CN105355870B - Expanded graphite and nanometer silicon composite material and preparation method thereof, electrode slice, battery - Google Patents
Expanded graphite and nanometer silicon composite material and preparation method thereof, electrode slice, battery Download PDFInfo
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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
A kind of preparation method of high density expanded graphite and nanometer silicon composite material, it comprises the following steps：Step S1, is aoxidized to graphite, and graphite oxide is made；Step S2, graphite oxide is heat-treated, and expanded graphite is made；Step S3, above-mentioned expanded graphite is mixed with nano-silicon, carbon source and carries out ball milling, obtain the high density expanded graphite and nanometer silicon composite material presoma for including multiple graphite linings, the carbon source being filled between graphite linings and nano-silicon；Step S4, above-specified high density expanded graphite and nanometer silicon composite material presoma are heat-treated, carbon source is converted into agraphitic carbon；Step S5, in above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma surface deposition carbon or nitrogen-doped carbon.In addition, the present invention also provides the electrode slice of a kind of high density expanded graphite and nanometer silicon composite material, a kind of application high density expanded graphite and nanometer silicon composite material, and a kind of lithium ion battery of the application electrode slice.
Description
Technical field
The present invention relates to the preparation method of a kind of expanded graphite and nanometer silicon composite material, expanded graphite and nano-silicon are compound
Material, the lithium ion battery using the expanded graphite and the electrode slice and application of nanometer silicon composite material electrode slice.
Background technology
Lithium ion battery has power density and the high characteristic of volume and capacity ratio and is widely used in each electronic product
In electric automobile.Silicium cathode material is because having very high specific capacity（4200mAh/g）, and there is good charge and discharge platform
With relatively low intercalation potential, and become ideal material of the substitution graphite as lithium ion battery negative material.But silicon materials
Volume can be expanded into the 300% of initial volume during embedding lithium, can cause electrode powder through iterative cycles embedding and removing process
Change, the cycle performance of battery is deteriorated.By silicon materials nanosizing, on the one hand can solve electrode powder caused by silicon materials expand repeatedly
Change, on the other hand can shorten lithium ion diffusion path, improve the fast charging and discharging performance of lithium ion battery.By silicon materials and carbon materials
Material is compounded to form negative material, on the one hand can improve the electric conductivity of composite, and the carbon material on the other hand with flexibility is
The volumetric expansion of silicon materials provides cushion space, alleviates due to electrode efflorescence caused by silicon volumetric expansion.However, existing side
Often tap density is very low for carbon-nanometer silicon composite material made from method, causes collector upper electrode material load capacity considerably less,
So as to cause relatively low volume and capacity ratio.
The content of the invention
In view of this, it is necessary to which a kind of preparation method of new high density expanded graphite and nanometer silicon composite material is provided.
A kind of high density expanded graphite and nanometer silicon composite material are provided in addition, there is a need to.
In addition, it is a kind of using above-specified high density expanded graphite and the electrode slice of nanometer silicon composite material to there is a need to offer.
A kind of lithium ion battery using above-mentioned electrode slice is provided in addition, there is a need to.
A kind of preparation method of high density expanded graphite and nanometer silicon composite material, it comprises the following steps：
Step S1, graphite is aoxidized using oxidant, graphite oxide is made, controlled by the dosage for adjusting oxidant
The degree of oxidation of graphite oxide；
Step S2, above-mentioned graphite oxide is heat-treated, expanded graphite is made；
Step S3, above-mentioned expanded graphite is mixed with nano-silicon, carbon source and carries out ball milling, obtain high density expanded graphite with
Nanometer silicon composite material presoma, the high density expanded graphite include multiple graphite linings with nanometer silicon composite material presoma, filled out
The carbon source and nano-silicon filled between graphite linings；
Step S4, above-specified high density expanded graphite and nanometer silicon composite material presoma are heat-treated, turn carbon source
Turn to agraphitic carbon；
Step S5, using chemical vapor deposition in above-mentioned heat treated high density expanded graphite and nanometer silicon composite material
Presoma surface deposits one layer of carbon or nitrogen-doped carbon.
A kind of high density expanded graphite and nanometer silicon composite material, the high density expanded graphite and nanometer silicon composite material bag
The nano-silicon and carbon for including multiple graphite linings and being filled between adjacent graphite linings, the structure of the material is silicon nanoparticle
It is embedded between the graphite linings of extruded expanded graphite, expanded graphite gap is filled with carbon；Expanded graphite as conducting matrix grain,
Gap between compressed expanded graphite is as the cushion space expanded in nano-silicon charge and discharge process, carbon connection nano-silicon and swollen
The density of the graphite linings formation three-dimensional conductive network of swollen graphite, the high density expanded graphite and nanometer silicon composite material is 0.5 ~ 1
g/cm3。
A kind of electrode slice, it includes conducting base and the above-specified high density expanded graphite that is attached on the conducting base is with receiving
Rice silicon composite.
A kind of lithium ion battery, it includes positive pole, negative pole and electrolyte, and it is swollen that the negative or positive electrode includes above-specified high density
Swollen graphite and nanometer silicon composite material.
The high density expanded graphite of the present invention and the preparation method of nanometer silicon composite material are by preparing graphite oxide, by this
Graphite oxide is thermally treated to obtain the larger expanded graphite of dilation, nano-silicon and carbon source is mixed embedded expansion stone by ball milling
In the graphite linings of ink, then it is thermally treated, you can obtain the high density expanded graphite with high-tap density and high-volume and capacity ratio
With nanometer silicon composite material.The structure of the high density expanded graphite and nanometer silicon composite material is that silicon nanoparticle is embedded into by crowded
Between the graphite linings of the expanded graphite of pressure, expanded graphite gap is filled by agraphitic carbon；Expanded graphite is pressurized as conducting matrix grain
Gap between contracting expanded graphite as the cushion space in nano-silicon charge and discharge process, agraphitic carbon can connect nano-silicon and
Expanded graphite forms three-dimensional conductive network；Surface coating further can be carried out to nano-silicon using chemical vapor deposition plating carbon,
At utmost avoid contact of the nano-silicon with electrolyte；It can be improved inside plated film carbon by introducing nitrogen inside above-mentioned plated film carbon
The defects of concentration, further improve transmission rate of the lithium ion inside plated film carbon so as to improve its performance.The high density expands
The preparation technology of the preparation method of graphite and nanometer silicon composite material is simple, power consumption is low, environmentally friendly.In addition, use above method system
When the high density expanded graphite obtained is used for the electrode material of lithium ion battery with nanometer silicon composite material, the lithium ion battery follows
Ring performance is good and stably, and the high rate performance of the lithium ion battery is excellent, and volume energy density is larger.
Brief description of the drawings
Fig. 1 be better embodiment of the present invention high density expanded graphite and nanometer silicon composite material preparation method stream
Cheng Tu.
Fig. 2 is the schematic diagram of expanded graphite.
Fig. 3 is the schematic diagram of high density expanded graphite and nanometer silicon composite material presoma.
Fig. 4 is the schematic diagram of high density expanded graphite and nanometer silicon composite material.
Fig. 5 is the scanning electron microscope (SEM) photograph of the high density expanded graphite and nanometer silicon composite material obtained by embodiment 1.
Fig. 6 is the X-ray diffractogram of the high density expanded graphite and nanometer silicon composite material obtained by embodiment 1.
High density expanded graphites of the Fig. 7 obtained by Application Example 1 ~ 3 is with nanometer silicon composite material as electrode material
Lithium ion battery cycle performance test result curve map.
High density expanded graphites of the Fig. 8 obtained by Application Example 1 ~ 3 is with nanometer silicon composite material as electrode material
Lithium ion battery high rate performance test result curve map.
Main element symbol description
| Expanded graphite | 100 |
| Graphite linings | 10 |
| High density expanded graphite and nanometer silicon composite material presoma | 200 |
| Carbon source | 201 |
| Nano-silicon | 202 |
| High density expanded graphite and nanometer silicon composite material | 300 |
| Agraphitic carbon | 301 |
Following embodiment will combine above-mentioned accompanying drawing and further illustrate the present invention.
Embodiment
Referring to Fig. 1, the present invention provides the preparation method of a kind of high density expanded graphite and nanometer silicon composite material 300,
The high density expanded graphite can be applied to the electrode of lithium ion battery with nanometer silicon composite material 300（It is not shown）In, it includes
Following steps.
Step S1, there is provided graphite, aoxidized, made to the graphite as oxidant by the use of the concentrated sulfuric acid, potassium permanganate, nitrate
Graphite oxide is obtained, and the degree of oxidation of graphite oxide is controlled by adjusting the dosage of oxidant.
Specifically, above-mentioned steps S1 comprises the following steps.
Step S11, graphite, nitrate are added in the concentrated sulfuric acid according to certain ratio, in temperature T1It is lower stirring one section when
Between t1, obtain mixed solution.
The mass ratio of wherein described graphite and nitrate is 2:1, the mass ratio of the concentrated sulfuric acid and graphite is（30~60）：
1, the mass fraction of the concentrated sulfuric acid is 90% ~ 100%, temperature T1Preferably -10 DEG C ~ 0 DEG C, time t1Preferably 10 ~ 30min.
The one or more that the nitrate includes but is not limited in sodium nitrate, potassium nitrate, ammonium nitrate and calcium nitrate.It is described
Nitrate ion in nitrate has strong oxidizing property in acid condition, can improve graphite as oxidant and intercalator
Degree of oxidation, make expanded graphite dilation made from successive process higher.
The one or more that the graphite includes but is not limited in natural scale graphite, spherical graphite and micro crystal graphite.
Step S12, a certain amount of potassium permanganate is slowly added in above-mentioned mixed solution, in temperature T1It is lower stirring one section when
Between t2After be warming up to temperature T2, continue to stir a period of time t3, obtain precursor solution.
Wherein, the quality of the potassium permanganate added is 0.5 ~ 2 times of the quality of graphite in step S11, the time t2
Preferably 1 ~ 3h, the temperature T2Preferably 25 ~ 40 DEG C, the time t3Preferably 0.5 ~ 2h.
Wherein -10 DEG C ~ 0 DEG C of low temperature environment, be advantageous to the oxidation at the edge of graphite flake layer, and the low temperature environment is advantageous to
Nitrate ion, potassium permanganate and the concentrated sulfuric acid enter between graphite flake layer, and when being easy to subsequent high temperature to graphite flake layer inside
Oxidation.
Step S13, a certain amount of water is slowly added in above-mentioned precursor solution, and is warming up to temperature T3, stir one section
Time t4So that nitrate ion, sulfate ion are incorporated into the surface of graphite flake layer, filter, that is, obtain graphite oxide.
Wherein, the volume of the water added is 1 ~ 3 times of the volume of the concentrated sulfuric acid in step S11, the temperature T3It is preferred that
For 90 ~ 100 DEG C, the time t4Preferably 1 ~ 3h.
Step S2, referring to Fig. 2, above-mentioned graphite oxide is heat-treated, graphite oxide is expanded, that is, expansion stone is made
Ink 100.The expanded graphite 100 has 5 ~ 10 times of volumetric expansion degree compared to graphite raw material.The expanded graphite 100 has more
Individual graphite linings 10.
Specifically, above-mentioned graphite oxide is placed on into 900 DEG C, is heat-treated 2h under protective atmosphere, expand graphite oxide, i.e.,
Expanded graphite 100 is made.
Wherein, the protective atmosphere is the conventional use of protective atmospheres such as nitrogen, argon gas.
Step S3, referring to Fig. 3, above-mentioned expanded graphite 100 is mixed with nano-silicon 202, carbon source 201 and carries out ball milling,
Nano-silicon 202 and carbon source 201 is embedded in the graphite linings 10 of expanded graphite 100, obtain high density expanded graphite and answered with nano-silicon
Condensation material presoma 200.The high density expanded graphite and nanometer silicon composite material presoma 200 include multiple graphite linings 10, with
And it is filled in carbon source 201 and nano-silicon 202 between adjacent graphite linings 10.The high density expanded graphite and nano-silicon composite wood
Material precursor 200 is black powder.The volume of high density expanded graphite and nanometer silicon composite material presoma 200 after ball milling is
1 ~ 2 times of graphite raw material, density are 0.3 ~ 0.7 times of graphite raw material.
Specifically, according to mass ratio it is 1 by expanded graphite 100 and nano-silicon 202, carbon source 201：（0.01~2）：（0.01~
2）Ratio add ball grinder in, be according to ratio of grinding media to material（10~30）：1 adds mill ball, and then adding appropriate dispersant will be upper
State expanded graphite, nano-silicon 202, carbon source 201 to soak, 6 ~ 10h of ball milling, obtains black slurry under 300rpm ~ 600rpm rotating speed
Material, the black paste is dried to remove dispersant, obtain high density expanded graphite and nanometer silicon composite material presoma 200.
Wherein, the nano-silicon 202 can be commercial nano-silicon, and the particle diameter of the nano-silicon 202 is preferably 1 ~ 500nm.It is described
Carbon source 201 is preferably macromolecule carbon source, and the macromolecule carbon source includes but is not limited to polyacrylonitrile, polyacrylic acid, polyvinyl pyrrole
One or more in alkanone and pitch.The dispersant includes but is not limited to ethanol, methanol, ethylene glycol, isopropanol and positive third
One or more in alcohol.
Step S4, above-specified high density expanded graphite and nanometer silicon composite material presoma 200 are heat-treated, make carbon source
201 are converted into agraphitic carbon 301.
Specifically, above-specified high density expanded graphite and nanometer silicon composite material presoma 200 are placed in atmosphere furnace,
Under protective atmosphere, 150 ~ 300 DEG C are warming up to, is incubated 1 ~ 3h, then is warming up to 500 ~ 800 DEG C, is incubated 1 ~ 3h, it is then natural with furnace temperature
It is cooled to room temperature.
Step S5, using chemical vapor deposition in above-mentioned heat treated high density expanded graphite and nanometer silicon composite material
The surface of presoma 200 deposits one layer of carbon or nitrogen-doped carbon（It is not shown）, that is, high density expanded graphite is made and nano-silicon is compound
Material 300.The pattern of the high density expanded graphite and nanometer silicon composite material 300 is bulk.
Specifically, using acetonitrile as carbon source and nitrogen source, to above-mentioned heat treated high density at 500 ~ 800 DEG C in tube furnace
Expanded graphite carries out chemical vapor deposition plating carbon or nitrogen-doped carbon with the surface of nanometer silicon composite material presoma 200.Utilize change
Learn vapour deposition plating carbon further can carry out Surface coating to nano-silicon 202, at utmost avoid nano-silicon 202 and electrolyte
Contact；By inside above-mentioned plated film carbon introduce nitrogen can improve inside plated film carbon the defects of concentration, further improve lithium from
Transmission rate of the son inside plated film carbon is so as to improving its performance.
Referring to Fig. 4, the high density expanded graphite includes multiple graphite linings 10 with nanometer silicon composite material 300 and filled out
The nano-silicon 202 and agraphitic carbon 301 filled between adjacent graphite linings 10.Nano-silicon 202 is connected to by the agraphitic carbon 301
Together, should be with flexible agraphitic carbon and when high density expanded graphite and nanometer silicon composite material 300 are as electrode material
301 provide cushion space for the volumetric expansion caused by embedding lithium of nano-silicon 202, can alleviate due to the volumetric expansion of nano-silicon 202
Caused electrode efflorescence.
High density expanded graphite made from the preparation method of above-specified high density expanded graphite and nanometer silicon composite material 300 with
The pattern of nanometer silicon composite material 300 is bulk, and particle diameter is 5 ~ 10 μm.The high density expanded graphite and nanometer silicon composite material 300
Tap density be 0.4 ~ 0.5g/cm3, higher than the tap density of Si-C composite material made from existing method, the vibration density
The higher high density expanded graphite of degree and nanometer silicon composite material 300, the load capacity on conducting base is more, makes obtained
Electrode slice has higher volume and capacity ratio.And the volume and capacity ratio of the high density expanded graphite and nanometer silicon composite material 300
For 1050 ~ 1200mAh/cm3, the density of the high density expanded graphite and nanometer silicon composite material is 0.5 ~ 1 g/cm3。
Below by specific embodiment, the present invention will be further described.
Embodiment 1
8g scale graphites, 4g sodium nitrate are added to 200ml mass fractions among 98% concentrated sulfuric acid, to be stirred at -5 DEG C
15min, obtain mixed solution；Then 8g potassium permanganate is slowly added in mixed solution, after stirring 2h at a temperature of -5 DEG C
35 DEG C are warming up to, and continues to stir 1h, obtains precursor solution；400ml water is added in precursor solution, and is warming up to 98
DEG C, 2h is stirred, then filters, that is, obtains the graphite oxide with intercalation.
The above-mentioned graphite oxide with intercalation is heat-treated into 2h under the conditions of 900 DEG C, nitrogen protection atmosphere to obtain expanding stone
Ink.
Weigh the above-mentioned expanded graphites of 100mg, 100mg commercializations nano-silicon, 100mg polyacrylonitrile to add in ball grinder, add
5g mill balls, 10ml ethanol wet materials are then added, ball milling 8h, obtains black paste under 400rpm rotating speed, and this is black
Mill base material is dried, and obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Above-specified high density expanded graphite and nanometer silicon composite material presoma 200 are placed in atmosphere furnace, protected in nitrogen
Protect under atmosphere, be warming up to 300 DEG C, be incubated 2h, then be warming up to 600 DEG C, be incubated 2h, then naturally cool to room temperature with furnace temperature.
Further using acetonitrile as carbon source and nitrogen source, to above-mentioned heat treated high density at 500 ~ 800 DEG C in tube furnace
Expanded graphite and nanometer silicon composite material presoma 200 carry out chemical vapor deposition plating carbon, that is, be made high density expanded graphite with
Nanometer silicon composite material 300.
Embodiment 2
8g scale graphites, 4g sodium nitrate are added to 190ml mass fractions among 98% concentrated sulfuric acid, to be stirred at -5 DEG C
15min, obtain mixed solution；Then 16g potassium permanganate is slowly added in mixed solution, after stirring 1h at a temperature of -5 DEG C
35 DEG C are warming up to, and continues to stir 1h, obtains precursor solution；380ml water is added in precursor solution, and is warming up to 98
DEG C, 2h is stirred, then filters, that is, obtains the graphite oxide with intercalation.
The above-mentioned graphite oxide with intercalation is heat-treated into 2h under the conditions of 900 DEG C, argon atmosphere to obtain expanding stone
Ink.
Weigh the above-mentioned expanded graphites of 200mg, 100mg commercializations nano-silicon, 100mg polyacrylonitrile to add in ball grinder, add
8g mill balls, 10ml ethanol wet materials are then added, ball milling 8h, obtains black paste under 500rpm rotating speed, and this is black
Mill base material is dried, and obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Above-specified high density expanded graphite and nanometer silicon composite material presoma 200 are placed in atmosphere furnace, protected in nitrogen
Protect under atmosphere, be warming up to 300 DEG C, be incubated 2h, then be warming up to 700 DEG C, be incubated 2h, then naturally cool to room temperature with furnace temperature.
Further using acetonitrile as carbon source and nitrogen source, to above-mentioned heat treated high density at 500 ~ 800 DEG C in tube furnace
Expanded graphite and nanometer silicon composite material presoma 200 carry out chemical vapor deposition plating carbon, that is, be made high density expanded graphite with
Nanometer silicon composite material 300.
Embodiment 3
16g scale graphites, 8g sodium nitrate are added to 400ml mass fractions among 98% concentrated sulfuric acid, to be stirred at -5 DEG C
15min, obtain mixed solution；Then 8g potassium permanganate is slowly added in mixed solution, after stirring 1h at a temperature of -5 DEG C
35 DEG C are warming up to, and continues to stir 2h, obtains precursor solution；800ml water is added in precursor solution, and is warming up to 98
DEG C, 2h is stirred, then filters, that is, obtains the graphite oxide with intercalation.
The above-mentioned graphite oxide with intercalation is heat-treated into 2h under the conditions of 900 DEG C, argon atmosphere to obtain expanding stone
Ink.
Weigh the above-mentioned expanded graphites of 100mg, 100mg commercializations nano-silicon, 200mg polyacrylonitrile to add in ball grinder, add
10g mill balls, 10ml ethanol wet materials are then added, ball milling 10h, obtains black paste under 400rpm rotating speed, by this
Black paste is dried, and obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Above-specified high density expanded graphite and nanometer silicon composite material presoma 200 are placed in atmosphere furnace, protected in nitrogen
Protect under atmosphere, be warming up to 250 DEG C, be incubated 2h, then be warming up to 650 DEG C, be incubated 2h, then naturally cool to room temperature with furnace temperature.
Further using acetonitrile as carbon source and nitrogen source, to above-mentioned heat treated high density at 500 ~ 800 DEG C in tube furnace
Expanded graphite and nanometer silicon composite material presoma 200 carry out chemical vapor deposition plating carbon, that is, be made high density expanded graphite with
Nanometer silicon composite material 300.
Fig. 5 is the ESEM of the high density expanded graphite obtained by above-described embodiment 1 and nanometer silicon composite material 300
Figure.Obtained high density expanded graphite and the pattern of nanometer silicon composite material 300 can be seen that as bulk by the scanning electron microscope (SEM) photograph,
Particle diameter is 5 ~ 10 μm.
Fig. 6 is the X-ray diffraction of the high density expanded graphite obtained by above-described embodiment 1 and nanometer silicon composite material 300
Figure.It can be seen that obtained high density expanded graphite is silicon with nanometer silicon composite material 300 and expanded by the X-ray diffractogram
The compound of graphite.
Respectively by the high density expanded graphite obtained by above-described embodiment 1 ~ 3 and nanometer silicon composite material 300 and conductive charcoal
Black, polyacrylic acid presses 8:1:1 ratio mixing, adds water stirring that slurry is made, is applied on copper-foil conducting electricity and electrode slice is made, use
The electrode slice makes lithium ion battery（Button cell）.Wherein, use lithium piece to be used as to electrode in the lithium ion battery, the lithium from
The electrolyte of sub- battery is 4.5 by mass ratio:4.5:1 dimethyl carbonate, ethylene carbonate and fluorinated ethylene carbonate composition.
The lithium ion battery prepared to high density expanded graphite made from Application Example 1 ~ 3 with nanometer silicon composite material 300 follows
Ring performance and high rate performance test, respectively obtain cycle performance test result curve map（Join Fig. 7）With high rate performance test result
Curve map（Join Fig. 8）.
As seen from Figure 7, the electrode material of the lithium ion battery should have high density under 500mA/g discharge and recharges
The initial mass specific capacity of expanded graphite and the electrode slice of nanometer silicon composite material 300 is 1056mAh/g, after circulation 50 weeks,
Specific discharge capacity conservation rate is 84.7%, shows very excellent cyclical stability.
As seen from Figure 8, specific discharge capacity of the lithium ion battery in 100mA/g discharge and recharges is 1480mAh/g,
Specific discharge capacity during 200mA/g discharge and recharges is 1280mAh/g, and specific discharge capacity during 500mA/g discharge and recharges is 1050mAh/
Specific discharge capacity when g, 1A/g discharge and recharge is 810mAh/g, and specific discharge capacity during 2A/g discharge and recharges is 520mAh/g, performance
Go out excellent high rate performance.
A kind of electrode slice（It is not shown）, the electrode slice includes conducting base（It is not shown）And it is attached to the upper of the conducting base
State high density expanded graphite and nanometer silicon composite material 300.
A kind of lithium ion battery（It is not shown）, it is used in the electronic installations such as mobile phone, computer, electronic reader, electric car.
The lithium ion battery includes positive pole, negative pole and electrolyte, and the negative or positive electrode includes above-mentioned electrode slice.
The high density expanded graphite of the present invention passes through at low temperature by stone with the preparation method of nanometer silicon composite material 300
Ink, the concentrated sulfuric acid, potassium permanganate, nitrate mixing, reheat and graphite oxide are made, the graphite oxide is thermally treated to obtain dilation
Larger expanded graphite 100, nano-silicon 202 and carbon source 201 is set to mix the graphite linings 10 of embedded expanded graphite 100 by ball milling
In, then it is thermally treated, you can obtain that there is the high density expanded graphite of high-tap density and high-volume and capacity ratio to be answered with nano-silicon
Condensation material 300.The structure of the high density expanded graphite and nanometer silicon composite material 300 is embedded into extruded for nano-silicon 202
Between the graphite linings 10 of expanded graphite 100, the gap of expanded graphite 100 is filled by agraphitic carbon 301；Expanded graphite 100 is used as and led
Electric skeleton, the gap between compressed expanded graphite 100 are unformed as the cushion space in the charge and discharge process of nano-silicon 202
Carbon 301 can connect nano-silicon 202 and expanded graphite 100 forms three-dimensional conductive network；Can be with using chemical vapor deposition plating carbon
Surface coating further is carried out to nano-silicon 202, at utmost avoids contact of the nano-silicon 202 with electrolyte；By above-mentioned
Nitrogen is introduced inside plated film carbon can improve concentration the defects of inside plated film carbon, further improve biography of the lithium ion inside plated film carbon
Defeated speed is so as to improving its performance.The high density expanded graphite and the preparation technology of the preparation method of nanometer silicon composite material 300
Simply, consume energy low, environmentally friendly.In addition, it is used for using high density expanded graphite made from the above method with nanometer silicon composite material 300
During the electrode material of lithium ion battery, the good cycle of the lithium ion battery and stably, and the lithium ion battery is forthright again
Can be excellent.
Those skilled in the art it should be appreciated that the embodiment of the above be intended merely to explanation the present invention,
And be not used as limitation of the invention, as long as within the spirit of the present invention, above example is made
It is appropriate to change and change all to fall within the scope of protection of present invention.
Claims (10)
1. the preparation method of a kind of high density expanded graphite and nanometer silicon composite material, it comprises the following steps：
Step S1, graphite is aoxidized using oxidant, graphite oxide is made, oxidation is controlled by the dosage for adjusting oxidant
The degree of oxidation of graphite；
Step S2, above-mentioned graphite oxide is heat-treated, expanded graphite is made；
Step S3, above-mentioned expanded graphite is mixed with nano-silicon, carbon source and carries out ball milling, obtains high density expanded graphite and nanometer
Silicon composite presoma, the high density expanded graphite include multiple graphite linings with nanometer silicon composite material presoma, are filled in
Carbon source and nano-silicon between graphite linings；
Step S4, above-specified high density expanded graphite and nanometer silicon composite material presoma are heat-treated, are converted into carbon source
Agraphitic carbon；
Step S5, using chemical vapor deposition in above-mentioned heat treated high density expanded graphite and nanometer silicon composite material forerunner
Body surface face deposits one layer of carbon or nitrogen-doped carbon.
2. the preparation method of high density expanded graphite as claimed in claim 1 and nanometer silicon composite material, it is characterised in that：It is right
The method that graphite is aoxidized is：The graphite is aoxidized with the concentrated sulfuric acid, potassium permanganate, nitrate, wherein graphite and nitric acid
The mass ratio of salt is 2:1, the mass ratio of the concentrated sulfuric acid and graphite is (30~60)：1, the quality of potassium permanganate is the quality of graphite
0.5~2 times.
3. the preparation method of high density expanded graphite as claimed in claim 2 and nanometer silicon composite material, it is characterised in that：Institute
State one or more of the nitrate in sodium nitrate, potassium nitrate, ammonium nitrate and calcium nitrate；The graphite is selected from natural phosphorus slabstone
One or more in ink, spherical graphite and micro crystal graphite；The carbon source is selected from polyacrylonitrile, polyacrylic acid, polyvinyl pyrrole
One or more in alkanone and pitch.
4. the preparation method of high density expanded graphite as claimed in claim 2 and nanometer silicon composite material, it is characterised in that：Institute
Stating step S1 includes：
Step S11, graphite, nitrate are added in the concentrated sulfuric acid according to certain ratio, in temperature T1Lower stirring a period of time t1,
Obtain mixed solution；
Step S12, a certain amount of potassium permanganate is slowly added in above-mentioned mixed solution, temperature T1Lower stirring a period of time t2Afterwards
It is warming up to a certain temperature T2, continue to stir a period of time t3, obtain precursor solution；
Step S13, a certain amount of water is slowly added in above-mentioned precursor solution, and is warming up to temperature T3, stir t4, filter, i.e.,
Obtain graphite oxide.
5. the preparation method of high density expanded graphite as claimed in claim 4 and nanometer silicon composite material, it is characterised in that：Institute
State temperature T1For -10 DEG C~0 DEG C, the temperature T2For 25~40 DEG C, the temperature T3For 90~100 DEG C, the time t1For 10
~30min, the time t2For 1~3h, the time t3For 0.5~2h, the time t4For 1~3h.
6. the preparation method of high density expanded graphite as claimed in claim 1 and nanometer silicon composite material, it is characterised in that：Institute
Stating step S2 is：
By above-mentioned graphite oxide, it is placed on 900 DEG C, is heat-treated 2h under protective atmosphere, that is, expanded graphite is made.
7. the preparation method of high density expanded graphite as claimed in claim 1 and nanometer silicon composite material, it is characterised in that：Institute
Stating step S3 is：According to mass ratio it is 1 to expanded graphite and nano-silicon, carbon source：(0.01~2)：The ratio of (0.01~2) is carried out
Ball milling, obtain high density expanded graphite and nanometer silicon composite material presoma；
The step S4 is：Above-specified high density expanded graphite and nanometer silicon composite material are placed under protective atmosphere, are warming up to
150~300 DEG C, 1~3h is incubated, then is warming up to 500~800 DEG C, 1~3h is incubated, then naturally cools to room temperature with furnace temperature；
The step S5 is：Using acetonitrile as carbon source and nitrogen source, at 500~800 DEG C to above-mentioned heat treated height in tube furnace
Density expanded graphite carries out chemical vapor deposition plating carbon or nitrogen-doped carbon with nanometer silicon composite material presoma surface, that is, height is made
Density expanded graphite and nanometer silicon composite material.
8. a kind of high density expanded graphite and nanometer silicon composite material, it is characterised in that：The high density expanded graphite and nano-silicon
Composite includes multiple graphite linings and the nano-silicon and carbon that are filled between adjacent graphite linings, the structure of the material are
Silicon nanoparticle is embedded between the graphite linings of extruded expanded graphite, and expanded graphite gap is filled with carbon；Expanded graphite is made
For conducting matrix grain, the gap between compressed expanded graphite connects as the cushion space expanded in nano-silicon charge and discharge process, carbon
The graphite linings for connecing nano-silicon and expanded graphite form three-dimensional conductive network, the high density expanded graphite and nanometer silicon composite material
Density is 0.5~1g/cm3, one layer of the high density expanded graphite and nanometer silicon composite material Surface coating use chemical gaseous phase
The carbon or nitrogen-doped carbon of deposition method.
A kind of 9. electrode slice, it is characterised in that：The electrode slice include conducting base and be attached on the conducting base such as right
It is required that high density expanded graphite and nanometer silicon composite material described in 8.
10. a kind of lithium ion battery, it includes positive pole, negative pole and electrolyte, it is characterised in that：The negative or positive electrode is included such as
Right wants high density expanded graphite and the nanometer silicon composite material described in 8.
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