CN105226254B - A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application - Google Patents
A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application Download PDFInfo
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- CN105226254B CN105226254B CN201510669576.1A CN201510669576A CN105226254B CN 105226254 B CN105226254 B CN 105226254B CN 201510669576 A CN201510669576 A CN 201510669576A CN 105226254 B CN105226254 B CN 105226254B
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Abstract
The invention provides a kind of silicon nanoparticle graphite flake carbon fibre composite and preparation method and application.The preparation method, with graphite nano plate and carbon fiber（Or CNT）Based on, using coupled method or Electrostatic Absorption method by nano silicon particles uniform load on the surface of graphite nano plate and carbon fiber, then the surface of silicon nanoparticle graphite nano plate carbon fibre composite is uniformly coated, and surface coating layer carbonization is caused by high-temperature heat treatment method, form carbon（Graphite nano plate+carbon fiber or CNT）Silicon（Nano particle）Carbon（Carbon coating layer）Sandwich so that the carbon fiber nanometer silicon grain graphite flake composite has stronger mechanical strength, big by the capacity of its lithium battery being prepared from, good cycle, the discharge and recharge time is few；In the case of fast charging and discharging, compared with normal charge-discharge velocity, its capacity attenuation is small.
Description
Technical field
The present invention relates to lithium ion battery anode active material field, more particularly, to a kind of silicon nanoparticle-graphite
Nanometer sheet-carbon fibre composite and preparation method and application.
Background technology
As the miniaturization and electric automobile of various portable electric appts are to large-capacity high-power electrochmical power source
Widespread demand, explore height ratio capacity, long circulation life and low cost lithium ion battery negative material turn into study hotspot.Mesh
The 350mAh/g capacity of preceding commercial li-ion battery graphite cathode material is not much close to theoretical capacity (372mAh/g)
Room for promotion, explore novel anode material it is imperative.
Compared with traditional graphite cathode, silicon (theoretical capacity 4200mAh/g) has the theoretical capacity for decupling graphite,
Higher than charging/discharging voltage (the 0.4V/vs Li/Li of carbon-based material+) Li dendrite can be avoided to be formed, with more preferable security,
Therefore it is considered as the most promising candidate of lithium ion battery negative material of future generation.But it exists serious in charge and discharge process
Bulk effect (~300%) and low conductivity (6.7 × 10-4S/cm the cyclical stability bottleneck and initial coulomb efficiency) produced
It is low, and Si synthesis control is difficult, complex process, yield poorly, cost height is hinder its industrial applications and popularization main
Problem.In order to solve these problems, design silicon microscopic structure suppresses its Volume Changes, improves silicon productive technique and improve it and lead
Electrically, it is always research emphasis to prepare with higher capacity and excellent cycle performance, high yield, inexpensive silica-base material.
The content of the invention
There is provided a kind of silicon nanoparticle-graphite nano plate-carbon fibre to overcome the defect described in above-mentioned prior art by the present invention
Tie up the preparation method of composite.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
S1. the surface of silicon nanoparticle is carried out using amino-type silane coupler amido modified；
S2. acid treatment is carried out to the carbon material being made up of graphite nano plate and carbon fiber；
S3. the carbon material through peracid treatment is dispersed in water, the nano-silicon then added after amido modified
Grain, stirring, obtains mixed solution；The mass ratio of the nano-silicon after amido modified and the carbon material is 1:9~3:
7；
S4. the mixed solution is filtered, dries, obtain the carbon material of supporting silicon nanoparticles；
S5. the carbon material of the supporting silicon nanoparticles is added to the solution containing polymer monomer, occurs polymerization anti-
Should, filter, dry；The polymer monomer is the combination of the wherein one or more of pyrroles, aniline or dopamine.
S6. high-temperature heat treatment is then carried out, the condition of high-temperature heat treatment is：Under the protection of inert gas, 850 DEG C~
1250 DEG C of 5 ~ 120 min of heating, obtain carbon fiber-silicon nanoparticle-graphite nano plate composite.
Silicon nanoparticle is incorporated into graphite cathode to increase the capacity of whole graphite cathode by above-mentioned preparation method, and it is with stone
Based on black nanometer sheet, silicon nanoparticle is equably supported in the way of chemical bonds in the solution graphite nano plate with
On carbon fiber surface, then the surface of silicon nanoparticle-graphite nano plate-carbon fibre composite is uniformly coated,
And cause the clad on the silicon nanoparticle-graphite nano plate-carbon fibre composite surface by high-temperature heat treatment method
Carbonization, forms carbon（Graphite nano plate+carbon fiber or CNT）- silicon（Nano particle）- carbon（Carbon coating layer）Composite junction
Structure material, further improve the silicon nanoparticle-graphite nano plate-carbon fibre composite mechanical strength, cycle performance and
Stability, makes it in the case of quick charge-discharge, capacity attenuation is small.
It is described amido modified to comprise the following steps in step S1：Nano silica fume particle is scattered in dry dimethylbenzene,
Amino-type silane coupler is added dropwise, then under the protection of inert gas, flow back 12 h in 80 DEG C, filters, washs, dries, obtain
To amido modified nano silica fume.The amino-type silane coupler be 3- aminopropyl triethoxysilanes and/or N- aminoethyls-
3- aminopropyl triethoxysilanes.The mass ratio of the amino-type silane coupler and silicon nanoparticle is 0.5 ~ 2：10, it is excellent
Elect 1 as：10.
The mass ratio of the nano-silicon after amido modified and the graphite nano plate is 1：9~3：7, more preferably
2：8.By the mass ratio for properly setting nano-silicon and nano graphite flakes so that portion's silicon nanoparticle big absolutely is effectively attached to stone
Black nanometer sheet and carbon fiber surface, and sufficiently large space is kept between silicon nanoparticle, to tackle silicon in storage lithium process
In volumetric expansion and maintain stabilization of the silicon nanoparticle on graphite flake surface to depend on.In addition, keeping foot between silicon nanoparticle
Enough big spaces can also increase the straightforward contact between nano graphite flakes, to form a highly conductive carbon-based um porous frame
Frame.So composite can preferably tackle silicon than the material that is simply mixed and be produced during storage lithium because of volumetric expansion
Mechanical stress, so as to extend cycle life, it is ensured that the high stability of lithium ion battery and high invertibity.
In step S5, the polymerisation comprises the following steps：1 V% 1M HCl are added in water, load is then added
The graphite nano plate of silicon nanoparticle, adds in polymer monomer, ice-water bath and ammonium persulfate is added dropwise（Dopamine polymerization then need not
Plus）, stir 12 h.The quality of the polymer monomer and the mass ratio of the silicon nanoparticle are 0.5 ~ 2.5：5, be preferably
1：5.
The mass ratio of the graphite nano plate and the carbon fiber is 99：1~9：1, preferably 95：5.By further
The amount ratio of the graphite nano plate and the carbon fiber is controlled, further to optimize the structure of the carbon material, with preferably
The mechanical stress that reply silicon is produced during storage lithium by volumetric expansion, it is ensured that lithium ion battery is steady in fast charging and discharging
It is qualitative.
In step S6, the condition of high-temperature heat treatment is：Under the protection of inert gas, under 3~5 DEG C of rates of heat addition,
850 DEG C~1250 DEG C 5 ~ 30 min of heating.It is highly preferred that heating 5 ~ 30 min at 1050 DEG C ~ 1250 DEG C.The inert gas is excellent
Choosing uses argon gas or nitrogen.
Preferably, the graphite nano plate through peracid treatment is dispersed in water, after regulation pH to 5~8, added through amino
Silicon nanoparticle after modification, stirring, obtains mixed solution.It is highly preferred that regulation pH is 6.
Preferably, in step S3, coupling agent is added into the mixed solution；The coupling agent isN- hydroxysuccinimidyl acyl is sub-
Amine and/or 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides.The consumption of the coupling agent is：The matter of the mixed solution
Measure percentage 1%~5%.
Preferably, the acid treatment comprises the following steps：Carbon fiber and graphite nano plate are added into 1 ~ 3 mol/L nitric acid
In, at 25~100 DEG C, flow back 0.5~3h.
Preferably, the particle diameter of the nano-silicon is 5 ~ 100 nm.Nano-silicon under this scope can greatly shorten lithium from
Son is in the diffusion admittance distance of material, and this is conducive to the fast charging and discharging of battery.
Preferably, the thickness of the nano graphite flakes is 5 ~ 500 nm.The ratio surface of graphite nano plate under this scope
Product is big, and this is conducive to silicon nanoparticle to be preferably supported on graphite nano plate surface, while composite can also be kept
Good electric conductivity and enough porositys.
It is a further object to provide silicon nanoparticle-Nano graphite that a kind of use above method is prepared from
Piece-carbon fibre composite.
It is a further object to provide a kind of lithium ion battery anode active material, the negative electrode of lithium ion battery
The component that active material is calculated by following mass percent is constituted：90% ~ 98% silicon nanoparticle-graphite nano plate-carbon fiber is multiple
Condensation material, 2% ~ 10% carbon nano-fiber or multi-walled carbon nanotube.
The lithium ion battery anode active material is a kind of multiple dimensioned composite, in this multiple dimensioned composite wood
In material, carbon nano-fiber materials account for the 2%-10% of its weight, primarily serve the effect of mechanical support, to form suitable porosity
And strengthen the overall electric conductivity and mechanical stability of negative active core-shell material.
Preferably, the diameter of the carbon nano-fiber or many wall CNTs is about 10 ~ 300 nm, and length is about 10 ~ 500
μm。
It is a further object to provide a kind of preparation method of negative electrode of lithium ion battery, comprise the following steps：
Above-mentioned lithium ion battery anode active material is mixed with binding agent, the active material of above-mentioned negative electrode of lithium ion battery
Material accounts for the 90% ~ 95% of electrode material gross weight, and binding agent accounts for the 5% ~ 10% of electrode material gross weight, and binding agent includes polyvinylidene fluoride
Alkene（PVDF）, sodium alginate and carbonaceous additive, then by the coating of gained mixing material on a current collector.
The collector is metal copper foil, nickel foam, foam copper, the one of which of carbon cloth；The nickel foam or bubble
The aperture of foam copper is 20 ~ 500 μm；It is highly preferred that aperture is 100~300 μm.
A diameter of 0.5 ~ 20 μm of the carbon fiber, length is 5 ~ 500 mm.When collector is nickel foam or foam copper
When, filled therewith is made in the mixing material and is coated in the space of nickel foam, foam copper or carbon cloth.
Compared with prior art, the beneficial effects of the invention are as follows：
The invention provides a kind of silicon nanoparticle-graphite nano plate-carbon fibre composite and preparation method thereof with answering
With.The preparation method, with graphite nano plate and carbon fiber（Or CNT）Based on, using coupled method or Electrostatic Absorption method
By nano silicon particles uniform load on the surface of graphite nano plate and carbon fiber, then to silicon nanoparticle-graphite nano plate-
The surface of carbon fibre composite is uniformly coated, and causes the silicon nanoparticle-stone by high-temperature heat treatment method
The clad carbonization on black nanometer sheet-carbon fibre composite surface, forms carbon（Graphite nano plate+carbon fiber or carbon nanometer
Pipe）- silicon（Nano particle）- carbon（Carbon coating layer）Sandwich so that the carbon fiber-silicon nanoparticle-graphite flake is multiple
Condensation material has stronger mechanical strength, big by the capacity of its lithium battery being prepared from, good cycle, discharge and recharge time
It is few；In the case of quick charge-discharge, compared with normal charge-discharge velocity, its capacity attenuation is small.
Brief description of the drawings
Fig. 1 is the saturating of silicon nanoparticle-graphite nano plate-carbon fibre composite of carbon-coating cladding described in embodiment 1
Penetrate electron microscope.
Fig. 2 is the transmission electron microscope picture of composite multiple dimensioned described in embodiment 3.
Fig. 3 is the cycle performance figure of lithium ion battery described in embodiment 4.
Fig. 4 is the scanning electron microscope (SEM) photograph of foam copper described in embodiment 4.
Embodiment
The features of the present invention and advantage is expanded on further below by way of example, example is only limitted in the implementation of the explanation present invention
Appearance is not limited to the present invention.
The specification for the material that the embodiment of the present invention is used is as follows：
The particle diameter of nano-silicon is 10 ~ 200 nm；Nano graphite flakes：Stretched dimensions are 0.5-50 μm, and thickness is 5 ~ 500
nm；The diameter of carbon nano-fiber or multi-walled carbon nanotube is about 10 ~ 300 nm, and length is about 10 ~ 500 μm；Carbon microfibre it is straight
Footpath is 0.5 ~ 20 μm, and length is 5 ~ 500 mm.
Embodiment 1
A kind of preparation method of silicon nanoparticle-graphite nano plate-carbon fibre composite, comprises the following steps：
Surface progress to silicon nanoparticle is amido modified；Silicon nanoparticle ultrasonic disperse is made into dimethylbenzene
50mg/ml homogeneous solution, is added dropwise the 3- aminopropyl triethoxysilanes of 10% silicon nanoparticle quality, then in then stirring
Under the protection of inert gas, 80 DEG C of backflow 12h are cooled down, filter, dried.
To the carbon material being made up of graphite nano plate and carbon fiber（The mass ratio of graphite nano plate and carbon fiber is 95：
5）Carry out acid treatment：Nano graphite flakes and carbon fiber are added in 1 ~ 3 mol/L nitric acid, at 80 DEG C, flow back 0.5~3h.
Graphite nano plates of 4 g through peracid treatment is dispersed in water, regulation pH is 5, then adds 1 g and is repaiied through amino
Silicon nanoparticle after decorations, stirs 12 h, obtains mixed solution, the mixed solution is filtered, and dries, obtains load and receive
The carbon material of rice silicon grain.
In the aqueous solution that the carbon material of supporting silicon nanoparticles is added to the 1M HCl containing 1 V%, disperse, then add
Polymer monomer, polymer monomer is the combination of the wherein one or more of pyrroles, aniline or dopamine, polymer monomer
Quality and silicon nanoparticle mass ratio be 1：5, it is 1 then to be added in ice-water bath with polymer monomer mol ratio:1
Ammonium persulfate aqueous solution, stirs 12h, filters, and dries, then under the protection of argon gas, 1250 DEG C of heating are warming up to 3 DEG C/min
5 min.（It need not add ammonium persulfate during from dopamine auto polymerization, only need stirring at normal temperature 12h）, obtain silicon nanoparticle-stone
Black nanometer sheet-carbon fibre composite.
Silicon nanoparticle-graphite nano plate-the carbon fibre composite coated to above-mentioned carbon-coating, carries out TEM signs, such as schemes
Shown in 1：
Lithium ion half-cell is made using above-mentioned silicon nanoparticle-graphite nano plate-carbon fibre composite, method is such as
Under：By 80 wt.% silicon nanoparticles-graphite flake composite and 20 wt.% binding agent（10 wt.% Kynoar and
10 wt.% carbonaceous additives）Mixed, then gained mixing material is coated on collector metal copper foil, pole piece is made.
With above-mentioned plate and metal lithium sheet assembling half-cell, electrolyte uses LiPF6。
Test
Test condition：Between the V of 0.01 V~1.5 charge-discharge test is carried out with 2.5 A/g current densities after tested.
After tested, the capacity of the preparation-obtained lithium ion battery of the present embodiment is 725.8 mAh/g.Battery fills-put
0.55h the time required to electricity circulation.During quick charge-discharge（Charge-discharge velocity from 0.1C increase 8C when）, more normal charge-discharge speed
Rate, its capacity attenuation 22.9%.Cycle life：Through 100 circulations, capability retention is still up to 90%.
Embodiment 2
A kind of preparation method of silicon nanoparticle-graphite nano plate-carbon fibre composite, comprises the following steps：
Surface progress to silicon nanoparticle is amido modified；Silicon nanoparticle ultrasonic disperse is made into dimethylbenzene
50mg/ml homogeneous solution, is added dropwise the N- aminoethyl -3- aminopropyl-triethoxies of 10% silicon nanoparticle quality in then stirring
Silane, then under the protection of inert gas, 80 DEG C of backflow 12h are cooled down, filter, dried.
To the carbon material being made up of graphite nano plate and carbon fiber（The mass ratio of graphite nano plate and carbon fiber is 95：
5）Carry out acid treatment：Nano graphite flakes and carbon fiber are added in 1 ~ 3 mol/L nitric acid, at 80 DEG C, flow back 0.5~3h.
By carbon materials of 4 g through peracid treatment in disperse water, regulation pH is 5, then adds 1 g receiving after modification
Rice silicon grain, obtains mixed solution, adds 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides, 1- (3- dimethylaminos third
Base) -3- ethyl carbodiimides consumption be 4 wt.% mixed solution, stir 12h, filter, dry, obtain load nano-silicon
The carbon material of grain；
In the aqueous solution that the carbon material of supporting silicon nanoparticles is added to the 1M HCl containing 1 V%, disperse, then add
Polymer monomer, polymer monomer is the combination of the wherein one or more of pyrroles, aniline or dopamine, polymer monomer
Quality and silicon nanoparticle mass ratio be 1：5, it is 1 then to be added in ice-water bath with polymer monomer mol ratio:1
Ammonium persulfate aqueous solution, stirs 12h, filters, and dries, then under the protection of argon gas, 1250 DEG C of heating are warming up to 3 DEG C/min
5 min.（It need not add ammonium persulfate during from dopamine auto polymerization, only need stirring at normal temperature 12h）, obtain silicon nanoparticle-stone
Black nanometer sheet-carbon fibre composite.
Lithium ion half-cell, method are made using the above-mentioned silicon nanoparticle-graphite nano plate-carbon fibre composite that obtains
It is as follows：By 80 wt.% silicon nanoparticles-graphite flake composite and 20wt.% binding agent（10 wt.% Kynoar and
10 wt.% carbonaceous additives）Mixed, then gained mixing material is coated on collector metal copper foil, pole piece is made.
With above-mentioned pole piece and metal lithium sheet assembling half-cell, electrolyte uses LiPF6。
Test
Test condition：It is same as Example 1.
After tested, the capacity of the preparation-obtained lithium ion battery of the present embodiment is 778.8mAh/g.The charge-discharge of battery
0.58h the time required to circulation.During quick charge-discharge（Charge-discharge velocity from 0.1C increase 8C when）, more normal charge-discharge speed,
Its capacity attenuation 18.7%.Cycle life：Through 100 circulations, capability retention is still up to 92%.
Embodiment 3
2 carbon coatings prepared will be implemented and obtain silicon nanoparticle-graphite nano plate-carbon fibre composite and carbon
Nanofiber is mixed, and obtains a kind of multiple dimensioned composite, wherein it is fine to obtain silicon nanoparticle-graphite nano plate-carbon
Dimension composite accounts for the 90% of its weight, and carbon nano-fiber accounts for the 10% of its weight.
SEM or TEM is carried out to above-mentioned multiple dimensioned composite to characterize, as shown in Figure 2：
Lithium ion battery is made using above-mentioned multiple dimensioned composite, its preparation method is identical with implementing 2.
Test
Test condition：It is same as Example 1.
After tested, the capacity of the preparation-obtained lithium ion battery of the present embodiment is 847.5 mAh/g.2.5 A/g electric currents
0.56h the time required to the charge-discharge circulation of densitybattery.During quick charge-discharge（Charge-discharge velocity from 0.1C increase 8C when）, compared with
Normal charge-discharge speed, its capacity attenuation 12.1%.Cycle life：Through 100 circulations, capability retention is still up to 95%.
Embodiment 4
The preparation method of multiple dimensioned composite in the present embodiment and the preparation method of lithium ion battery and embodiment 3
Identical, its different place is that collector is foam copper（Aperture is 100 μm）Such as Fig. 4, or using the diameter of carbon fiber paper
For 0.5 ~ 20 μm, length is 5 ~ 500 mm.
Test
Test condition：It is same as Example 1.
After tested, when collector uses the capacity of the preparation-obtained lithium ion battery of foam copper for 884.9mAh/g；Electricity
0.48h the time required to the charge-discharge circulation in pond；During quick charge-discharge（Charge-discharge velocity from~0.1C increases~8C when）, calibration
Normal charge-discharge speed, its capacity attenuation 9.1%；Cycle life：Through 100 circulations, capability retention is still up to 95%（Such as Fig. 3）.
When collector uses the capacity of the preparation-obtained lithium ion battery of carbon fiber paper for 861.3 mAh/g；Battery
0.47 h the time required to charge-discharge circulation；During quick charge-discharge（Charge-discharge velocity from 0.1C increase 8C when）, more normally fill-put
Electric speed, its capacity attenuation is 10.7%；Cycle life：Through 100 circulations, capability retention is still up to 95%.
Embodiment 5 ~ 8
Obtained in embodiment 5 ~ 8 preparation method and lithium of silicon nanoparticle-graphite nano plate-carbon fibre composite from
The preparation method of sub- battery is same as Example 2, and its different place is the mass ratio of nano-silicon and carbon material（A）, it is high
Warm the temperature of processing（B）And the mass ratio of graphite nano plate and carbon fiber（C）As shown in table 1：
Table 1
| A | B/℃ | C | |
| Embodiment 5 | 1:9 | 1127 | 99：1 |
| Embodiment 6 | 3:7 | 1250 | 95：5 |
| Embodiment 7 | 1:9 | 850 | 9：1 |
| Embodiment 8 | 1:4 | 1050 | 95：5 |
Test
Test condition：Same as Example 2, its result is as shown in table 2：
Table 2
| Capacity/mAh/g | Charge-discharge circulates required time/h | During quick charge-discharge, attenuation rate/% of capacity | |
| Embodiment 5 | 638.9 | 0.46 | 10.3 |
| Embodiment 6 | 737.6 | 0.60 | 27.3 |
| Embodiment 7 | 575.3 | 0.46 | 26.7 |
| Embodiment 8 | 813.9 | 0.55 | 16.3 |
Embodiment 9 ~ 11
The preparation method and lithium of silicon nanoparticle-graphite nano plate-carbon fibre composite are obtained in embodiment 9 ~ 11
The preparation method of ion battery is same as Example 4, and its different place is, nano-silicon in multiple dimensioned composite
The mass percent of grain-graphite nano plate-carbon fibre composite（D）, foam copper aperture be（E）, as shown in table 3：
Table 3
| D/% | E/μm | |
| Embodiment 9 | 90 | 20 |
| Embodiment 10 | 98 | 500 |
| Embodiment 11 | 95 | 300 |
Test
Test condition：Same as Example 1, its result is as shown in table 4：
Table 4
| Capacity/mAh/g | Charge-discharge circulates required time/h | During quick charge-discharge, attenuation rate/% of capacity | |
| Embodiment 9 | 835.2 | 0.51 | 13.7 |
| Embodiment 10 | 826.5 | 0.53 | 15.3 |
| Embodiment 11 | 865.2 | 0.50 | 10.2 |
Comparative example 1 ~ 2
The preparation method and lithium of the silicon nanoparticle-graphite nano plate-carbon fibre composite obtained in comparative example 1 ~ 2
The preparation method of ion battery is same as Example 2, and its different place is the mass ratio of nano-silicon and nano graphite flakes
（A）, high-temperature heat treatment temperature（B）And the mass ratio of graphite nano plate and carbon fiber（C）, as shown in table 5：
Table 5
| A | B/℃ | C | |
| Comparative example 1 | 3:7 | 1420 | 95：5 |
| Comparative example 2 | 1:9 | 800 | 9：1 |
Test
Test condition：Same as Example 1, its result is as shown in table 6：
Table 6
| Capacity/mAh/g | Charge-discharge circulates required time/h | During quick charge-discharge, attenuation rate/% of capacity | |
| Comparative example 1 | 701.2 | 0.86 | 54.7 |
| Comparative example 2 | 565.3 | 0.56 | 36.1 |
Reference examples
Preparation method in this reference examples is substantially the same manner as Example 1, and its difference is, the carbon material is comprised only
Nano graphite flakes, and silicon nanoparticle-graphite nano plate composite is not coated.
The preparation method of the lithium ion battery of this reference examples is same as Example 1.
Test
Test condition：It is same as Example 1.
After tested, the capacity of the preparation-obtained lithium ion battery of this reference examples is 407.3 mAh.g-1；Battery fills-put
0.78h the time required to electricity circulation；During quick charge-discharge（Charge-discharge velocity from 0.1C increase 8C when）, more normal charge-discharge speed
Rate, its capacity attenuation is 53.3%；Cycle life：Through 100 circulations, capability retention is 63%.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Any modifications, equivalent substitutions and improvements made within the spirit and principle of invention etc., should be included in the claims in the present invention
Protection domain within.
Claims (10)
1. a kind of preparation method of silicon nanoparticle-graphite nano plate-carbon fibre composite, it is characterised in that including following
Step：
S1. the surface of silicon nanoparticle is carried out using amino-type silane coupler amido modified；
S2. acid treatment is carried out to the carbon material being made up of graphite nano plate and carbon fiber；
S3. the carbon material through peracid treatment is dispersed in water, the silicon nanoparticle then added after amido modified is stirred
Mix, obtain mixed solution；The mass ratio of the nano-silicon after amido modified and the carbon material is 1:9~3:7；
S4. the mixed solution is filtered, dries, obtain the carbon material of supporting silicon nanoparticles；
S5. the carbon material of the supporting silicon nanoparticles is added to the solution containing polymer monomer, occurs polymerisation,
Filtering, is dried；The polymer monomer is the combination of the wherein one or more of pyrroles, aniline or dopamine；
S6. high-temperature heat treatment is then carried out, the condition of high-temperature heat treatment is：Under the protection of inert gas, 850 DEG C~1250
DEG C heating 5 ~ 120 min, obtain carbon fiber-silicon nanoparticle-graphite nano plate composite.
2. preparation method according to claim 1, it is characterised in that in step S3, by the carbon material through peracid treatment point
Dissipate in water, after regulation pH to 5~8, the silicon nanoparticle added after amido modified, stirring obtains mixed solution.
3. preparation method according to claim 1 or 2, it is characterised in that in step S3, is added into the mixed solution
Coupling agent；The coupling agent isN- HOSu NHS and/or 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides.
4. preparation method according to claim 1, it is characterised in that the quality of the graphite nano plate and the carbon fiber
The ratio between be 99：1~9：1.
5. preparation method according to claim 1, it is characterised in that the particle diameter of the nano-silicon is 5 ~ 100 nm.
6. preparation method according to claim 1, it is characterised in that the thickness of the nano graphite flakes is 5 ~ 500 nm.
7. a kind of carbon fiber-silicon nanoparticle-graphite nano plate composite, it is characterised in that any using claim 1 ~ 6
Described in preparation method and be made.
8. a kind of lithium ion battery anode active material, it is characterised in that the component calculated by following mass percent is constituted：
Carbon fiber-silicon nanoparticle-graphite nano plate composite described in 90% ~ 98% claim 7,2% ~ 10% carbon nano-fiber
Or CNT.
9. lithium ion battery anode active material according to claim 8, it is characterised in that the carbon nano-fiber is more
A diameter of 10 ~ 300 nm of wall carbon nano tube, length is 10 ~ 500 μm.
10. a kind of preparation method of negative electrode of lithium ion battery, it is characterised in that comprise the following steps：
Lithium ion battery anode active material described in claim 8 or 9 is mixed with binding agent, and is coated on collector
On, the collector is the one of which of copper foil, nickel foam, foam copper and carbon cloth；The nickel foam or foam copper
Aperture is 20 ~ 500 μm；A diameter of 0.5 ~ 20um of the carbon microfibre, length is 5 ~ 500mm.
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| CN105762337B (en) * | 2016-01-22 | 2017-11-14 | 三峡大学 | A kind of silicon/graphene/carbon fiber composite negative material and preparation method thereof |
| CN107195874B (en) * | 2017-04-19 | 2019-05-28 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the Si-C composite material of polypyrrole cladding |
| CN107189354B (en) * | 2017-07-07 | 2019-08-16 | 齐鲁工业大学 | A kind of preparation method of graphene nanometer sheet enhancing carbon fibre composite |
| CN113594455B (en) * | 2017-12-12 | 2023-03-24 | 贝特瑞新材料集团股份有限公司 | Silicon-based negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN109860567A (en) * | 2019-02-26 | 2019-06-07 | 成都爱敏特新能源技术有限公司 | A kind of Copper substrate graphene/silicon/carbon nitrogen combination electrode and preparation method thereof |
| CN112421032B (en) * | 2019-08-23 | 2022-02-18 | 中国科学院福建物质结构研究所 | Adhesive composition and application thereof |
| CN111092204A (en) * | 2019-12-12 | 2020-05-01 | 银隆新能源股份有限公司 | Hollow carbon fiber modified silicon-carbon material, preparation method and application thereof |
| CN112467134B (en) * | 2020-09-09 | 2022-08-30 | 珠海中科兆盈丰新材料科技有限公司 | Preparation method of carbon nano tube-silicon carbon composite negative electrode material |
| CN114094107B (en) * | 2022-01-17 | 2022-04-08 | 湖南金阳烯碳新材料有限公司 | Graphite negative electrode material and preparation method and application thereof |
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