CN110085842A - A kind of silicon-carbon composite cathode material and preparation method thereof - Google Patents
A kind of silicon-carbon composite cathode material and preparation method thereof Download PDFInfo
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- CN110085842A CN110085842A CN201910387084.1A CN201910387084A CN110085842A CN 110085842 A CN110085842 A CN 110085842A CN 201910387084 A CN201910387084 A CN 201910387084A CN 110085842 A CN110085842 A CN 110085842A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 present invention relates to electrochemical fields, and in particular to a kind of silicon-carbon composite cathode material and preparation method thereof.Silicon-carbon composite cathode material of the present invention is made of three kinds of graphite, silicon ball and bitumencarb components, specific preparation method including the following steps: 1) silicon ball is added in the mixed solution of second alcohol and water, ultrasonic disperse, it stirs evenly, sequentially add ammonium hydroxide and TEOS reaction, centrifugation, obtains the composite balls of silicon dioxide coated nano silicon；2) composite balls are distributed in organic solvent, ultrasonic disperse, asphalt powder stirring and dissolving is added into the solution；3) silicon ball@silica@bitumen ball is formed using drying process with atomizing；4) by silicon ball@silica@bitumen ball by the carbonization treatment under pre-oxidation treatment and inert gas shielding; it is mixed with graphite; carry out high-energy ball milling processing; removal coated with silica layer is impregnated using hydrofluoric acid weak solution and obtains cavity structure, finally obtains silicon ball@cavity@bitumencarb and graphite powder homogeneously mixed product.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of silicon-carbon composite cathode material and preparation method thereof.
Background technique
With the development of science and technology and society, demand of the people to movable equipment is increasingly vigorous.As movable equipment electricity
The development of the principal mode in source, lithium ion battery is concerned.The current energy density of lithium ion battery, power density, circulation
Service life etc. all needs to be further increased, and cost needs further decrease.Lithium cell cathode material is most widely used also at present
It is graphite, but the relatively low only 372mAh/g of its theoretical capacity, it is difficult to meet the needs of high-energy density.By improving battery work
Skill is the main means for promoting energy density early period, but is also difficult to play remarkable effect at this stage.Silicon has known highest
Theoretical capacity (4200mAh/g), energy density can satisfy following a period of time completely and is more than to battery energy density
The requirement of 300Wh/kg, it is considered to be lithium cell cathode material of new generation, receive the extensive concern of material circle and industrial circle with
Research.But when silicon itself is used as lithium cell negative pole material, poor circulation, coulombic efficiency are low, and main cause is silicon body in embedding lithium
Product expands more than 300%, and for micron silicon, the huge stress that embedding lithium generates cannot be effectively relieved in deintercalation and powder occurs
It is broken, and poorly conductive itself, easily cause electrode material to crush, the problems such as capacity attenuation is serious, and coulombic efficiency is low.Commonly
Solution is: 1) nanosizing, and general 100nm silicon below may return to original pattern expansion；And carbon material 2)
Compound, carbon material provides conductive network for silicon, makes up the defect of silicon poorly conductive itself；3) carbon coating, can prevent SEI film because
It constantly ruptures and is formed caused by the volume expansion of silicon, and consume lithium ion；4) pore structure abundant is designed and prepared, is silicon
Volume expansion provide cushion space.These schemes are all embodied in the paper delivered at present and the patent declared.
CN105932245A discloses a kind of preparation method and applications of high compacted density silicon-carbon cathode material, material by
Core layer and core layer external coating composition, core layer is by being spray-dried and forging after nano-silicon, graphite and additive wet-mixing
Burning obtains, and calcining obtains the negative electrode material with clad after then mixing with covering liquid phase.
CN201811242706.3 discloses a kind of lithium battery high stability silicon-carbon cathode material and preparation method thereof, institute
Stating composite material is three layers of clad structure；Composite inner is substrate carbon material, and middle layer is by nano-silicon, carbon nanotube, soft
Carbon and/or hard carbon composition, composite material outer layer are the soft carbon layers formed after pitch is sintered.It is silicon by constructing multilayered structure
Volume expansion provides repeatedly effectively buffering, the shortcomings that by constructing micro conductive network around nano-silicon, improving silicon poorly conductive,
Effective protection aquiclude is designed simultaneously, silicon is avoided to contact with the direct of electrolyte.
CN201710730146.5 discloses lithium-ion battery silicon-carbon anode material and its preparation side of a kind of high stable
Method coats one layer of organic cracking carbon in simple substance silicon face, which can be effectively relieved the volume expansion of elemental silicon.Realize N, S
The codope of element can further improve the wetability of material, increase the lithium storage content of porous carbon.It is last again with graphene coated,
The uniformity and compactness that elemental silicon is wrapped by are increased, it is avoided and is contacted with the direct of electrolyte, and improve material
Conductivity.
CN103730644B disclose it is a kind of by silicon, Si oxide and graphite carry out high-energy ball milling, then with organic carbon source
The method that cladding prepares silicon-carbon cathode with high temperature cabonization is carried out, the spheric granules tap density which obtains is high, recycles and steady
It is qualitative preferably, but particle surface only one layer of indefiniteness carbon-coating of this method preparation, the silicon in material is easy to be exposed to electrolyte
In, it is difficult to stable SEI film is formed, leads to that material efficiency for charge-discharge is low, capacity attenuation trend is more apparent.
Numerous related patents all show above-mentioned resolving ideas in various degree, but mostly without reserving enough for nano-silicon
Expansion space, the silicon components in composite material are easily broken, lead to inducing capacity fading, and cycle performance is deteriorated.And deliver at present
Some academic papers all in perfect condition, disregard cost greatly, it is difficult to industrialized production.
Summary of the invention
The invention proposes a kind of silicon-carbon composite cathode materials and preparation method thereof to be used by designing reasonable structure
The process of universality, while being embodied as nano-silicon and improving enough cushion spaces, improve carbon coating and conductive network, preparation
Spherical composite material realizes high-bulk-density out, and the content for controlling silicon realizes the silicon-carbon cathode material specific capacity in 500-
1200mAh/g controllable adjustment.
The technical solution that the present invention takes to achieve the above object are as follows:
A kind of silicon-carbon composite cathode material, the composite negative pole material are made of three kinds of graphite, silicon ball and bitumencarb components,
The silicon ball is covered by bitumencarb shell, there is cavity, structure silicon ball cavity bitumencarb between silicon ball and carbon shell
It indicates.
Further, the complex microsphere that graphite and silicon ball@cavity@bitumencarb are constituted in composite negative pole material of the present invention is uniform
Dispersion.
Further, the present invention is on the basis of composite negative pole material total weight, the weight of each component in composite negative pole material
Percentage are as follows: graphite 0~70%, silicon ball 5~20%, bitumencarb 10~80%.
Further, graphite of the present invention be one of natural flake graphite, spherical graphite or artificial graphite or
The mixture of the two or more arbitrary proportions of person, bitumencarb are that the coal tar asphalt or petroleum with softening point at 100~280 DEG C drip
Blueness is raw material, and carbonization treatment is carried out under inert atmosphere protection and is obtained.
Further, silicon ball of the present invention is 300nm simple substance silicon particle below, and the simple substance silicon particle is that business is received
Rice silicon powder, or by micron silicon powder into crossing the obtained partial size of ball-milling treatment in 300nm nano silica fume below, or from receiving
The 300nm nano silicon spheres below that the thermal reduction of form of the rice silica spheres by magnesium heat, aluminothermy or carbon high-temp reduction obtains.
Further, the volume of silicon ball@cavity@bitumencarb cavity of the present invention is 3~5 times of silicon ball, bitumencarb shell
5~100nm of thickness degree, numerous silicon ball cavity pitch coke build-ups form micron order composite balls, and composite balls partial size is micro- 0.5~5
Rice.
A kind of preparation method of silicon-carbon composite cathode material, including the following steps:
1) silicon ball is added in the mixed solution of second alcohol and water, then ultrasonic disperse 30min or more is stirred evenly, upper
It states and sequentially adds ammonium hydroxide and TEOS in the suspension of silicon ball, after reaction, centrifugation is washed till neutrality with water and ethyl alcohol, obtains titanium dioxide
The composite balls of silicon cladding nano-silicon；
2) composite balls are distributed in the organic solvent dissolved with polyvinylpyrrolidone, ultrasonic disperse 30min or more, to this
Asphalt powder, stirring and dissolving are added in solution；
3) drying process with atomizing is used, 2) gained mixed solution is spraying, form silicon ball silica bitumen ball；
4) by the silicon ball@silica@bitumen ball of step 3) by the carbonization under pre-oxidation treatment and inert gas shielding
Processing, mixes with graphite, carries out high-energy ball milling processing by solvent of dehydrated alcohol, impregnates removal dioxy using hydrofluoric acid weak solution
SiClx clad obtains cavity structure, finally obtains silicon ball@cavity@bitumencarb and graphite powder homogeneously mixed product.
Further, the ratio of second alcohol and water is arbitrary proportion in step 1) of the present invention, and the additional amount of TEOS is root
According to the corresponding volume conversion (1mlTEOS theory can obtain 0.28g silica) of 2~20 times of silica of silicon ball quality, ammonia
The mass percent of water be 25%, and the additional amount of ammonium hydroxide be total volume 1%-5%, the reaction time be 2~for 24 hours；
In the step 2) organic solvent be one of N-methyl pyrrolidones, toluene, tetrahydrofuran or two kinds with
The mixture of upper arbitrary proportion, the weight of asphalt powder obtain after being converted according to the corresponding carbon yield of different softening point pitch；It is poly-
The additional amount of vinylpyrrolidone is 1-5 times of asphalt powder weight, and the weight fraction of asphalt powder in organic solvent is
0.1-5%.
Pre-oxidation treatment refers to that in air mass flow be 20~100ml/min in the step 4), and heating rate is 1 DEG C/min
Rising to 300 DEG C, constant temperature handles 2h, and carbonization treatment refers to that in heating rate be 1~10 DEG C/min, carbonization treatment temperature 600~
1000 DEG C, the carbonization treatment time be 1~5h, inert gas be nitrogen or argon gas, high-energy ball milling processing when rotational speed of ball-mill 100~
500rpm, Ball-milling Time are 10~120min, and hydrofluoric acid weak solution etching condition is to dilute 40wt.% hydrogen with ethyl alcohol or distilled water
The hydrofluoric acid weak solution that the mass percent that fluoric acid obtains is 5%~20%, 5~60min of etch period.
Silicon-carbon composite cathode material of the present invention is used to prepare electrode and lithium ion battery.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the XRD diagram of the embodiment of the present invention 1；
Fig. 2 is 1 scanning electron microscope (SEM) photograph of the embodiment of the present invention；
Fig. 3 is 1 charging and discharging curve figure of the embodiment of the present invention；
Fig. 4 is 1 cycle performance figure of the embodiment of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
Composite negative pole material in the present embodiment the preparation method is as follows:
1) 100mg nano silicon spheres are added in the 200ml mixed solution of second alcohol and water (ethyl alcohol: water volume ratio 6:4), ultrasound
Disperse 30min, then stir evenly, it is 25% that 5mL mass percent is sequentially added into the suspension of above-mentioned nano silicon spheres
Ammonium hydroxide and 1.428mlTEOS, after reacting 6h, centrifugation is washed till neutrality with water and ethyl alcohol, obtains answering for silicon dioxide coated nano silicon
Close ball；
2) composite balls obtained by step 1) are distributed to 100mL dissolved with the N-methyl pyrroles of 4g polyvinylpyrrolidone (PVP)
In alkanone (NMP) solvent, the asphalt powder that 0.8g softening point is 130 DEG C, stirring are added into the solution by ultrasonic disperse 30min
Dissolution；
3) use drying process with atomizing, by above-mentioned steps 2) in acquired solution, utilize peristaltic pump (wriggling pump speed is adjustable)
It is pumped into atomizer, using atomizer by solution atomization at micron order droplet, the solvent of drop is by the contact with high-temperature hot-air
It volatilizees rapidly, the solute in drop reconfigures to obtain spray dried products.The present embodiment uses peristaltic pump 10mL/min, high temperature
180℃.Form 1-5 microns of silicon ball@silica@bitumen ball；
4) by the silicon ball@silica@bitumen ball of step 3) by the carbonization treatment under pre-oxidation treatment and nitrogen protection
The HF solution etches 10min for being 20% by mass percent, removal clad obtain cavity structure, it is empty to finally obtain silicon ball@
Chamber@bitumencarb.
It is 20mL/min that wherein the pre-oxidation treatment, which is in air mass flow, and heating rate is that 1 DEG C/min rises to 300 DEG C,
Constant temperature handles 2h；
The carbonization heat treatment heating rate be 2 DEG C/min, 800 DEG C of heat treatment temperature, heat treatment time 2h；
Hydrofluoric acid weak solution etching condition is to dilute the mass percent that 40wt.% hydrofluoric acid obtains with ethyl alcohol or distilled water
For 20% hydrofluoric acid weak solution.
The XRD spectrum (Fig. 1) of the product shows the feature of silicon clearly, and the feature of bitumencarb is then by stronger silicon peak
Compacting.
It can be seen that, when amplification factor is 30000 times, can clearly it be seen from the stereoscan photograph (Fig. 2) of embodiment 1
To nano-silicon in the cavity surrounded by bitumencarb, therefore the enormousness expansion that nano-silicon generates in charge and discharge process
(300% or so) would not damage pitch carbon structure, to guarantee the stability of structure.And nano-silicon and bitumencarb are
Contact, also ensure that the electric conductivity of electrode material, therefore this structure is conducive to the stabilization of electrode material.Pitch and silicon
Composite material is micron ball, is conducive to the bulk density for improving electrode material.
The charging and discharging curve of the sample of the present embodiment is as shown in Figure 3, it can be seen that the sample shows bitumencarb and silicon
Charge-discharge characteristics, charging and discharging curve gently increase (charging) or reduce (electric discharge), and this curvilinear characteristic shows that the material is conducive to
Realize the voltage control of battery management system.
According to Fig. 4, it can be seen that, the stable circulation performance of the sample of the embodiment of the present invention 1 is preferable, in the electric current of 200mA/g
It under density, recycles 100 times, still keeps stablizing, reversible specific capacity is maintained at 800mAh/g.
Embodiment 2
Composite negative pole material in the present embodiment the preparation method is as follows:
1) 100mg nano silicon spheres are added in the 200mL mixed solution of second alcohol and water (ethyl alcohol: water volume ratio 9:1), ultrasound
Disperse 35min, then stir evenly, it is 25% that 2mL mass percent is sequentially added into the suspension of above-mentioned nano silicon spheres
Ammonium hydroxide and 0.714mLTEOS, after reaction for 24 hours, centrifugation is washed till neutrality with water and ethyl alcohol, obtains silicon dioxide coated nano silicon
Composite balls；
2) composite balls obtained by step 1) are distributed to 100mL dissolved with the toluene solvant of 0.5g polyvinylpyrrolidone (PVP)
In, the asphalt powder that 0.5g softening point is 150 DEG C, stirring and dissolving are added into the solution by ultrasonic disperse 35min；
3) drying process with atomizing is used, above-mentioned mixed solution is sprayed, forms 1-5 microns of silicon ball silica pitch
Ball；
4) the silicon ball@silica@bitumen ball of step 3) is passed through into the carbonization treatment under pre-oxidation treatment and nitrogen protection,
It is mixed again with 0.6g graphite powder, carries out ball-milling treatment by solvent of dehydrated alcohol, finally pass through 10%HF solution etches 30min,
Removal clad obtains cavity structure, finally obtains silicon ball@cavity@bitumencarb and graphite powder homogeneously mixed product；
It is 40mL/min that wherein the pre-oxidation treatment, which is in air mass flow, and heating rate is that 1 DEG C/min rises to 300 DEG C,
Constant temperature handles 2h；
The carbonization heat treatment heating rate be 5 DEG C/min, 600 DEG C of heat treatment temperature, heat treatment time 3h；
Rotational speed of ball-mill 100rpm when high-energy ball milling processing, Ball-milling Time 120min, hydrofluoric acid weak solution etch item
Part is the hydrofluoric acid weak solution for being 10% with the mass percent that ethyl alcohol or distilled water dilution 40wt.% hydrofluoric acid obtain.
Embodiment 3
Silicon-carbon composite cathode material in the present embodiment the preparation method is as follows:
1) 100mg nano silicon spheres are added in the 200mL mixed solution of second alcohol and water (ethyl alcohol: water volume ratio 4:6), ultrasound
Disperse 45min, then stir evenly, sequentially added into the suspension of above-mentioned nano silicon spheres 25% ammonium hydroxide of 10mL with
3.57mlTEOS, after reacting 3h, centrifugation is washed till neutrality with water and ethyl alcohol, obtains the composite balls of silicon dioxide coated nano silicon；
2) that composite balls obtained by step 1) are distributed to 100mL is molten dissolved with the tetrahydrofuran of 2g polyvinylpyrrolidone (PVP)
In agent, the asphalt powder that 0.5g softening point is 280 DEG C, stirring and dissolving are added into the solution by ultrasonic disperse 45min；
3) drying process with atomizing is used, step 2) mixed solution is spraying, form 1-5 microns of silicon ball silica drip
Green ball；
4) the silicon ball@silica@bitumen ball of step 3) is passed through into the carbonization treatment under pre-oxidation treatment and nitrogen protection,
It is mixed again with 0.55g graphite powder, carries out ball-milling treatment by solvent of dehydrated alcohol, finally pass through 5%HF solution etches 60min,
Removal clad obtains cavity structure, finally obtains silicon ball@cavity@bitumencarb and graphite powder homogeneously mixed product.
It is 60mL/min that wherein the pre-oxidation treatment, which is in air mass flow, and heating rate is that 1 DEG C/min rises to 300 DEG C,
Constant temperature handles 2h；
The carbonization heat treatment heating rate be 8 DEG C/min, 1000 DEG C of heat treatment temperature, heat treatment time 1h；
Rotational speed of ball-mill 300rpm when high-energy ball milling processing, Ball-milling Time 60min, hydrofluoric acid weak solution etching condition
The hydrofluoric acid weak solution for being 20% for the mass percent obtained with ethyl alcohol or distilled water dilution 40wt.% hydrofluoric acid.
Embodiment 4
Silicon-carbon composite cathode material in the present embodiment the preparation method is as follows:
1) 200mg nano silicon spheres are added in the 200mL mixed solution of second alcohol and water (ethyl alcohol: water volume ratio 1:9), ultrasound
Disperse 50min, then stir evenly, sequentially added into the suspension of above-mentioned nano silicon spheres 25% ammonium hydroxide of 6mL with
3.57mlTEOS, after reacting 12h, centrifugation is washed till neutrality with water and ethyl alcohol, obtains the composite balls of silicon dioxide coated nano silicon；
2) composite balls obtained by step 1) are distributed to 100mL dissolved with the volume ratio of 0.5g polyvinylpyrrolidone (PVP) is
The toluene of 1:9 and the in the mixed solvent of tetrahydrofuran, ultrasonic disperse 50min, it is 220 that 0.167g softening point is added into the solution
DEG C asphalt powder, stirring and dissolving；
3) drying process with atomizing is used, will be spraying by step 2) mixed solution, form 1-5 microns of silicon ball silica
Bitumen ball；
4) the silicon ball@silica@bitumen ball of step 3) is passed through into the carbonization treatment under pre-oxidation treatment and nitrogen protection,
It is mixed again with 0.7g graphite powder, carries out ball-milling treatment by solvent of dehydrated alcohol, finally pass through 10%HF solution etches 60min,
Removal clad obtains cavity structure, finally obtains silicon ball@cavity@bitumencarb and graphite powder homogeneously mixed product.
It is 80mL/min that wherein the pre-oxidation treatment, which is in air mass flow, and heating rate is that 1 DEG C/min rises to 300 DEG C,
Constant temperature handles 2h；
The carbonization heat treatment heating rate be 10 DEG C/min, 700 DEG C of heat treatment temperature, heat treatment time 4h；
Rotational speed of ball-mill 500rpm when high-energy ball milling processing, Ball-milling Time 20min, hydrofluoric acid weak solution etching condition
The hydrofluoric acid weak solution for being 20% for the mass percent obtained with ethyl alcohol or distilled water dilution 40wt.% hydrofluoric acid.
Claims (9)
1. a kind of silicon-carbon composite cathode material, which is characterized in that the composite negative pole material is by graphite, silicon ball and three kinds of bitumencarb
Component is constituted, and the silicon ball is covered by bitumencarb shell, there is cavity, structure silicon ball sky between silicon ball and carbon shell
Chamber@bitumencarb indicates.
2. silicon-carbon composite cathode material according to claim 1, which is characterized in that graphite and silicon in composite negative pole material
The complex microsphere that ball@cavity@bitumencarb is constituted is evenly dispersed.
3. silicon-carbon composite cathode material according to claim 1, which is characterized in that using composite negative pole material total weight as base
Standard, the weight percent of each component in composite negative pole material are as follows: graphite 0~70%, silicon ball 5~20%, bitumencarb 10~80%.
4. silicon-carbon composite cathode material according to claim 1, which is characterized in that the graphite be natural flake graphite,
The mixture of one of spherical graphite or artificial graphite or two or more arbitrary proportions, bitumencarb are existed with softening point
100~280 DEG C of coal tar asphalt or asphalt is raw material, and carbonization treatment is carried out under inert atmosphere protection and is obtained.
5. silicon-carbon composite cathode material according to claim 1, which is characterized in that the silicon ball is 300nm list below
Matter silicon particle, the simple substance silicon particle are business nano silica fume, or are existed by micron silicon powder into the partial size that ball-milling treatment obtains is crossed
300nm nano silica fume below, or the form of magnesium heat, aluminothermy or carbon high-temp reduction is crossed from nano silica ball warp
Heat-treat obtained 300nm nano silicon spheres below.
6. silicon-carbon composite cathode material according to claim 1, which is characterized in that the silicon ball@cavity@bitumencarb cavity
Volume be 3~5 times of silicon ball, 5~100nm of bitumencarb shell thickness, numerous silicon ball cavity pitch coke build-ups form microns
Grade composite balls, composite balls partial size is at 0.5~5 micron.
7. the preparation method of silicon-carbon composite cathode material described in any one of claims 1-6, which is characterized in that including following several
A step:
1) silicon ball is added in the mixed solution of second alcohol and water, then ultrasonic disperse 30min or more is stirred evenly, in above-mentioned silicon
Ammonium hydroxide and TEOS are sequentially added in the suspension of ball, after reaction, centrifugation is washed till neutrality with water and ethyl alcohol, obtains silica packet
Cover the composite balls of nano-silicon；
2) composite balls are distributed in the organic solvent dissolved with polyvinylpyrrolidone, ultrasonic disperse 30min or more, to the solution
Middle addition asphalt powder, stirring and dissolving；
3) drying process with atomizing is used, 2) gained mixed solution is spraying, form silicon ball silica bitumen ball；
4) the silicon ball@silica@bitumen ball of step 3) is passed through into the carbonization treatment under pre-oxidation treatment and inert gas shielding,
It is mixed with graphite, carries out high-energy ball milling processing by solvent of dehydrated alcohol, removal silica is impregnated using hydrofluoric acid weak solution
Clad obtains cavity structure, finally obtains silicon ball@cavity@bitumencarb and graphite powder homogeneously mixed product.
8. the preparation method of silicon-carbon composite cathode material according to claim 7, which is characterized in that second in the step 1)
The ratio of alcohol and water is arbitrary proportion, and the additional amount of TEOS is the corresponding body of silica according to 2~20 times of silicon ball quality
Product conversion (1mlTEOS theory can obtain 0.28g silica), the mass percent of ammonium hydroxide is 25%, and the additional amount of ammonium hydroxide is
The 1%-5% of total volume, the reaction time be 2~for 24 hours；
Organic solvent is one of N-methyl pyrrolidones, toluene, tetrahydrofuran or two or more in the step 2)
The mixture of meaning ratio, the weight of asphalt powder obtain after being converted according to the corresponding carbon yield of different softening point pitch；Polyethylene
The additional amount of pyrrolidones is 1-5 times of asphalt powder weight, and the weight fraction of asphalt powder in organic solvent is 0.1-
5%.
Pre-oxidation treatment refers to that in air mass flow be 20~100ml/min in the step 4), and heating rate is that 1 DEG C/min rises to
300 DEG C, constant temperature handle 2h, carbonization treatment refer to heating rate be 1~10 DEG C/min, 600~1000 DEG C of carbonization treatment temperature,
The carbonization treatment time is 1~5h, and inert gas is nitrogen or argon gas, 100~500rpm of rotational speed of ball-mill when high-energy ball milling is handled, ball
Time consuming is 10~120min, and hydrofluoric acid weak solution etching condition is to dilute 40wt.% hydrofluoric acid with ethyl alcohol or distilled water to obtain
Mass percent be 5%~20% hydrofluoric acid weak solution, 5~60min of etch period.
9. the application of silicon-carbon composite cathode material described in claim 1-6, it is characterized in that being used to prepare electrode and lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504430A (en) * | 2019-08-28 | 2019-11-26 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof |
| CN110589794A (en) * | 2019-09-06 | 2019-12-20 | 鞍钢化学科技有限公司 | Preparation method of large-size porous carbon material |
| CN111342035A (en) * | 2020-03-11 | 2020-06-26 | 西安越遴新材料研究院有限公司 | Method for modifying silicon-carbon composite negative electrode by asphalt modification process derivative |
| CN111564611A (en) * | 2020-04-07 | 2020-08-21 | 河南电池研究院有限公司 | Silicon-oxygen-carbon composite material, preparation method and lithium battery material |
| CN111900347A (en) * | 2020-07-14 | 2020-11-06 | 中国科学院山西煤炭化学研究所 | Method for preparing silicon-carbon composite material based on ball milling method in air atmosphere and application thereof |
| CN112072115A (en) * | 2020-09-17 | 2020-12-11 | 内蒙古欣源石墨烯科技股份有限公司 | Method for constructing graphite porous silicon-carbon composite negative electrode material by synchronously purifying graphite and preparing porous silicon-carbon |
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| CN112164773A (en) * | 2020-08-31 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Preparation method of silicon-carbon composite negative electrode material |
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| CN113054178A (en) * | 2021-03-24 | 2021-06-29 | 浙江锂宸新材料科技有限公司 | Polo honey-like silicon-carbon shell-core structure composite negative electrode material and preparation method and application thereof |
| CN114105133A (en) * | 2021-10-19 | 2022-03-01 | 湖南金硅科技有限公司 | Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof |
| CN114388755A (en) * | 2021-12-14 | 2022-04-22 | 鞍钢化学科技有限公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
| CN114744178A (en) * | 2022-04-29 | 2022-07-12 | 中国有色桂林矿产地质研究院有限公司 | Nano silicon-graphite composite negative electrode material with carbon-coated and aluminum metaphosphate composite modification layer on surface and preparation method thereof |
| CN114975962A (en) * | 2022-06-24 | 2022-08-30 | 内蒙古瑞盛天然石墨应用技术研究院 | Method for preparing silicon-carbon cathode material by using photovoltaic waste silicon powder and graphene oxide |
| CN117352711A (en) * | 2023-12-06 | 2024-01-05 | 上海巴库斯超导新材料有限公司 | Preparation process of novel carbon-coated silicon and graphite composite negative electrode material |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504430A (en) * | 2019-08-28 | 2019-11-26 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof |
| CN110589794A (en) * | 2019-09-06 | 2019-12-20 | 鞍钢化学科技有限公司 | Preparation method of large-size porous carbon material |
| CN111342035B (en) * | 2020-03-11 | 2021-12-21 | 西安英纳吉科技有限公司 | Method for modifying silicon-carbon composite negative electrode by asphalt modification process derivative |
| CN111342035A (en) * | 2020-03-11 | 2020-06-26 | 西安越遴新材料研究院有限公司 | Method for modifying silicon-carbon composite negative electrode by asphalt modification process derivative |
| CN111564611A (en) * | 2020-04-07 | 2020-08-21 | 河南电池研究院有限公司 | Silicon-oxygen-carbon composite material, preparation method and lithium battery material |
| CN111900347A (en) * | 2020-07-14 | 2020-11-06 | 中国科学院山西煤炭化学研究所 | Method for preparing silicon-carbon composite material based on ball milling method in air atmosphere and application thereof |
| CN112164773A (en) * | 2020-08-31 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Preparation method of silicon-carbon composite negative electrode material |
| CN112133894A (en) * | 2020-09-03 | 2020-12-25 | 深圳石墨烯创新中心有限公司 | Negative electrode material for lithium battery and preparation method of material |
| CN112072115A (en) * | 2020-09-17 | 2020-12-11 | 内蒙古欣源石墨烯科技股份有限公司 | Method for constructing graphite porous silicon-carbon composite negative electrode material by synchronously purifying graphite and preparing porous silicon-carbon |
| CN112635734A (en) * | 2020-12-21 | 2021-04-09 | 惠州亿纬锂能股份有限公司 | Preparation method and application of carbon-coated silica material loaded by carbon nano tube |
| CN112635734B (en) * | 2020-12-21 | 2022-04-12 | 惠州亿纬锂能股份有限公司 | Preparation method and application of carbon-coated silica material loaded by carbon nano tube |
| CN113054178A (en) * | 2021-03-24 | 2021-06-29 | 浙江锂宸新材料科技有限公司 | Polo honey-like silicon-carbon shell-core structure composite negative electrode material and preparation method and application thereof |
| CN113054178B (en) * | 2021-03-24 | 2022-01-11 | 浙江锂宸新材料科技有限公司 | Polo honey-like silicon-carbon shell-core structure composite negative electrode material and preparation method and application thereof |
| CN114105133A (en) * | 2021-10-19 | 2022-03-01 | 湖南金硅科技有限公司 | Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof |
| CN114105133B (en) * | 2021-10-19 | 2023-09-05 | 湖南金硅科技有限公司 | Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof |
| CN114388755A (en) * | 2021-12-14 | 2022-04-22 | 鞍钢化学科技有限公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
| CN114744178A (en) * | 2022-04-29 | 2022-07-12 | 中国有色桂林矿产地质研究院有限公司 | Nano silicon-graphite composite negative electrode material with carbon-coated and aluminum metaphosphate composite modification layer on surface and preparation method thereof |
| CN114975962A (en) * | 2022-06-24 | 2022-08-30 | 内蒙古瑞盛天然石墨应用技术研究院 | Method for preparing silicon-carbon cathode material by using photovoltaic waste silicon powder and graphene oxide |
| CN117352711A (en) * | 2023-12-06 | 2024-01-05 | 上海巴库斯超导新材料有限公司 | Preparation process of novel carbon-coated silicon and graphite composite negative electrode material |
| CN117352711B (en) * | 2023-12-06 | 2024-01-30 | 上海巴库斯超导新材料有限公司 | Preparation process of novel carbon-coated silicon and graphite composite negative electrode material |
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