CN105226254A - A kind of silicon nanoparticle-graphite nano plate-carbon fibre composite and preparation method thereof and application - Google Patents
A kind of silicon nanoparticle-graphite nano plate-carbon fibre composite and preparation method thereof and application Download PDFInfo
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- CN105226254A CN105226254A CN201510669576.1A CN201510669576A CN105226254A CN 105226254 A CN105226254 A CN 105226254A CN 201510669576 A CN201510669576 A CN 201510669576A CN 105226254 A CN105226254 A CN 105226254A
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of silicon nanoparticle-graphite flake-carbon fibre composite and preparation method thereof and application.Described preparation method, based on graphite nano plate and carbon fiber (or carbon nano-tube), adopt coupled method or Electrostatic Absorption method by nano silicon particles uniform load on the surface of graphite nano plate and carbon fiber, then carry out coated uniformly to the surface of silicon nanoparticle-graphite nano plate-carbon fibre composite, and make surface coating layer carbonization by high-temperature heat treatment method, form carbon (graphite nano plate+carbon fiber or carbon nano-tube)-silicon (nano particle)-carbon (carbon coating layer) sandwich, described carbon fiber-silicon nanoparticle-graphite flake composite material is made to have stronger mechanical strength, the capacity of the lithium battery be prepared from by it is large, good cycle, the discharge and recharge time is few, when quick charge-discharge, compared with normal charge-discharge velocity, its capacity attenuation is little.
Description
Technical field
The present invention relates to lithium ion battery anode active material field, more specifically, relate to a kind of silicon nanoparticle-graphite nano plate-carbon fibre composite and preparation method thereof and application.
Background technology
Along with the miniaturization of various portable electric appts and electric automobile are to the widespread demand of large-capacity high-power chemical power source, the lithium ion battery negative material exploring height ratio capacity, long circulation life and low cost becomes study hotspot.The 350mAh/g capacity of current commercial li-ion battery graphite cathode material, close to theoretical capacity (372mAh/g), has not had great room for promotion, explores Novel anode material imperative.
Compare with traditional graphite cathode, silicon (theoretical capacity 4200mAh/g) has the theoretical capacity decupling graphite, higher than the charging/discharging voltage (0.4V/vsLi/Li of carbon-based material
+) Li dendrite can be avoided to be formed, there is better fail safe, be therefore considered to the most promising candidate of lithium ion battery negative material of future generation.But there is serious bulk effect (~ 300%) and low conductivity (6.7 × 10 in it in charge and discharge process
-4s/cm) the cyclical stability bottleneck produced and initial coulomb efficiency low, and the synthesis of Si controls difficulty, complex process, yield poorly, cost height is the subject matter hindering its industrial applications and popularization.In order to address these problems, design silicon microscopic structure suppresses its change in volume, improves silicon productive technique improve its conductivity, and the silica-base material that preparation has more high power capacity and excellent cycle performance, high yield, low cost is research emphasis always.
Summary of the invention
The present invention, for overcoming the defect described in above-mentioned prior art, provides a kind of preparation method of silicon nanoparticle-graphite nano plate-carbon fibre composite.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
S1. amino-type silane coupler is adopted to carry out amido modified to the surface of silicon nanoparticle;
S2. acid treatment is carried out to the material with carbon element be made up of graphite nano plate and carbon fiber;
S3. will be scattered in water through acid-treated material with carbon element, and then add the silicon nanoparticle after amido modified, and stir, obtain mixed solution; The mass ratio of described nano-silicon after amido modified and described material with carbon element is 1:9 ~ 3:7;
S4. described mixed solution is filtered, dry, obtain the material with carbon element of supporting silicon nanoparticles;
S5. the material with carbon element of described supporting silicon nanoparticles is joined the solution containing polymer monomer, polymerization reaction take place, filter, dry; Described polymer monomer is wherein one or more the combination of pyrroles, aniline or dopamine.
S6. then carry out high-temperature heat treatment, the condition of high-temperature heat treatment is: under the protection of inert gas, and 850 DEG C ~ 1250 DEG C heating 5 ~ 120min, obtain carbon fiber-silicon nanoparticle-graphite nano plate composite material.
Silicon nanoparticle is incorporated into graphite cathode to increase the capacity of whole graphite cathode by above-mentioned preparation method, it is based on graphite nano plate, by silicon nanoparticle in the solution equably with the mode load of chemical bonds on graphite nano plate and carbon fiber surface, then carry out coated uniformly to the surface of silicon nanoparticle-graphite nano plate-carbon fibre composite, and the coating layer carbonization on described silicon nanoparticle-graphite nano plate-carbon fibre composite surface is made by high-temperature heat treatment method, form carbon (graphite nano plate+carbon fiber or carbon nano-tube)-silicon (nano particle)-carbon (carbon coating layer) sandwich, described silicon nanoparticle-graphite nano plate-carbon fibre composite the mechanical strength of further raising, cycle performance and stability, make it when quick charge-discharge, capacity attenuation is little.
In step S1, describedly amido modifiedly to comprise the following steps: by nano silica fume Granular composite in the dimethylbenzene of drying, drip amino-type silane coupler; then, under the protection of inert gas, in 80 DEG C of backflow 12h, filter; washing, dry, obtain amido modified nano silica fume.Described amino-type silane coupler is 3-aminopropyl triethoxysilane and/or N-aminoethyl-3-aminopropyl triethoxysilane.The mass ratio of described amino-type silane coupler and silicon nanoparticle is 0.5 ~ 2:10, is preferably 1:10.
The mass ratio of described nano-silicon after amido modified and described graphite nano plate is 1:9 ~ 3:7, is more preferably 2:8.By the suitable mass ratio arranging nano-silicon and nano graphite flakes, large absolutely portion silicon nanoparticle is made effectively to be attached to graphite nano plate and carbon fiber surface, and between silicon nanoparticle, keep enough large space, depend at the stable of graphite flake surface to tackle the volumetric expansion of silicon in storage lithium process and to maintain silicon nanoparticle.In addition, the space keeping enough large between silicon nanoparticle also can increase the straightforward contact between nano graphite flakes, to form the carbon back um porous framework of a high connductivity.Such composite material can be tackled silicon better than the simple material mixed and stored up the mechanical stress produced because of volumetric expansion in lithium process, thus extends cycle life, ensures the high stability of lithium ion battery and high invertibity.
In step S5, described polymerization reaction comprises the following steps: the 1MHCl adding 1V% in water, then adds the graphite nano plate of supporting silicon nanoparticles, adds polymer monomer, drip ammonium persulfate (dopamine polymerization does not then need to add) in ice-water bath, stir 12h.The quality of described polymer monomer and the mass ratio of described silicon nanoparticle are 0.5 ~ 2.5:5, are preferably 1:5.
The mass ratio of described graphite nano plate and described carbon fiber is 99:1 ~ 9:1, is preferably 95:5.By controlling the amount ratio of described graphite nano plate and described carbon fiber further, to optimize the structure of described material with carbon element further, to tackle the mechanical stress that silicon produces because of volumetric expansion in storage lithium process better, ensure the stability of lithium ion battery when fast charging and discharging.
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, at 850 DEG C ~ 1250 DEG C heating 5 ~ 30min.More preferably, at 1050 DEG C ~ 1250 DEG C heating 5 ~ 30min.Described inert gas preferably adopts argon gas or nitrogen.
Preferably, will be scattered in water through acid-treated graphite nano plate, after regulating pH to 5 ~ 8, then add the silicon nanoparticle after amido modified, and stir, obtain mixed solution.More preferably, pH is regulated to be 6.
Preferably, in step S3, in described mixed solution, add coupling agent; Described coupling agent is
n-HOSu NHS and/or 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide.The consumption of described coupling agent is: the mass percent 1% ~ 5% of described mixed solution.
Preferably, described acid treatment comprises the following steps: carbon fiber and graphite nano plate are added in 1 ~ 3mol/L nitric acid, at 25 ~ 100 DEG C, and backflow 0.5 ~ 3h.
Preferably, the particle diameter of described nano-silicon is 5 ~ 100nm.Nano-silicon under this scope can shorten the diffusion admittance distance of lithium ion at material greatly, and this is conducive to the fast charging and discharging of battery.
Preferably, the thickness of described nano graphite flakes is 5 ~ 500nm.The specific area of the graphite nano plate under this scope is large, this be conducive to silicon nanoparticle better load at graphite nano plate on the surface, the good electric conductivity of composite material and enough porositys can also be kept simultaneously.
Another object of the present invention is to provide a kind of silicon nanoparticle-graphite nano plate-carbon fibre composite adopting said method to be prepared from.
Another object of the present invention is to provide a kind of lithium ion battery anode active material, the component that described lithium ion battery anode active material is calculated by following mass percent forms: 90% ~ 98% silicon nanoparticle-graphite nano plate-carbon fibre composite, 2% ~ 10% carbon nano-fiber or multi-walled carbon nano-tubes.
Described lithium ion battery anode active material is a kind of multiple dimensioned composite material, in this multiple dimensioned composite material, carbon nano-fiber materials accounts for the 2%-10% of its weight, mainly play the effect of mechanical support, to form suitable porosity and to strengthen conductivity and the mechanical stability of the entirety of negative active core-shell material.
Preferably, the diameter of described carbon nano-fiber or many ancient piece of jade, round, flat and with a hole in its centres carbon nano-tube is about 10 ~ 300nm, and length is about 10 ~ 500 μm.
Another object of the present invention is to provide a kind of preparation method of lithium ion battery negative, comprises the following steps:
Above-mentioned lithium ion battery anode active material is mixed with binding agent, above-mentioned lithium ion battery anode active material accounts for 90% ~ 95% of electrode material total weight, binding agent accounts for 5% ~ 10% of electrode material total weight, binding agent comprises Kynoar (PVDF), sodium alginate and carbonaceous additive, then by the coating of gained composite material on a current collector.
Described collector is the wherein one of metal copper foil, nickel foam, foam copper, carbon cloth; The aperture of described nickel foam or foam copper is 20 ~ 500 μm; More preferably, aperture is 100 ~ 300 μm.
The diameter of described carbon fiber is 0.5 ~ 20 μm, and length is 5 ~ 500mm.When collector be nickel foam or foam copper time, described composite material is made filled therewith be coated in the space of nickel foam, foam copper or carbon cloth.
Compared with prior art, the invention has the beneficial effects as follows:
The invention provides a kind of silicon nanoparticle-graphite nano plate-carbon fibre composite and preparation method thereof and application.Described preparation method, based on graphite nano plate and carbon fiber (or carbon nano-tube), adopt coupled method or Electrostatic Absorption method by nano silicon particles uniform load on the surface of graphite nano plate and carbon fiber, then carry out coated uniformly to the surface of silicon nanoparticle-graphite nano plate-carbon fibre composite, and the coating layer carbonization on described silicon nanoparticle-graphite nano plate-carbon fibre composite surface is made by high-temperature heat treatment method, form carbon (graphite nano plate+carbon fiber or carbon nano-tube)-silicon (nano particle)-carbon (carbon coating layer) sandwich, described carbon fiber-silicon nanoparticle-graphite flake composite material is made to have stronger mechanical strength, the capacity of the lithium battery be prepared from by it is large, good cycle, the discharge and recharge time is few, when quick charge-discharge, compared with normal charge-discharge velocity, its capacity attenuation is little.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the coated silicon nanoparticle-graphite nano plate-carbon fibre composite of carbon-coating described in embodiment 1.
Fig. 2 is the transmission electron microscope picture of composite material 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
Set forth characteristics and advantages of the present invention further below by way of example, example is only limitted to illustrate that implementation content of the present invention is not limited to the present invention.
The specification of the material that the embodiment of the present invention adopts is as follows:
The particle diameter of nano-silicon is 10 ~ 200nm; Nano graphite flakes: stretched dimensions is 0.5-50 μm, thickness is 5 ~ 500nm; The diameter of carbon nano-fiber or multi-walled carbon nano-tubes is about 10 ~ 300nm, and length is about 10 ~ 500 μm; The diameter of carbon microfibre is 0.5 ~ 20 μm, and length is 5 ~ 500mm.
embodiment 1
A preparation method for silicon nanoparticle-graphite nano plate-carbon fibre composite, comprises the following steps:
Carry out amido modified to the surface of silicon nanoparticle; Silicon nanoparticle ultrasonic disperse is made in dimethylbenzene the homogeneous solution of 50mg/ml, in then stirring, drips the 3-aminopropyl triethoxysilane of 10% silicon nanoparticle quality, then under the protection of inert gas, 80 DEG C of backflow 12h, cooling, filtration, drying.
Acid treatment is carried out to the material with carbon element be made up of graphite nano plate and carbon fiber (mass ratio of graphite nano plate and carbon fiber is 95:5): nano graphite flakes and carbon fiber are added in 1 ~ 3mol/L nitric acid, at 80 DEG C, backflow 0.5 ~ 3h.
4g is scattered in water through acid-treated graphite nano plate, regulates pH to be 5, and then add the silicon nanoparticle of 1g after amido modified, stir 12h, obtain mixed solution, described mixed solution is filtered, drying, obtains the material with carbon element of supporting silicon nanoparticles.
The material with carbon element of supporting silicon nanoparticles is added in the aqueous solution of the 1MHCl containing 1V%; dispersion; then polymer monomer is added; polymer monomer is wherein one or more the combination of pyrroles, aniline or dopamine; the quality of polymer monomer and the mass ratio of silicon nanoparticle are 1:5; then adding in ice-water bath with polymer monomer mol ratio is the ammonium persulfate aqueous solution of 1:1; stir 12h; filter; dry; then, under the protection of argon gas, 1250 DEG C of heating 5min are warming up to 3 DEG C/min.(select during dopamine auto polymerization and do not need to add ammonium persulfate, only need stirring at normal temperature 12h), obtains silicon nanoparticle-graphite nano plate-carbon fibre composite.
Silicon nanoparticle-graphite nano plate-the carbon fibre composite coated to above-mentioned carbon-coating, carries out TEM sign, as shown in Figure 1:
Above-mentioned silicon nanoparticle-graphite nano plate-carbon fibre composite is used to make lithium ion half-cell, method is as follows: mixed by the binding agent (10wt.% Kynoar and 10wt.% carbonaceous additive) of 80wt.% silicon nanoparticle-graphite flake composite material and 20wt.%, then gained composite material is coated on collector metal copper foil, makes pole piece.With above-mentioned plate and metal lithium sheet assembling half-cell, electrolyte adopts LiPF
6.
test
Test condition: carry out charge-discharge test after tested with 2.5A/g current density between 0.01V ~ 1.5V.
After tested, the capacity of the preparation-obtained lithium ion battery of the present embodiment is 725.8mAh/g.The charge-discharge circulation required time 0.55h of battery.During quick charge-discharge (when charge-discharge velocity increases 8C from 0.1C), compared with normal charge-discharge speed, its capacity attenuation 22.9%.Cycle life: through 100 circulations, capability retention still reaches 90%.
embodiment 2
A preparation method for silicon nanoparticle-graphite nano plate-carbon fibre composite, comprises the following steps:
Carry out amido modified to the surface of silicon nanoparticle; Silicon nanoparticle ultrasonic disperse is made in dimethylbenzene the homogeneous solution of 50mg/ml; then the N-aminoethyl-3-aminopropyl triethoxysilane of 10% silicon nanoparticle quality is dripped in stirring; then under the protection of inert gas, 80 DEG C of backflow 12h, cooling, filtration, drying.
Acid treatment is carried out to the material with carbon element be made up of graphite nano plate and carbon fiber (mass ratio of graphite nano plate and carbon fiber is 95:5): nano graphite flakes and carbon fiber are added in 1 ~ 3mol/L nitric acid, at 80 DEG C, backflow 0.5 ~ 3h.
By 4g through acid-treated material with carbon element in disperse water, pH is regulated to be 5, and then add 1g modified after silicon nanoparticle, obtain mixed solution, add 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide, the consumption of 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide is the mixed solution of 4wt.%, stir 12h, filter, dry, obtain the material with carbon element of supporting silicon nanoparticles;
The material with carbon element of supporting silicon nanoparticles is added in the aqueous solution of the 1MHCl containing 1V%; dispersion; then polymer monomer is added; polymer monomer is wherein one or more the combination of pyrroles, aniline or dopamine; the quality of polymer monomer and the mass ratio of silicon nanoparticle are 1:5; then adding in ice-water bath with polymer monomer mol ratio is the ammonium persulfate aqueous solution of 1:1; stir 12h; filter; dry; then, under the protection of argon gas, 1250 DEG C of heating 5min are warming up to 3 DEG C/min.(select during dopamine auto polymerization and do not need to add ammonium persulfate, only need stirring at normal temperature 12h), obtains silicon nanoparticle-graphite nano plate-carbon fibre composite.
Above-mentioned silicon nanoparticle-graphite nano plate-the carbon fibre composite that obtains is used to make lithium ion half-cell, method is as follows: mixed by the binding agent (10wt.% Kynoar and 10wt.% carbonaceous additive) of 80wt.% silicon nanoparticle-graphite flake composite material and 20wt.%, then gained composite material is coated on collector metal copper foil, makes pole piece.With above-mentioned pole piece and metal lithium sheet assembling half-cell, electrolyte adopts LiPF
6.
test
Test condition: identical with embodiment 1.
After tested, the capacity of the preparation-obtained lithium ion battery of the present embodiment is 778.8mAh/g.The charge-discharge circulation required time 0.58h of battery.During quick charge-discharge (when charge-discharge velocity increases 8C from 0.1C), compared with normal charge-discharge speed, its capacity attenuation 18.7%.Cycle life: through 100 circulations, capability retention still reaches 92%.
embodiment 3
What carbon enforcement 2 prepared was coated obtain silicon nanoparticle-graphite nano plate-carbon fibre composite mixes with carbon nano-fiber, obtain a kind of multiple dimensioned composite material, wherein obtain silicon nanoparticle-graphite nano plate-carbon fibre composite and account for 90% of its weight, carbon nano-fiber accounts for 10% of its weight.
Carry out SEM or TEM to above-mentioned multiple dimensioned composite material to characterize, as shown in Figure 2:
Use above-mentioned multiple dimensioned composite material to make lithium ion battery, its preparation method is identical with enforcement 2.
test
Test condition: identical with embodiment 1.
After tested, the capacity of the preparation-obtained lithium ion battery of the present embodiment is 847.5mAh/g.The charge-discharge circulation required time 0.56h of 2.5A/g current density x Cell.During quick charge-discharge (when charge-discharge velocity increases 8C from 0.1C), compared with normal charge-discharge speed, its capacity attenuation 12.1%.Cycle life: through 100 circulations, capability retention still reaches 95%.
embodiment 4
The preparation method of multiple dimensioned composite material in the present embodiment and the preparation method of lithium ion battery identical with embodiment 3, its different place is, collector be foam copper (aperture is 100 μm) as Fig. 4, or adopt the diameter of carbon fiber paper to be 0.5 ~ 20 μm, length is 5 ~ 500mm.
test
Test condition: identical with embodiment 1.
After tested, when collector adopts the capacity of the preparation-obtained lithium ion battery of foam copper to be 884.9mAh/g; The charge-discharge circulation required time 0.48h of battery; During quick charge-discharge when 0.1C increase ~ 8C (charge-discharge velocity from ~), compared with normal charge-discharge speed, its capacity attenuation 9.1%; Cycle life: through 100 circulations, capability retention still reaches 95%(as Fig. 3).
The capacity adopting the preparation-obtained lithium ion battery of carbon fiber paper when collector is 861.3mAh/g; The charge-discharge circulation required time 0.47h of battery; During quick charge-discharge (when charge-discharge velocity increases 8C from 0.1C), compared with normal charge-discharge speed, its capacity attenuation is 10.7%; Cycle life: through 100 circulations, capability retention still reaches 95%.
embodiment 5 ~ 8
Obtain the silicon nanoparticle-preparation method of graphite nano plate-carbon fibre composite in embodiment 5 ~ 8 and the preparation method of lithium ion battery identical with embodiment 2, its different place be the mass ratio (A) of nano-silicon and material with carbon element, the temperature (B) of high-temperature heat treatment and graphite nano plate and carbon fiber mass ratio (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: identical with embodiment 2, its result is as shown in table 2:
Table 2
| Capacity/mAh/g | Charge-discharge circulation required time/h | During quick charge-discharge, the 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
Obtain the silicon nanoparticle-preparation method of graphite nano plate-carbon fibre composite in embodiment 9 ~ 11 and the preparation method of lithium ion battery identical with embodiment 4, its different place is, in multiple dimensioned composite material, the mass percent (D) of silicon nanoparticle-graphite nano plate-carbon fibre composite, the aperture of foam copper are (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: identical with embodiment 1, its result is as shown in table 4:
Table 4
| Capacity/mAh/g | Charge-discharge circulation required time/h | During quick charge-discharge, the 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
Silicon nanoparticle-the preparation method of graphite nano plate-carbon fibre composite obtained in comparative example 1 ~ 2 and the preparation method of lithium ion battery identical with embodiment 2, its different place is the mass ratio (C) of the mass ratio (A) of nano-silicon and nano graphite flakes, the temperature (B) of high-temperature heat treatment and graphite nano plate and carbon fiber, 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: identical with embodiment 1, its result is as shown in table 6:
Table 6
| Capacity/mAh/g | Charge-discharge circulation required time/h | During quick charge-discharge, the 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, described material with carbon element only containing nano graphite flakes, and does not carry out coated to silicon nanoparticle-graphite nano plate composite material.
The preparation method of the lithium ion battery of this reference examples is identical with embodiment 1.
test
Test condition: identical with embodiment 1.
After tested, the capacity of the preparation-obtained lithium ion battery of this reference examples is 407.3mAh.g
-1; The charge-discharge circulation required time 0.78h of battery; During quick charge-discharge (when charge-discharge velocity increases 8C from 0.1C), compared with normal charge-discharge speed, 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 for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all execution modes.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection range that all should be included in the claims in the present invention.
Claims (10)
1. a preparation method for silicon nanoparticle-graphite nano plate-carbon fibre composite, is characterized in that, comprise the following steps:
S1. amino-type silane coupler is adopted to carry out amido modified to the surface of silicon nanoparticle;
S2. acid treatment is carried out to the material with carbon element be made up of graphite nano plate and carbon fiber;
S3. will be scattered in water through acid-treated material with carbon element, and then add the silicon nanoparticle after amido modified, and stir, obtain mixed solution; The mass ratio of described nano-silicon after amido modified and described material with carbon element is 1:9 ~ 3:7;
S4. described mixed solution is filtered, dry, obtain the material with carbon element of supporting silicon nanoparticles;
S5. the material with carbon element of described supporting silicon nanoparticles is joined the solution containing polymer monomer, polymerization reaction take place, filter, dry; Described polymer monomer is wherein one or more the combination of pyrroles, aniline or dopamine;
S6. then carry out high-temperature heat treatment, the condition of high-temperature heat treatment is: under the protection of inert gas, and 850 DEG C ~ 1250 DEG C heating 5 ~ 120min, obtain carbon fiber-silicon nanoparticle-graphite nano plate composite material.
2. preparation method according to claim 1, is characterized in that, in step S3, will be scattered in water through acid-treated material with carbon element, after regulating pH to 5 ~ 8, then adds the silicon nanoparticle after amido modified, stirs, obtains mixed solution.
3. preparation method according to claim 1 and 2, is characterized in that, in step S3, in described mixed solution, adds coupling agent; Described coupling agent is
n-HOSu NHS and/or 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide.
4. preparation method according to claim 1, is characterized in that, the mass ratio of described graphite nano plate and described carbon fiber is 99:1 ~ 9:1.
5. preparation method according to claim 1, is characterized in that, the particle diameter of described nano-silicon is 5 ~ 100nm.
6. preparation method according to claim 1, is characterized in that, the thickness of described nano graphite flakes is 5 ~ 500nm.
7. carbon fiber-silicon nanoparticle-graphite nano plate composite material, is characterized in that, adopts the preparation method described in any one of claim 1 ~ 6 and makes.
8. a lithium ion battery anode active material, is characterized in that, the component calculated by following mass percent forms: 90% ~ 98% carbon fiber-silicon nanoparticle-graphite nano plate composite material according to claim 7,2% ~ 10% carbon nano-fiber or carbon nano-tube.
9. lithium ion battery anode active material according to claim 8, is characterized in that, the diameter of described carbon nano-fiber or multi-walled carbon nano-tubes is about 10 ~ 300nm, and length is about 10 ~ 500 μm.
10. a preparation method for lithium ion battery negative, is characterized in that, comprises the following steps:
Mixed with binding agent by lithium ion battery anode active material described in claim 8 or 9, and coating on a current collector, described collector is the wherein a kind of of Copper Foil, nickel foam, foam copper and carbon cloth; The aperture of described nickel foam or foam copper is 20 ~ 500 μm; The diameter of described carbon microfibre is 0.5 ~ 20um, and length is 5 ~ 500mm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762337A (en) * | 2016-01-22 | 2016-07-13 | 三峡大学 | Silicon/graphene/carbon fiber composite cathode material and preparation method thereof |
| CN107195874A (en) * | 2017-04-19 | 2017-09-22 | 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 |
| CN107189354A (en) * | 2017-07-07 | 2017-09-22 | 齐鲁工业大学 | A kind of graphene nanometer sheet strengthens the preparation method of carbon fibre composite |
| 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 |
| 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 |
| US20200280061A1 (en) * | 2017-12-12 | 2020-09-03 | Btr New Material Group Co., Ltd. | Silicon-based negative electrode material, preparation method therefor and use thereof in lithium-ion battery |
| CN112421032A (en) * | 2019-08-23 | 2021-02-26 | 中国科学院福建物质结构研究所 | Adhesive composition and application thereof |
| CN112467134A (en) * | 2020-09-09 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | Carbon nanotube-silicon carbon composite negative electrode material and preparation method thereof |
| CN114094107A (en) * | 2022-01-17 | 2022-02-25 | 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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| CN103346293A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
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| CN103346293A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762337A (en) * | 2016-01-22 | 2016-07-13 | 三峡大学 | Silicon/graphene/carbon fiber composite cathode material and preparation method thereof |
| CN107195874A (en) * | 2017-04-19 | 2017-09-22 | 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 |
| 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 |
| CN107189354A (en) * | 2017-07-07 | 2017-09-22 | 齐鲁工业大学 | A kind of graphene nanometer sheet strengthens the preparation method of carbon fibre composite |
| 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 |
| US20200280061A1 (en) * | 2017-12-12 | 2020-09-03 | Btr New Material Group Co., Ltd. | Silicon-based negative electrode material, preparation method therefor and use thereof in lithium-ion battery |
| US11515530B2 (en) * | 2017-12-12 | 2022-11-29 | Btr New Material Group Co., Ltd. | Silicon-based negative electrode material, preparation method therefor and use 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 |
| CN112421032A (en) * | 2019-08-23 | 2021-02-26 | 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 |
| CN112467134A (en) * | 2020-09-09 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | Carbon nanotube-silicon carbon composite negative electrode material and preparation method thereof |
| CN114094107A (en) * | 2022-01-17 | 2022-02-25 | 湖南金阳烯碳新材料有限公司 | Graphite negative electrode material and preparation method and application thereof |
| 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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