometer holes of the multi-layer graphene-multi-wall carbon nanotube three-dimensional carbon material; centrifuging, spattering the nanometer silicon into the nanometer holes of the multi-layer graphene-multi-wall carbon nanotube three-dimensional carbon material, and generating a multi-layer graphene-multi-wall carbon nanotube three-dimensional carbon material-filled nanometer silicon composite material; magnetically separating the multi-layer graphene-multi-wall carbon nanotube three-dimensional carbon material from the excessive nanometer silicon ethanol solution. The prepared multi-layer graphene carbon nanotube three-dimensional carbon material-filled nanometer silicon composite material has good application value on electrode materials and energy-storage materials.
Description
Technical field
The invention belongs to material technology is and in particular to a kind of multi-layer graphene CNT three-dimensional material with carbon element fills nano-silicon
Composite and preparation method thereof, this composite has good use value on electrode material, energy storage material.
Background technology
The lithium ion battery negative material commercially produced mainly includes native graphite, Delanium, hard carbon and soft carbon etc.,
But their capacity awaits improving further.Become because silicon materials have the theoretical lithium storage content of 4200mAh/g recently
Study hotspot, studies, to it, the lithium ion battery negative material being expected to become high power capacity of future generation, long circulation life further.Mesh
The subject matter that front silicon exists as negative pole is that change in volume is big in charge and discharge process, is easily caused chemical property decay,
Active substance easily comes off from conductive network, and leads to silicon grain to crack efflorescence, thus having a strong impact on silica-base material
Chemical property.Silicon is carried out with nanorize, Composite and prepares the research direction that loose structure becomes main.Nanorize is conducive to
Shorten the evolving path of lithium ion, improve the cycle performance of material, reduce the impact that silicon grain change in volume is brought.Composite is just
It is to introduce the expansion issues that " cushioning frame " can be effectively improved material in silicon based anode material.Loose structure can be silicon
Volumetric expansion provides certain space, thus reducing bulk effect.Mainly adopt CNT and multi-layer graphene and silicon at present
Formed compound, for obtaining uniform silicon distribution and providing silicon expansion space, through frequently with complicated technique.It is necessary to be ground in fact
Study carefully, a kind of simple, effective, inexpensive to develop, and the method that can effectively buffer the volumetric expansion of silicon.
Content of the invention
Have problems in background technology, the technical problem to be solved in the present invention is to provide a kind of multi-layer graphene nanometer
Carbon pipe three-dimensional material with carbon element filling nanometer silicon composite material and preparation method thereof.The present invention utilizes the Multi-layer graphite of applicant's invention
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element is template, using the collision of nano-particle and multi-layer graphene-multiple-wall carbon nanotube,
Make silicon nanoparticle be packed into the space between CNT, and adopt magnetic separation technique, not entering into Multi-layer graphite
The unnecessary nano-silicon of alkene-multiple-wall carbon nanotube three-dimensional material with carbon element carries out separating.
For solving above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of multi-layer graphene of the present invention-multiple-wall carbon nanotube three-dimensional material with carbon element fills the preparation of nanometer silicon composite material
Method, comprises the steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution；
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element；
S30, addition multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element in nano-silicon ethanol solution, mechanical agitation,
Nano-silicon is made uniformly to mix, and make part nano-silicon enter multilamellar stone with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element
The nanometer in the hole of black alkene-multiple-wall carbon nanotube three-dimensional material with carbon element；
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material；
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.
Preferably, in S10, the quality of nano-silicon is 0.1-2.0mg/mL with respect to the ratio of alcohol solvent volume, ultrasonic
0.5-2h.
Preferably, S20 specifically includes：
S201, measures the DMF that volume ratio is 8: 2-9: 1 and distilled water, as mixed solvent after mixing, both volumes and work
It is used for calculating for mixed solvent volume；
S202, adds expanded graphite, sonic oscillation 2-7 hour, obtains multi-layer graphene；
S203, adds four hydration cobaltous acetate and four hydration manganese acetates in mixed solution, stirs 5-10 minute, solution is fallen
Enter hydrothermal reaction kettle, compactedness is 20%-50% to solution in a kettle., after insulation 1-3 hour at a temperature of 100 DEG C -130 DEG C
It is cooled to room temperature；
S204, takes out reactant ethanol and water and carries out each 3 times of eccentric cleaning, 60 DEG C of dryings 24 in drying baker after cleaning
Hour, obtain the supported catalyst multi-layer graphene of drying；
S205, quartz ampoule is heated to 500-650 DEG C of design temperature, and uses N2Emptying, then by supported catalyst multilamellar
Graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, keep 5-20 minute, its
Middle N2Air-flow 50-200mL/min, C2H2Air-flow 20-60mL/min；
S206, in N2Protection under be cooled to and take out after room temperature, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon materials
Material.
Preferably, in S30, multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 1:
1-5: 1, mechanical agitation 2-5 hour under room temperature.
Preferably, S40, specifically, pouring the solution after stirring into centrifuge tube, keeps under 4500-5500r/min rotating speed
5-15 minute, centrifugation terminate after retain clear liquid, with Glass rod, deposit is scatter again, re-starts centrifugal treating, by with
Upper step is centrifuged repeatedly 4～6 times.
Preferably, S50, specifically, pouring the mixed solution after centrifugation into beaker, Magnet is placed on the bottom of beaker, passes through
The magnetic action of Magnet adsorbs the composite of multi-layer graphene-multiple-wall carbon nanotube nano-carbon material and nano-silicon in bottom of the beaker
Portion, the unnecessary nano-silicon not entering into nano-pore is outwelled with ethanol solution, repeatedly after Magneto separate 3-5 time, dry at 50-70 DEG C
24-48h is dried in dry case, obtains the composite of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and nano-silicon.
Preferably, expanded graphite is 1.3-2.5mg/mL with respect to mixed solvent.
Preferably, the weight of four hydration cobaltous acetate is 14-25mg/mL with respect to the ratio of the volume of mixed solvent, and adds
During four hydration manganese acetates, Mn and Co atomic ratio are 5%-20%.
Preferably, the number of plies of multi-layer graphene is below 100 layers.
A kind of multi-layer graphene CNT three-dimensional material with carbon element filling nanometer silicon composite material, is made by said method,
, in 50-80cm, in below 60nm, CNT is on multi-layer graphene surface close to vertical for the footpath grain of nano-silicon for the diameter of CNT
Straight growth, uniform diameter, it is evenly distributed, between CNT, there is space, silicon nanoparticle is uniformly filled in a nanometer air, inhale
Invest CNT surface.
Following beneficial effect is had using the present invention：
1st, the nano-silicon of present invention preparation enters into the nano-pore of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element
Gap, the CNT of multi-layer graphene surface high density distribution can effectively isolate nano-silicon, thus reducing the group of nano-silicon
Poly-.
2nd, nano-silicon is located at the space between CNT, and space can provide space for the change in volume of nano-silicon.
3rd, multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element composition three-dimensional conductive network, can provide good for electronics
Good electron channel, can improve the transfer velocity of electronics, thus improving the high rate performance of material.
4th, multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and nano-silicon are prepared respectively, are not subject to another kind of material
Performance impact, therefore, the method for the present invention is the other nanometer materials of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling
Material method provides conventional method.
5th, pass through stirring, the method for centrifugation prepares multilamellar multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and nanometer
The preparation method is simple of silicon, is easy to batch and prepares composite.
Brief description
Fig. 1 is the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon composite wood of the embodiment of the present invention
The flow chart of steps of the preparation method of material；
Fig. 2 is the structural representation of the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element of the embodiment of the present invention；
Fig. 3 is the low power scanning electron microscope (SEM) photograph of the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element of the embodiment of the present invention；
Fig. 4 is the transmission electron microscope picture of the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element of the embodiment of the present invention；
Fig. 5 is the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon composite wood of the embodiment of the present invention
The high power electron microscope of material；
Fig. 6 is the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon composite wood of the embodiment of the present invention
The low power electron microscope of material；
Fig. 7 is the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon composite wood of the embodiment of the present invention 3
The XRD figure of material；
Fig. 8 is the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon composite wood of the embodiment of the present invention 3
The charging and discharging curve figure of material.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation description is it is clear that described embodiment a part of embodiment that is the present invention, rather than whole embodiments.Based on this
Embodiment in bright, the every other enforcement that those of ordinary skill in the art are obtained under the premise of not making creative work
Example, broadly falls into the scope of protection of the invention.
Referring to Fig. 1, it show the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer of the embodiment of the present invention
The flow chart of steps of the preparation method of silicon composite, it comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Amount is 0.1-2.0mg/mL, ultrasonic 0.5-2h with respect to the ratio of alcohol solvent volume.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is 8:
2-9: 1 DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；
S202, add expanded graphite, sonic oscillation 2-7 hour, obtain multi-layer graphene, the number of plies of multi-layer graphene below 100 layers,
Expanded graphite is 1.3-2.5mg/mL with respect to mixed solvent；S203, adds four hydration cobaltous acetate and four water in mixed solution
Close manganese acetate, stir 5-10 minute, solution is poured into hydrothermal reaction kettle, compactedness is 20%-50% to solution in a kettle.,
At a temperature of 100 DEG C -130 DEG C, insulation is cooled to room temperature after 1 hour, and four are hydrated the volume with respect to mixed solvent for the weight of cobaltous acetate
Ratio be 14-25mg/mL, and when adding four hydration manganese acetates, Mn and Co atomic ratio are 5%-20%；S204, takes out reactant
Carry out each 3 times of eccentric cleaning with ethanol and water, after cleaning in drying baker 60 DEG C of dryings 24 hours, obtain the supported catalyst of drying
Agent multi-layer graphene；S205, quartz ampoule is heated to 500-650 DEG C of design temperature, and uses N2Emptying, then by supported catalyst
Multi-layer graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, keep 5-20 to divide
Clock, wherein N2Air-flow 50-200mL/min, C2H2Air-flow 20-60mL/min；S206, in N2Protection under be cooled to room temperature after take
Go out, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, addition multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element in nano-silicon ethanol solution, mechanical agitation,
Nano-silicon is made uniformly to mix, and make part nano-silicon enter multilamellar stone with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element
The nanometer in the hole of black alkene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, multi-layer graphene-multiple-wall carbon nanotube three-dimensional carbon materials
Material is 1: 1-5: 1 with the mass ratio of nano-silicon, mechanical agitation 2-5 hour under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 5-15 minute under 4500-5500r/min rotating speed, centrifugation retains clear liquid after terminating, with Glass rod heavy
Long-pending thing 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 material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 3-5 time, 24-48h is dried, obtains multilamellar stone in 50-70 DEG C of drying baker
Black alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Nanometer silicon composite material is filled by a kind of multi-layer graphene CNT three-dimensional material with carbon element that said method is obtained,
, in 50-80cm, in below 60nm, CNT is on multi-layer graphene surface close to vertical for the footpath grain of nano-silicon for the diameter of CNT
Straight growth, uniform diameter, it is evenly distributed, between CNT, there is space, silicon nanoparticle is uniformly filled in a nanometer air, inhale
Invest CNT surface, its structural representation is shown in Figure 2.
The implementation process of the present invention to be described 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 material with carbon element fills the system of nanometer silicon composite material
Preparation Method, comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Measure as 2mg, the volume of ethanol solution is 10mL, the quality of nano-silicon is 0.2mg/mL with respect to the ratio of alcohol solvent volume, surpasses
Sound 1h.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is 8: 2
DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；S202, adds
20mg expanded graphite, sonic oscillation 3 hours, obtain multi-layer graphene, the number of plies of multi-layer graphene, below 100 layers, expands stone
Ink is 2mg/mL with respect to mixed solvent；S203, adds four hydration cobaltous acetate and four hydration manganese acetates, stirring in mixed solution
7 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 30% to solution in a kettle., is incubated 2 hours at a temperature of 120 DEG C
After be cooled to room temperature, the weight of four hydration cobaltous acetate for 200mg, the weight of four hydration cobaltous acetate is with respect to the body of mixed solvent
Long-pending ratio is 20mg/mL, and the quality of four hydration manganese acetates is 10% for 19.7mg, Mn and Co atomic ratio；S204, takes out reactant
Carry out each 3 times of eccentric cleaning with ethanol and water, after cleaning in drying baker 60 DEG C of dryings 24 hours, obtain the supported catalyst of drying
Agent multi-layer graphene；S205, quartz ampoule is heated to 650 DEG C of design temperature, and uses N2Emptying, then by supported catalyst multilamellar
Graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, holding 10 minutes, wherein
N2Air-flow 200mL/min, C2H2Air-flow 40mL/min；S206, in N2Protection under be cooled to and take out after room temperature, obtain multilamellar stone
Black alkene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, adds 10mg by multi-layer graphene-many walls nanometer of the method preparation of S20 in nano-silicon ethanol solution
Carbon pipe three-dimensional material with carbon element, mechanical agitation, so that nano-silicon is uniformly mixed with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
And make part nano-silicon enter the nanometer in the hole of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, Multi-layer graphite
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 5: 1, mechanical agitation 2 hours under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 5 minutes under 5000r/min rotating speed, centrifugation retains clear liquid, with Glass rod deposit again after terminating
It scatter, re-start centrifugal treating, be centrifuged repeatedly 6 times by above step.
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 5 times, 48h is dried in 60 DEG C of drying baker, obtains multi-layer graphene-many
Wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Referring to Fig. 3 and Fig. 4, Fig. 3 is the low of the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element of the embodiment of the present invention
Times scanning electron microscope (SEM) photograph, Fig. 4 is the transmission electron microscope of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element of the embodiment of the present invention
Figure, fills nanometer silicon composite material, nanometer by a kind of multi-layer graphene CNT three-dimensional material with carbon element that said method is obtained
, in 50cm, in 60nm, CNT is on multi-layer graphene surface close to vertical-growth, diameter for the footpath grain of nano-silicon for the diameter of carbon pipe
Uniformly, it is evenly distributed, between CNT, there is space, silicon nanoparticle is uniformly filled in a nanometer air, is adsorbed in nano-sized carbon
Pipe surface.
Embodiment 2
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional material with carbon element fills the system of nanometer silicon composite material
Preparation Method, comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Measure as 3.3mg, the volume of ethanol solution is 10mL, the quality of nano-silicon is 0.33mg/mL with respect to the ratio of alcohol solvent volume,
Ultrasonic 0.8h.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is 8.5
: 1.5 DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；S202,
Add 15mg expanded graphite, sonic oscillation 2 hours, obtain multi-layer graphene, the number of plies of multi-layer graphene is below 100 layers, swollen
Swollen graphite-phase is 1.5mg/mL for mixed solvent；S203, adds four hydration cobaltous acetate and four hydration acetic acid in mixed solution
Manganese, stirs 8 minutes, solution is poured into hydrothermal reaction kettle, and compactedness is 30% to solution in a kettle., protects at a temperature of 100 DEG C
Temperature was cooled to room temperature after 2 hours, the weight of four hydration cobaltous acetate for 140mg, the weight of four hydration cobaltous acetate is with respect to mixing
The ratio of the volume of solvent is 14mg/mL, and the quality of four hydration manganese acetates is 15% for 20.7mg, Mn and Co atomic ratio；S204, takes
Go out reactant ethanol and water carry out each 3 times of eccentric cleaning, after cleaning in drying baker 70 DEG C of dryings 30 hours, obtain drying
Supported catalyst multi-layer graphene；S205, quartz ampoule is heated to 600 DEG C of design temperature, and uses N2Then load is urged by emptying
Agent multi-layer graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, keep 5 points
Clock, wherein N2Air-flow 100mL/min, C2H2Air-flow 30mL/min；S206, in N2Protection under be cooled to and take out after room temperature, obtain
Multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, adds 10mg by multi-layer graphene-many walls nanometer of the method preparation of S20 in nano-silicon ethanol solution
Carbon pipe three-dimensional material with carbon element, mechanical agitation, so that nano-silicon is uniformly mixed with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
And make part nano-silicon enter the nanometer in the hole of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, Multi-layer graphite
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 3: 1, mechanical agitation 4 hours under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 15 minutes under 4500r/min rotating speed, centrifugation retains clear liquid, with Glass rod deposit weight after terminating
Newly it scatter, re-start centrifugal treating, be centrifuged repeatedly 5 times by above step.
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 4 times, 40h is dried in 50 DEG C of drying baker, obtains multi-layer graphene-many
Wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Referring to Fig. 5 and Fig. 6, Fig. 5 is the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling of the embodiment of the present invention
The high power electron microscope of nanometer silicon composite material, Fig. 6 is the 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 CNT being obtained by said method is three-dimensional
Material with carbon element fills nanometer silicon composite material, and, in 80cm, in 59nm, CNT is many for the footpath grain of nano-silicon for the diameter of CNT
Layer graphene surface, close to vertical-growth, uniform diameter, is evenly distributed, and there is space between CNT, and silicon nanoparticle is equal
Even be filled in a nanometer air, be adsorbed in CNT surface.
Embodiment 3
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional material with carbon element fills the system of nanometer silicon composite material
Preparation Method, comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Measure as 5mg, the volume of ethanol solution is 10mL, the quality of nano-silicon is 0.5mg/mL with respect to the ratio of alcohol solvent volume, surpasses
Sound 2h.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is 9: 1
DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；S202, adds
13mg expanded graphite, sonic oscillation 2 hours, obtain multi-layer graphene, the number of plies of multi-layer graphene, below 100 layers, expands stone
Ink is 1.3mg/mL with respect to mixed solvent；S203, adds four hydration cobaltous acetate and four hydration manganese acetates in mixed solution, stirs
Mix 6 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 25% to solution in a kettle., and insulation 3 is little at a temperature of 100 DEG C
When after be cooled to room temperature, the weight of four hydration cobaltous acetate for 140mg, the weight of four hydration cobaltous acetate is with respect to mixed solvent
The ratio of volume is 14mg/mL, and the quality of four hydration manganese acetates is 20% for 27.6mg, Mn and Co atomic ratio；S204, takes out reaction
Thing ethanol and water carry out each 3 times of eccentric cleaning, after cleaning in drying baker 50 DEG C of dryings 36 hours, the load obtaining drying is urged
Agent multi-layer graphene；S205, quartz ampoule is heated to 500 DEG C of design temperature, and uses N2Emptying, then that supported catalyst is many
Layer graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, keep 5 minutes, its
Middle N2Air-flow 50mL/min, C2H2Air-flow 20mL/min；S206, in N2Protection under be cooled to and take out after room temperature, obtain multilamellar stone
Black alkene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, adds 10mg by multi-layer graphene-many walls nanometer of the method preparation of S20 in nano-silicon ethanol solution
Carbon pipe three-dimensional material with carbon element, mechanical agitation, so that nano-silicon is uniformly mixed with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
And make part nano-silicon enter the nanometer in the hole of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, Multi-layer graphite
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 2: 1, mechanical agitation 5 hours under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 10 minutes under 5500r/min rotating speed, centrifugation retains clear liquid, with Glass rod deposit weight after terminating
Newly it scatter, re-start centrifugal treating, be centrifuged repeatedly 5 times by above step.
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 3 times, 30h is dried in 52 DEG C of drying baker, obtains multi-layer graphene-many
Wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Nanometer silicon composite material is filled by a kind of multi-layer graphene CNT three-dimensional material with carbon element that said method is obtained,
The diameter of CNT in 60cm, the footpath grain of nano-silicon in 55nm, CNT on multi-layer graphene surface close to vertical-growth,
Uniform diameter, is evenly distributed, and there is space between CNT, and silicon nanoparticle is uniformly filled in a nanometer air, is adsorbed in and receives
Rice carbon pipe surface, Fig. 7 is that the multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon of the embodiment of the present invention is combined
The XRD figure of material, angle of incidence is to obtain peak value when 13.5 °, and Fig. 8 is multi-layer graphene-many walls nano-sized carbon of the embodiment of the present invention
Pipe three-dimensional material with carbon element fills the charging and discharging curve figure of nanometer silicon composite material, contrasts first three charging and discharging curve and understands to fill for the first time
There is larger irreversible capacity loss in discharge process, main relevant with electrode surface formation SEI film；In process of intercalation,
0.2V about voltage platform occurs, this voltage potential be silicon intercalation potential.During de- lithium, near 0.4V, occurs one
Significantly voltage platform, this voltage potential is 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 material with carbon element fills the system of nanometer silicon composite material
Preparation Method, comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Measure as 6.7mg, the volume of ethanol solution is 10mL, the quality of nano-silicon is 0.67mg/mL with respect to the ratio of alcohol solvent volume,
Ultrasonic 1.5h.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is 8: 2
DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；S202, adds
25mg expanded graphite, sonic oscillation 7 hours, obtain multi-layer graphene, the number of plies of multi-layer graphene, below 100 layers, expands stone
Ink is 2.5mg/mL with respect to mixed solvent；S203, adds four hydration cobaltous acetate and four hydration manganese acetates in mixed solution, stirs
Mix 10 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 50% to solution in a kettle., and insulation 2 is little at a temperature of 120 DEG C
When after be cooled to room temperature, the weight of four hydration cobaltous acetate for 250mg, the weight of four hydration cobaltous acetate is with respect to mixed solvent
The ratio of volume is 25mg/mL, and the quality of four hydration manganese acetates is 20% for 49.2mg, Mn and Co atomic ratio；S204, takes out reaction
Thing ethanol and water carry out each 5 times of eccentric cleaning, after cleaning in drying baker 55 DEG C of dryings 24 hours, the load obtaining drying is urged
Agent multi-layer graphene；S205, quartz ampoule is heated to 650 DEG C of design temperature, and uses N2Emptying, then that supported catalyst is many
Layer graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, keep 20 minutes, its
Middle N2Air-flow 200mL/min, C2H2Air-flow 40mL/min；S206, in N2Protection under be cooled to and take out after room temperature, obtain multilamellar
Graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, adds 20mg by multi-layer graphene-many walls nanometer of the method preparation of S20 in nano-silicon ethanol solution
Carbon pipe three-dimensional material with carbon element, mechanical agitation, so that nano-silicon is uniformly mixed with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
And make part nano-silicon enter the nanometer in the hole of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, Multi-layer graphite
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 3: 1, mechanical agitation 3 hours under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 8 minutes under 4750r/min rotating speed, centrifugation retains clear liquid, with Glass rod deposit again after terminating
It scatter, re-start centrifugal treating, be centrifuged repeatedly 4 times by above step.
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 5 times, 24h is dried in 54 DEG C of drying baker, obtains multi-layer graphene-many
Wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Nanometer silicon composite material is filled by a kind of multi-layer graphene CNT three-dimensional material with carbon element that said method is obtained,
The diameter of CNT in 70cm, the footpath grain of nano-silicon in 54nm, CNT on multi-layer graphene surface close to vertical-growth,
Uniform diameter, is evenly distributed, and there is space between CNT, and silicon nanoparticle is uniformly filled in a nanometer air, is adsorbed in and receives
Rice carbon pipe surface.
Embodiment 5
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional material with carbon element fills the system of nanometer silicon composite material
Preparation Method, comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Measure as 10mg, the volume of ethanol solution is 10mL, the quality of nano-silicon is 1mg/mL with respect to the ratio of alcohol solvent volume, ultrasonic
1.1h.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is
8.3：1.7 DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；
S202, adds 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 with respect to mixed solvent；S203, adds four hydration cobaltous acetate and four hydrations in mixed solution
Manganese acetate, stirs 5 minutes, solution is poured into hydrothermal reaction kettle, and compactedness is 40% to solution in a kettle., in 130 DEG C of temperature
Lower insulation was cooled to room temperature after 1 hour, the weight of four hydration cobaltous acetate for 180mg, the weight of four hydration cobaltous acetate with respect to
The ratio of the volume of mixed solvent is 18mg/mL, and the quality of four hydration manganese acetates is 5% for 8.9mg, Mn and Co atomic ratio；S204,
Take out reactant ethanol and water and carry out each 3 times of eccentric cleaning, after cleaning in drying baker 60 DEG C of dryings 36 hours, obtain drying
Supported catalyst multi-layer graphene；S205, quartz ampoule is heated to 550 DEG C of design temperature, and uses N2Emptying, then will load
Catalyst multi-layer graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, keep
20 minutes, wherein N2Air-flow 200mL/min, C2H2Air-flow 60mL/min；S206, in N2Protection under be cooled to and take out after room temperature,
Obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, adds 10mg by multi-layer graphene-many walls nanometer of the method preparation of S20 in nano-silicon ethanol solution
Carbon pipe three-dimensional material with carbon element, mechanical agitation, so that nano-silicon is uniformly mixed with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
And make part nano-silicon enter the nanometer in the hole of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, Multi-layer graphite
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 1: 1, mechanical agitation 5 hours under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 13 minutes under 5250r/min rotating speed, centrifugation retains clear liquid, with Glass rod deposit weight after terminating
Newly it scatter, re-start centrifugal treating, be centrifuged repeatedly 6 times by above step.
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 4 times, 36h is dried in 56 DEG C of drying baker, obtains multi-layer graphene-many
Wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Nanometer silicon composite material is filled by a kind of multi-layer graphene CNT three-dimensional material with carbon element that said method is obtained,
The diameter of CNT in 65cm, the footpath grain of nano-silicon in 55nm, CNT on multi-layer graphene surface close to vertical-growth,
Uniform diameter, is evenly distributed, and there is space between CNT, and silicon nanoparticle is uniformly filled in a nanometer air, is adsorbed in and receives
Rice carbon pipe surface.
Embodiment 6
The multi-layer graphene of the embodiment of the present invention-multiple-wall carbon nanotube three-dimensional material with carbon element fills the system of nanometer silicon composite material
Preparation Method, comprises the following steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution.Specifically, the matter of nano-silicon
Measure as 20mg, the volume of ethanol solution is 10mL, the quality of nano-silicon is 2mg/mL with respect to the ratio of alcohol solvent volume, ultrasonic
2h.
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, S201, measuring volume ratio is 8: 2
DMF and distilled water, as mixed solvent after mixing, both volumes and be used for calculating as mixed solvent volume；S202, adds
13mg expanded graphite, sonic oscillation 4 hours, obtain multi-layer graphene, the number of plies of multi-layer graphene, below 100 layers, expands stone
Ink is 1.3mg/mL with respect to mixed solvent；S203, adds four hydration cobaltous acetate and four hydration manganese acetates in mixed solution, stirs
Mix 9 minutes, solution is poured into hydrothermal reaction kettle, compactedness is 40% to solution in a kettle., and insulation 3 is little at a temperature of 110 DEG C
When after be cooled to room temperature, the weight of four hydration cobaltous acetate for 180mg, the weight of four hydration cobaltous acetate is with respect to mixed solvent
The ratio of volume is 18mg/mL, and the quality of four hydration manganese acetates is 5% for 8.9mg, Mn and Co atomic ratio；S204, takes out reactant
Carry out each 4 times of eccentric cleaning with ethanol and water, after cleaning in drying baker 60 DEG C of dryings 48 hours, obtain the supported catalyst of drying
Agent multi-layer graphene；S205, quartz ampoule is heated to 575 DEG C of design temperature, and uses N2Emptying, then by supported catalyst multilamellar
Graphene is placed in quartz ampoule, treats that quartz ampoule temperature rises to design temperature again, is passed through N2And C2H2, holding 15 minutes, wherein
N2Air-flow 125mL/min, C2H2Air-flow 50mL/min；S206, in N2Protection under be cooled to and take out after room temperature, obtain multilamellar stone
Black alkene-multiple-wall carbon nanotube three-dimensional material with carbon element.
S30, adds 80mg by multi-layer graphene-many walls nanometer of the method preparation of S20 in nano-silicon ethanol solution
Carbon pipe three-dimensional material with carbon element, mechanical agitation, so that nano-silicon is uniformly mixed with multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
And make part nano-silicon enter the nanometer in the hole of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.Specifically, Multi-layer graphite
Alkene-multiple-wall carbon nanotube three-dimensional material with carbon element and the mass ratio of nano-silicon are 4: 1, mechanical agitation 3 hours under room temperature.
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element,
Generate multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, by the solution after stirring
Pour centrifuge tube into, keep 11 minutes under 5400r/min rotating speed, centrifugation retains clear liquid, with Glass rod deposit weight after terminating
Newly it scatter, re-start centrifugal treating, be centrifuged repeatedly 6 times by above step.
S50, Magneto separate, make multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and unnecessary nano-silicon ethanol solution
After separating, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.Specifically, will
Mixed solution after centrifugation pours beaker into, Magnet is placed on the bottom of beaker, by the magnetic action of Magnet by multi-layer graphene-many
Wall carbon nanotube nano-carbon material is adsorbed in beaker bottom with the composite of nano-silicon, will not enter into the unnecessary of nano-pore
Nano-silicon is outwelled with ethanol solution, repeatedly after Magneto separate 3 times, 24h is dried in 58 DEG C of drying baker, obtains multi-layer graphene-many
Wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon.
Nanometer silicon composite material is filled by a kind of multi-layer graphene CNT three-dimensional material with carbon element that said method is obtained,
The diameter of CNT in 55cm, the footpath grain of nano-silicon in 57nm, CNT on multi-layer graphene surface close to vertical-growth,
Uniform diameter, is evenly distributed, and there is space between CNT, and silicon nanoparticle is uniformly filled in a nanometer air, is adsorbed in and receives
Rice carbon pipe surface.
It should be appreciated that exemplary embodiment as herein described is illustrative and be not restrictive.Although retouching in conjunction with accompanying drawing
State one or more embodiments of the invention, it should be understood by one skilled in the art that without departing from appended right
In the case of requiring limited the spirit and scope of the present invention, 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 material with carbon element fills the preparation method of nanometer silicon composite material, and it is special
Levy and be, comprise the steps：
S10, adds nano-silicon in ethanol solution, ultrasonic, prepares nano-silicon ethanol solution；
S20, prepares multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element；
S30, adds multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element, mechanical agitation in nano-silicon ethanol solution, makes to receive
Rice silicon and multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element uniformly mixes, and make part nano-silicon entrance multi-layer graphene-
The nanometer in the hole of multiple-wall carbon nanotube three-dimensional material with carbon element；
S40, centrifugation, make nano-silicon be sputtered nanometer in the hole into multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element, generate
Multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material；
S50, Magneto separate, so that multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element is separated with unnecessary nano-silicon ethanol solution
Afterwards, it is dried, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material.
2. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that in S10, the quality of described nano-silicon is 0.1mg/mL- with respect to the ratio of alcohol solvent volume
2.0mg/mL, ultrasonic 0.5-2h.
3. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that S20 specifically includes：
S201, measures the DMF that volume ratio is 8: 2-9: 1 and distilled water, and as mixed solvent after mixing, both volumes and conduct are mixed
Bonding solvent volume is used for calculating；
S202, adds expanded graphite, sonic oscillation 2-7 hour, obtains multi-layer graphene；
S203, adds four hydration cobaltous acetate and four hydration manganese acetates in mixed solution, stirs 5-10 minute, solution is poured into water
Thermal response kettle, compactedness is 20%-50% to solution in a kettle., cools down at a temperature of 100 DEG C -130 DEG C after insulation 1-3 hour
To room temperature；
S204, takes out reactant ethanol and water and carries out each 3 times of eccentric cleaning, after cleaning, 60 DEG C of dryings 24 are little in drying baker
When, obtain the supported catalyst multi-layer graphene of drying；
S205, quartz ampoule is heated to 500-650 DEG C of design temperature, and uses N2Emptying, then by supported catalyst multi-layer graphene
It is placed in quartz ampoule, treat that quartz ampoule temperature rises to design temperature again, be passed through N2And C2H2, keep 5-20 minute, wherein N2Gas
Stream 50-200mL/min, C2H2Air-flow 20-60mL/min；
S206, in N2Protection under be cooled to and take out after room temperature, obtain multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element.
4. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that in S30, the quality of multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and nano-silicon it
Than for 1: 1-5: 1, mechanical agitation 2-5 hour under room temperature.
5. multi-layer graphene according to claim 1-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that S40 specifically, by stirring after solution pour centrifuge tube into, in 4500-5500r/min rotating speed
Lower holding 5-15 minute, centrifugation retains clear liquid after terminating, and with Glass rod, deposit is scatter again, re-starts 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 material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that S50 specifically, by centrifugation after mixed solution pour beaker into, Magnet is placed on the bottom of beaker
Multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element and the composite of nano-silicon are adsorbed by portion by the magnetic action of Magnet
In beaker bottom, the unnecessary nano-silicon not entering into nano-pore is outwelled with ethanol solution, repeatedly after Magneto separate 3-5 time,
24-48h is dried in 50-70 DEG C of drying baker, obtains multi-layer graphene-multiple-wall carbon nanotube three-dimensional material with carbon element compound with nano-silicon
Material.
7. multi-layer graphene according to claim 3-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that expanded graphite is 1.3-2.5mg/mL with respect to mixed solvent.
8. multi-layer graphene according to claim 3-multiple-wall carbon nanotube three-dimensional material with carbon element filling nanometer silicon composite material
Preparation method it is characterised in that four hydration cobaltous acetate weight with respect to the volume of mixed solvent ratio be 14-25mg/mL,
And when adding four hydration manganese acetates, Mn and Co atomic ratio are 5%-20%.
9. the multi-layer graphene according to claim 1 or 3 or 7 or 8-multiple-wall carbon nanotube three-dimensional material with carbon element filling nano-silicon
The preparation method of composite is it is characterised in that the number of plies of multi-layer graphene is below 100 layers.
10. a kind of multi-layer graphene CNT three-dimensional material with carbon element filling nanometer silicon composite material is it is characterised in that pass through as weighed
Profit requires the arbitrary described preparation method of 1-9 to make, and in 50-80cm, the footpath grain of nano-silicon exists the diameter of described CNT
Below 60nm, CNT, is evenly distributed close to vertical-growth, uniform diameter on multi-layer graphene surface, between CNT
There is space, silicon nanoparticle is uniformly filled in a nanometer air, be adsorbed in CNT surface.
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