CN105355870A - Expanded graphite and nano-silicon composite material, preparation method thereof, electrode plate and battery - Google Patents
Expanded graphite and nano-silicon composite material, preparation method thereof, electrode plate and 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
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- 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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Abstract
The invention provides a preparation method of a high-density expanded graphite and nano-silicon composite material. The preparation method comprises the following steps: step S1, oxidizing graphite to manufacture graphite oxide; step S2, carrying out heat treatment on the graphite oxide to manufacture expanded graphite; step S3, mixing the expanded graphite with nano-silicon and a carbon source and carrying out ball-milling to obtain a high-density expanded graphite and nano-silicon composite material precursor comprising a plurality of graphite layers, the carbon source and the nano-silicon filled among the graphite layers; step S4, carrying out heat treatment on the high-density expanded graphite and nano-silicon composite material precursor so that the carbon source is converted into amorphous carbon; and step S5, depositing carbon or doped carbon on the surface of the high-density expanded graphite and nano-silicon composite material precursor after the heat treatment. Moreover, the invention also provides the high-density expanded graphite and nano-silicon composite material, an electrode plate applying the high-density expanded graphite and nano-silicon composite material, and a lithium ion battery applying the electrode plate.
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 nanometer silicon composite material, apply the electrode slice of this expanded graphite and nanometer silicon composite material and apply the lithium ion battery of this 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 and electric automobile.Silicium cathode material because having very high specific capacity (4200mAh/g), and has good charge and discharge platform and lower intercalation potential, and becomes the ideal material of replacement graphite as lithium ion battery negative material.But silicon materials volume in the process of embedding lithium can expand into 300% of initial volume, can cause electrode efflorescence through the embedding lithium of iterative cycles and de-lithium process, makes the cycle performance of battery be deteriorated.By silicon materials nanometer, silicon materials can be solved on the one hand and repeatedly to expand the electrode efflorescence caused, lithium ion the evolving path can be shortened on the other hand, improve the fast charging and discharging performance of lithium ion battery.Silicon materials and material with carbon element are compounded to form negative material, can improve on the one hand the electric conductivity of composite material, having flexible material with carbon element is on the other hand that the volumetric expansion of silicon materials provides cushion space, alleviates the electrode efflorescence because silicon volumetric expansion causes.But often tap density is very low for carbon-nanometer silicon composite material that existing method obtains, and causes collector upper electrode material load capacity considerably less, thus causes lower volume and capacity ratio.
Summary of the invention
In view of this, the preparation method that a kind of new high density expanded graphite and nanometer silicon composite material are provided is necessary.
Separately, there is a need to provide a kind of high density expanded graphite and nanometer silicon composite material.
Separately, there is a need to provide a kind of electrode slice applying above-specified high density expanded graphite and nanometer silicon composite material.
Separately, there is a need to provide a kind of lithium ion battery applying above-mentioned electrode slice.
A preparation method for high density expanded graphite and nanometer silicon composite material, it comprises the steps:
Step S1, uses oxidant to be oxidized graphite, obtained graphite oxide, by adjusting the degree of oxidation of the consumption controlled oxidization graphite of oxidant;
Step S2, heat-treats above-mentioned graphite oxide, obtained expanded graphite;
Step S3, above-mentioned expanded graphite is mixed with nano-silicon, carbon source and carries out ball milling, obtain high density expanded graphite and nanometer silicon composite material presoma, this high density expanded graphite and nanometer silicon composite material presoma comprise multiple graphite linings, be filled in carbon source between graphite linings and nano-silicon;
Step S4, heat-treats above-specified high density expanded graphite and nanometer silicon composite material presoma, makes carbon source be converted into agraphitic carbon;
Step S5, uses chemical vapour deposition (CVD) at above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma surface deposition one deck carbon or nitrogen-doped carbon.
A kind of high density expanded graphite and nanometer silicon composite material, this high density expanded graphite and nanometer silicon composite material comprise multiple graphite linings and the nano-silicon be filled between adjacent graphite linings and carbon, the structure of this material is that silicon nanoparticle is embedded between the graphite linings of extruded expanded graphite, and expanded graphite gap is filled with carbon; Expanded graphite is as conducting matrix grain, gap by compression between expanded graphite is as the cushion space expanded in nano-silicon charge and discharge process, the graphite linings that carbon connects nano-silicon and expanded graphite forms three-dimensional conductive network, and the density of this high density expanded graphite and nanometer silicon composite material is 0.5 ~ 1g/cm
3.
A kind of electrode slice, it comprises conducting base and the above-specified high density expanded graphite that is attached on this conducting base and nanometer silicon composite material.
A kind of lithium ion battery, it comprises positive pole, negative pole and electrolyte, and this negative or positive electrode comprises above-specified high density expanded graphite and nanometer silicon composite material.
The preparation method of high density expanded graphite of the present invention and nanometer silicon composite material is by preparing graphite oxide, this graphite oxide is obtained the larger expanded graphite of dilation through heat treatment, nano-silicon and carbon source mixing is made to embed in the graphite linings of expanded graphite by ball milling, again through heat treatment, high density expanded graphite and the nanometer silicon composite material with high-tap density and high-volume and capacity ratio can be obtained.The structure of this high density expanded graphite and nanometer silicon composite material is that silicon nanoparticle is embedded between the graphite linings of extruded expanded graphite, and expanded graphite gap is filled by agraphitic carbon; Expanded graphite is as conducting matrix grain, and the gap by compression between expanded graphite is as the cushion space in nano-silicon charge and discharge process, and agraphitic carbon can connect nano-silicon and expanded graphite forms three-dimensional conductive network; Utilize chemical vapour deposition (CVD) to plate carbon and can carry out Surface coating to nano-silicon further, at utmost avoid the contact of nano-silicon and electrolyte; Defect density inside plated film carbon can be improved by introducing nitrogen inside above-mentioned plated film carbon, improving the transmission rate of lithium ion inside plated film carbon further thus improving its performance.The preparation technology of the preparation method of this high density expanded graphite and nanometer silicon composite material is simple, low, environmental protection of consuming energy.In addition, when using electrode material for lithium ion battery of the high density expanded graphite that obtains of said method and nanometer silicon composite material, the good cycle of this lithium ion battery and stablizing, and the high rate performance of this lithium ion battery is excellent, volume energy density is larger.
Accompanying drawing explanation
Fig. 1 is the flow chart of the high density expanded graphite of better embodiment of the present invention and the preparation method of nanometer silicon composite material.
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.
The high density expanded graphite of Fig. 5 obtained by embodiment 1 and the scanning electron microscope (SEM) photograph of nanometer silicon composite material.
The high density expanded graphite of Fig. 6 obtained by embodiment 1 and the X-ray diffractogram of nanometer silicon composite material.
The high density expanded graphite of Fig. 7 obtained by Application Example 1 ~ 3 and nanometer silicon composite material are as the cycle performance test result curve chart of the lithium ion battery of electrode material.
The high density expanded graphite of Fig. 8 obtained by Application Example 1 ~ 3 and nanometer silicon composite material are as the high rate performance test result curve chart of the lithium ion battery of electrode material.
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 further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Refer to Fig. 1, the invention provides the preparation method of a kind of high density expanded graphite and nanometer silicon composite material 300, this high density expanded graphite and nanometer silicon composite material 300 can be applicable in the electrode (not shown) of lithium ion battery, and it comprises the steps.
Step S1, provides graphite, is oxidized as oxidant with the concentrated sulfuric acid, potassium permanganate, nitrate to this graphite, obtained graphite oxide, and the degree of oxidation passing through the consumption controlled oxidization graphite of adjustment oxidant.
Concrete, above-mentioned steps S1 comprises the steps.
Step S11, adds in the concentrated sulfuric acid, at temperature T by graphite, nitrate according to certain ratio
1lower stirring a period of time t
1, obtain mixed solution.
The mass ratio of wherein said graphite and nitrate is 2:1, and the mass ratio of the described concentrated sulfuric acid and graphite is (30 ~ 60): 1, and the mass fraction of this concentrated sulfuric acid is 90% ~ 100%, temperature T
1be preferably-10 DEG C ~ 0 DEG C, time t
1be preferably 10 ~ 30min.
Described nitrate includes but not limited to one or more in sodium nitrate, potassium nitrate, ammonium nitrate and calcium nitrate.Nitrate ion in described nitrate has strong oxidizing property in acid condition, as oxidant and intercalator, can improve the degree of oxidation of graphite, and the expanded graphite dilation making successive process obtained is higher.
Described graphite includes but not limited to one or more in natural scale graphite, spherical graphite and micro crystal graphite.
Step S12, slowly adds a certain amount of potassium permanganate in above-mentioned mixed solution, at temperature T
1lower stirring a period of time t
2after be warming up to temperature T
2, continue to stir a period of time t
3, obtain precursor solution.
Wherein, the quality of the potassium permanganate added is 0.5 ~ 2 times of the quality of graphite in step S11, described time t
2be preferably 1 ~ 3h, described temperature T
2be preferably 25 ~ 40 DEG C, described time t
3be preferably 0.5 ~ 2h.
The low temperature environment of wherein-10 DEG C ~ 0 DEG C, is conducive to the oxidation at the edge of graphite flake layer, and this low temperature environment is conducive to nitrate ion, potassium permanganate and the concentrated sulfuric acid enters between graphite flake layer, and to the oxidation of graphite flake layer inside when being convenient to subsequent high temperature.
Step S13, slowly adds a certain amount of water in above-mentioned precursor solution, and is warming up to temperature T
3, stir a period of time t
4, make nitrate ion, surface that sulfate ion is incorporated into graphite flake layer, suction filtration, namely obtains graphite oxide.
Wherein, the volume of the water added is 1 ~ 3 times of the volume of the concentrated sulfuric acid in step S11, described temperature T
3be preferably 90 ~ 100 DEG C, described time t
4be preferably 1 ~ 3h.
Step S2, refers to Fig. 2, is heat-treated by above-mentioned graphite oxide, and graphite oxide is expanded, i.e. obtained expanded graphite 100.This expanded graphite 100 has the volumetric expansion degree of 5 ~ 10 times compared to graphite raw material.This expanded graphite 100 has multiple graphite linings 10.
Concrete, above-mentioned graphite oxide is placed on 900 DEG C, heat treatment 2h under protective atmosphere, graphite oxide is expanded, namely obtains expanded graphite 100.
Wherein, described protective atmosphere is the protective atmosphere that the routine such as nitrogen, argon gas uses.
Step S3, refer to Fig. 3, above-mentioned expanded graphite 100 mixed with nano-silicon 202, carbon source 201 and carries out ball milling, nano-silicon 202 and carbon source 201 being embedded in the graphite linings 10 of expanded graphite 100, obtains high density expanded graphite and nanometer silicon composite material presoma 200.This high density expanded graphite and nanometer silicon composite material presoma 200 comprise multiple graphite linings 10 and the carbon source 201 be filled between adjacent graphite linings 10 and nano-silicon 202.This high density expanded graphite and nanometer silicon composite material presoma 200 are black powder.High density expanded graphite after ball milling and the volume of nanometer silicon composite material presoma 200 are 1 ~ 2 times of graphite raw material, and density is 0.3 ~ 0.7 times of graphite raw material.
Concrete, be 1:(0.01 ~ 2 with nano-silicon 202, carbon source 201 according to mass ratio by expanded graphite 100): the ratio of (0.01 ~ 2) adds in ball grinder, be (10 ~ 30) according to ratio of grinding media to material: 1 adds mill ball, then add appropriate dispersant above-mentioned expanded graphite, nano-silicon 202, carbon source 201 are soaked, ball milling 6 ~ 10h under the rotating speed of 300rpm ~ 600rpm, obtain black paste, this black paste is dried to remove dispersant, obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Wherein, described nano-silicon 202 can be commercial nano-silicon, and the particle diameter of this nano-silicon 202 is preferably 1 ~ 500nm.Described carbon source 201 is preferably macromolecule carbon source, and this macromolecule carbon source includes but not limited to one or more in polyacrylonitrile, polyacrylic acid, polyvinylpyrrolidone and pitch.Described dispersant includes but not limited to one or more in ethanol, methyl alcohol, ethylene glycol, isopropyl alcohol and normal propyl alcohol.
Step S4, heat-treats above-specified high density expanded graphite and nanometer silicon composite material presoma 200, makes carbon source 201 be converted into agraphitic carbon 301.
Concrete, be placed in atmosphere furnace by above-specified high density expanded graphite and nanometer silicon composite material presoma 200, under protective atmosphere, be warming up to 150 ~ 300 DEG C, insulation 1 ~ 3h, then be warming up to 500 ~ 800 DEG C, insulation 1 ~ 3h, then naturally cools to room temperature with furnace temperature.
Step S5, uses chemical vapour deposition (CVD) in above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma 200 surface deposition one deck carbon or nitrogen-doped carbon (not shown), namely obtains high density expanded graphite and nanometer silicon composite material 300.The pattern of this high density expanded graphite and nanometer silicon composite material 300 is block.
Concrete, be Carbon and nitrogen sources with acetonitrile, in tube furnace, at 500 ~ 800 DEG C, chemical vapour deposition (CVD) carried out to above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma 200 surface plate carbon or nitrogen-doped carbon.Utilize chemical vapour deposition (CVD) to plate carbon and can carry out Surface coating to nano-silicon 202 further, at utmost avoid the contact of nano-silicon 202 and electrolyte; Defect density inside plated film carbon can be improved by introducing nitrogen inside above-mentioned plated film carbon, improving the transmission rate of lithium ion inside plated film carbon further thus improving its performance.
Refer to Fig. 4, this high density expanded graphite and nanometer silicon composite material 300 comprise multiple graphite linings 10 and the nano-silicon 202 be filled between adjacent graphite linings 10 and agraphitic carbon 301.Nano-silicon 202 links together by this agraphitic carbon 301, and when high density expanded graphite and nanometer silicon composite material 300 are as electrode material, this has flexible agraphitic carbon 301 is that nano-silicon 202 provides cushion space because of the volumetric expansion that embedding lithium causes, and can alleviate the electrode efflorescence because nano-silicon 202 volumetric expansion causes.
The high density expanded graphite that the preparation method of above-specified high density expanded graphite and nanometer silicon composite material 300 obtains and nanometer silicon composite material 300 pattern are for block, and particle diameter is 5 ~ 10 μm.The tap density of this high density expanded graphite and nanometer silicon composite material 300 is 0.4 ~ 0.5g/cm
3, higher than the tap density of the Si-C composite material that existing method obtains, the high density expanded graphite that this tap density is higher and nanometer silicon composite material 300, the load capacity on conducting base is more, makes obtained electrode slice have higher volume and capacity ratio.And the volume and capacity ratio of this high density expanded graphite and nanometer silicon composite material 300 is 1050 ~ 1200mAh/cm
3, the density of this high density expanded graphite and nanometer silicon composite material is 0.5 ~ 1g/cm
3.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
It is in the middle of 98% concentrated sulfuric acid that 8g scale graphite, 4g sodium nitrate are joined 200ml mass fraction, stirs 15min, obtain mixed solution at-5 DEG C; Then 8g potassium permanganate is slowly added in mixed solution, stir 2h at the temperature of-5 DEG C after, be warming up to 35 DEG C, and continue to stir 1h, obtain precursor solution; 400ml water is added in precursor solution, and is warming up to 98 DEG C, stir 2h, then suction filtration, namely obtain the graphite oxide with intercalation.
By the above-mentioned graphite oxide with intercalation 900 DEG C, heat treatment 2h obtains expanded graphite under nitrogen protection atmosphere condition.
Take the above-mentioned expanded graphite of 100mg, the commercial nano-silicon of 100mg, 100mg polyacrylonitrile add in ball grinder, add 5g mill ball, then 10ml ethanol wet material is added, ball milling 8h under the rotating speed of 400rpm, obtain black paste, this black paste is dried, obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Be placed in atmosphere furnace by above-specified high density expanded graphite and nanometer silicon composite material presoma 200, under nitrogen protection atmosphere, be warming up to 300 DEG C, insulation 2h, then be warming up to 600 DEG C, insulation 2h, then naturally cools to room temperature with furnace temperature.
Be Carbon and nitrogen sources further with acetonitrile, in tube furnace, at 500 ~ 800 DEG C, chemical vapour deposition (CVD) is carried out to above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma 200 plate carbon, be i.e. obtained high density expanded graphite and nanometer silicon composite material 300.
Embodiment 2
It is in the middle of 98% concentrated sulfuric acid that 8g scale graphite, 4g sodium nitrate are joined 190ml mass fraction, stirs 15min, obtain mixed solution at-5 DEG C; Then 16g potassium permanganate is slowly added in mixed solution, stir 1h at the temperature of-5 DEG C after, be warming up to 35 DEG C, and continue to stir 1h, obtain precursor solution; 380ml water is added in precursor solution, and is warming up to 98 DEG C, stir 2h, then suction filtration, namely obtain the graphite oxide with intercalation.
By the above-mentioned graphite oxide with intercalation 900 DEG C, heat treatment 2h obtains expanded graphite under argon atmosphere condition.
Take the above-mentioned expanded graphite of 200mg, the commercial nano-silicon of 100mg, 100mg polyacrylonitrile add in ball grinder, add 8g mill ball, then 10ml ethanol wet material is added, ball milling 8h under the rotating speed of 500rpm, obtain black paste, this black paste is dried, obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Be placed in atmosphere furnace by above-specified high density expanded graphite and nanometer silicon composite material presoma 200, under nitrogen protection atmosphere, be warming up to 300 DEG C, insulation 2h, then be warming up to 700 DEG C, insulation 2h, then naturally cools to room temperature with furnace temperature.
Be Carbon and nitrogen sources further with acetonitrile, in tube furnace, at 500 ~ 800 DEG C, chemical vapour deposition (CVD) is carried out to above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma 200 plate carbon, be i.e. obtained high density expanded graphite and nanometer silicon composite material 300.
Embodiment 3
It is in the middle of 98% concentrated sulfuric acid that 16g scale graphite, 8g sodium nitrate are joined 400ml mass fraction, stirs 15min, obtain mixed solution at-5 DEG C; Then 8g potassium permanganate is slowly added in mixed solution, stir 1h at the temperature of-5 DEG C after, be warming up to 35 DEG C, and continue to stir 2h, obtain precursor solution; 800ml water is added in precursor solution, and is warming up to 98 DEG C, stir 2h, then suction filtration, namely obtain the graphite oxide with intercalation.
By the above-mentioned graphite oxide with intercalation 900 DEG C, heat treatment 2h obtains expanded graphite under argon atmosphere condition.
Take the above-mentioned expanded graphite of 100mg, the commercial nano-silicon of 100mg, 200mg polyacrylonitrile add in ball grinder, add 10g mill ball, then 10ml ethanol wet material is added, ball milling 10h under the rotating speed of 400rpm, obtain black paste, this black paste is dried, obtains high density expanded graphite and nanometer silicon composite material presoma 200.
Be placed in atmosphere furnace by above-specified high density expanded graphite and nanometer silicon composite material presoma 200, under nitrogen protection atmosphere, be warming up to 250 DEG C, insulation 2h, then be warming up to 650 DEG C, insulation 2h, then naturally cools to room temperature with furnace temperature.
Be Carbon and nitrogen sources further with acetonitrile, in tube furnace, at 500 ~ 800 DEG C, chemical vapour deposition (CVD) is carried out to above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma 200 plate carbon, be i.e. obtained high density expanded graphite and nanometer silicon composite material 300.
The high density expanded graphite of Fig. 5 obtained by above-described embodiment 1 and the scanning electron microscope (SEM) photograph of nanometer silicon composite material 300.Can find out that obtained high density expanded graphite and nanometer silicon composite material 300 pattern are block by this scanning electron microscope (SEM) photograph, particle diameter is 5 ~ 10 μm.
The high density expanded graphite of Fig. 6 obtained by above-described embodiment 1 and the X-ray diffractogram of nanometer silicon composite material 300.Can find out that obtained high density expanded graphite and nanometer silicon composite material 300 are the compound of silicon and expanded graphite by this X-ray diffractogram.
Respectively the high density expanded graphite obtained by above-described embodiment 1 ~ 3 is mixed in the ratio of 8:1:1 with conductive black, polyacrylic acid with nanometer silicon composite material 300, slurry is made in the stirring that adds water, be applied on copper-foil conducting electricity and make electrode slice, use this electrode slice to make lithium ion battery (button cell).Wherein, in this lithium ion battery, use lithium sheet as to electrode, the electrolyte of this lithium ion battery by mass ratio be the dimethyl carbonate of 4.5:4.5:1, ethylene carbonate and fluorinated ethylene carbonate form.Lithium ion battery prepared by the high density expanded graphite obtained to Application Example 1 ~ 3 and nanometer silicon composite material 300 carries out cycle performance and high rate performance is tested, and obtains cycle performance test result curve chart (ginseng Fig. 7) and high rate performance test result curve chart (ginseng Fig. 8) respectively.
As seen from Figure 7, the electrode material of described lithium ion battery is under 500mA/g discharge and recharge, this initial mass specific capacity with the electrode slice of high density expanded graphite and nanometer silicon composite material 300 is 1056mAh/g, in circulation after 50 weeks, specific discharge capacity conservation rate is 84.7%, shows very excellent cyclical stability.
As seen from Figure 8, the specific discharge capacity of described lithium ion battery when 100mA/g discharge and recharge is 1480mAh/g, specific discharge capacity during 200mA/g discharge and recharge is 1280mAh/g, specific discharge capacity during 500mA/g discharge and recharge is 1050mAh/g, specific discharge capacity during 1A/g discharge and recharge is 810mAh/g, specific discharge capacity during 2A/g discharge and recharge is 520mAh/g, shows excellent high rate performance.
A kind of electrode slice (not shown), this electrode slice comprises conducting base (not shown) and is attached to above-specified high density expanded graphite and the nanometer silicon composite material 300 of this conducting base.
A kind of lithium ion battery (not shown), it is in the electronic installations such as mobile phone, computer, electronic reader, electric motor car.This lithium ion battery comprises positive pole, negative pole and electrolyte, and this negative or positive electrode comprises above-mentioned electrode slice.
The preparation method of high density expanded graphite of the present invention and nanometer silicon composite material 300 is by mixing graphite, the concentrated sulfuric acid, potassium permanganate, nitrate at low temperatures, the obtained graphite oxide of heating again, this graphite oxide obtains the larger expanded graphite of dilation 100 through heat treatment, nano-silicon 202 and carbon source 201 is made to mix in the graphite linings 10 embedding expanded graphite 100 by ball milling, again through heat treatment, high density expanded graphite and the nanometer silicon composite material 300 with high-tap density and high-volume and capacity ratio can be obtained.The structure of this high density expanded graphite and nanometer silicon composite material 300 is that nano-silicon 202 is embedded between the graphite linings 10 of extruded expanded graphite 100, and expanded graphite 100 gap is filled by agraphitic carbon 301; Expanded graphite 100 is as conducting matrix grain, and the gap by compression between expanded graphite 100 is as the cushion space in nano-silicon 202 charge and discharge process, and agraphitic carbon 301 can connect nano-silicon 202 and expanded graphite 100 forms three-dimensional conductive network; Utilize chemical vapour deposition (CVD) to plate carbon and can carry out Surface coating to nano-silicon 202 further, at utmost avoid the contact of nano-silicon 202 and electrolyte; Defect density inside plated film carbon can be improved by introducing nitrogen inside above-mentioned plated film carbon, improving the transmission rate of lithium ion inside plated film carbon further thus improving its performance.The preparation technology of the preparation method of this high density expanded graphite and nanometer silicon composite material 300 is simple, low, environmental protection of consuming energy.In addition, when using electrode material for lithium ion battery of the high density expanded graphite that obtains of said method and nanometer silicon composite material 300, the good cycle of this lithium ion battery and stablizing, and the high rate performance of this lithium ion battery is excellent.
Those skilled in the art will be appreciated that; above execution mode is only used to the present invention is described; and be not used as limitation of the invention; as long as within spirit of the present invention, the appropriate change do above embodiment and change all drop within the scope of protection of present invention.
Claims (10)
1. a preparation method for high density expanded graphite and nanometer silicon composite material, it comprises the steps:
Step S1, uses oxidant to be oxidized graphite, obtained graphite oxide, by adjusting the degree of oxidation of the consumption controlled oxidization graphite of oxidant;
Step S2, heat-treats above-mentioned graphite oxide, obtained expanded graphite;
Step S3, above-mentioned expanded graphite is mixed with nano-silicon, carbon source and carries out ball milling, obtain high density expanded graphite and nanometer silicon composite material presoma, this high density expanded graphite and nanometer silicon composite material presoma comprise multiple graphite linings, be filled in carbon source between graphite linings and nano-silicon;
Step S4, heat-treats above-specified high density expanded graphite and nanometer silicon composite material presoma, makes carbon source be converted into agraphitic carbon;
Step S5, uses chemical vapour deposition (CVD) at above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma surface deposition one deck 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 characterized in that: to the method that graphite is oxidized be: with the concentrated sulfuric acid, potassium permanganate, nitrate, this graphite is oxidized, wherein the mass ratio of graphite and nitrate is 2:1, the mass ratio of the concentrated sulfuric acid and graphite is (30 ~ 60): 1, and the quality of potassium permanganate is 0.5 ~ 2 times of the quality of graphite.
3. the preparation method of high density expanded graphite as claimed in claim 2 and nanometer silicon composite material, is characterized in that: described nitrate is selected from one or more in sodium nitrate, potassium nitrate, ammonium nitrate and calcium nitrate; Described graphite is selected from one or more in natural scale graphite, spherical graphite and micro crystal graphite; Described carbon source is selected from one or more in polyacrylonitrile, polyacrylic acid, polyvinylpyrrolidone and pitch.
4. the preparation method of high density expanded graphite as claimed in claim 2 and nanometer silicon composite material, is characterized in that: described step S1 comprises:
Step S11, adds in the concentrated sulfuric acid, at temperature T by graphite, nitrate according to certain ratio
1lower stirring a period of time t
1, obtain mixed solution;
Step S12, slowly adds a certain amount of potassium permanganate in above-mentioned mixed solution, temperature T
1lower stirring a period of time t
2after be warming up to a certain temperature T
2, continue to stir a period of time t
3, obtain precursor solution;
Step S13, slowly adds a certain amount of water in above-mentioned precursor solution, and is warming up to temperature T
3, stir t
4, suction filtration, namely obtains graphite oxide.
5. the preparation method of high density expanded graphite as claimed in claim 4 and nanometer silicon composite material, is characterized in that: described temperature T
1for-10 DEG C ~ 0 DEG C, described temperature T
2be 25 ~ 40 DEG C, described temperature T
3be 90 ~ 100 DEG C, described time t
1be 10 ~ 30min, described time t
2be 1 ~ 3h, described time t
3be 0.5 ~ 2h, described time t
4be 1 ~ 3h.
6. the preparation method of high density expanded graphite as claimed in claim 1 and nanometer silicon composite material, is characterized in that: described step S2 is:
By above-mentioned graphite oxide, be placed on 900 DEG C, heat treatment 2h under protective atmosphere, i.e. obtained expanded graphite.
7. the preparation method of high density expanded graphite as claimed in claim 1 and nanometer silicon composite material, it is characterized in that: described step S3 is: be 1:(0.01 ~ 2 to expanded graphite and nano-silicon, carbon source according to mass ratio): the ratio of (0.01 ~ 2) carries out ball milling, obtains high density expanded graphite and nanometer silicon composite material presoma;
Described step S4 is: under above-specified high density expanded graphite and nanometer silicon composite material are placed on protective atmosphere, be warming up to 150 ~ 300 DEG C, insulation 1 ~ 3h, then is warming up to 500 ~ 800 DEG C, and insulation 1 ~ 3h, then naturally cools to room temperature with furnace temperature;
Described step S5 is: take acetonitrile as Carbon and nitrogen sources, in tube furnace, at 500 ~ 800 DEG C, chemical vapour deposition (CVD) is carried out to above-mentioned heat treated high density expanded graphite and nanometer silicon composite material presoma surface plate carbon or nitrogen-doped carbon, be i.e. obtained high density expanded graphite and nanometer silicon composite material.
8. a high density expanded graphite and nanometer silicon composite material, it is characterized in that: this high density expanded graphite and nanometer silicon composite material comprise multiple graphite linings and the nano-silicon be filled between adjacent graphite linings and carbon, the structure of this material is that silicon nanoparticle is embedded between the graphite linings of extruded expanded graphite, and expanded graphite gap is filled with carbon; Expanded graphite is as conducting matrix grain, gap by compression between expanded graphite is as the cushion space expanded in nano-silicon charge and discharge process, the graphite linings that carbon connects nano-silicon and expanded graphite forms three-dimensional conductive network, and the density of this high density expanded graphite and nanometer silicon composite material is 0.5 ~ 1g/cm
3.
9. an electrode slice, is characterized in that: this electrode slice comprises conducting base and the high density expanded graphite as claimed in claim 8 that is attached on this conducting base and nanometer silicon composite material.
10. a lithium ion battery, it comprises positive pole, negative pole and electrolyte, it is characterized in that: this negative or positive electrode comprises as right wants high density expanded graphite as described in 8 and nanometer silicon composite material.
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