CN109449401A - Silicon-carbon cathode material and preparation method thereof, cathode and battery - Google Patents
Silicon-carbon cathode material and preparation method thereof, cathode and battery Download PDFInfo
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- CN109449401A CN109449401A CN201811261434.1A CN201811261434A CN109449401A CN 109449401 A CN109449401 A CN 109449401A CN 201811261434 A CN201811261434 A CN 201811261434A CN 109449401 A CN109449401 A CN 109449401A
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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
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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
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 provides silicon-carbon cathode material and preparation method thereof, cathode and batteries.Wherein, the method for preparing silicon-carbon cathode material includes: silicon particle to be dispersed in the first solvent to form the first mixed liquor；Porous carbon substrate is dispersed in the second solvent to form the second mixed liquor；First mixed liquor and second mixed liquor are mixed, to form third mixed liquor；The first roasting is carried out after the third mixed liquor is dried in the first inert atmosphere, to obtain the silicon-carbon cathode material, wherein the porous carbon substrate is prepared using biomass.Inventors have found that this method is simple, convenient, it is easy to accomplish, the performance for obtaining silicon-carbon cathode material is preferable.
Description
Technical field
The present invention relates to battery technology fields, specifically, being related to silicon-carbon cathode material and preparation method thereof, cathode and electricity
Pond.
Background technique
Currently, most widely used negative electrode material is silicon based anode material, theoretical specific capacity (high temperature with higher
4200mAh/g, room temperature 3580mAh/g), low de- lithium current potential (< 0.5V), environmental-friendly, rich reserves, cost is relatively low
Etc. advantages and be considered as great potential next-generation lithium ion battery with high energy density negative electrode material.But silicon-based anode material
There are still two critical issues to need to solve in scale use process for material: 1, silicon materials during removal lithium embedded receive repeatedly by expansion
Contracting, swelling volume cause negative electrode material dusting, fall off up to 300%, and eventually lead to negative electrode material and lose electrical contact and make battery
Thoroughly failure；2, the continued propagation of silicon materials surface SEI film can irreversibly consume always limited electrolyte in battery and come
From the lithium of anode, the rapid decaying of battery capacity is eventually led to.
Thus, current negative electrode material still has much room for improvement.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is that the method that proposition prepares silicon-carbon cathode material, this method are simple, convenient, it is easy to accomplish, it can be effective
The expansion for weakening silicon particle effectively reduces silicon particle and reunites or the phenomenon that dusting, the silicon-carbon cathode material for utilizing this method to obtain
The first effect of material or specific capacity are higher.
In one aspect of the invention, the present invention provides a kind of methods for preparing silicon-carbon cathode material.According to the present invention
Embodiment, this method comprises: silicon particle is dispersed in the first solvent to form the first mixed liquor；By porous carbon substrate point
It is dispersed in the second solvent to form the second mixed liquor；First mixed liquor and second mixed liquor are mixed, so as to shape
At third mixed liquor；The first roasting is carried out after the third mixed liquor is dried in the first inert atmosphere, with
Just the silicon-carbon cathode material is obtained, wherein the porous carbon substrate is prepared using biomass.Inventors have found that
This method is simple, convenient, it is easy to accomplish, prepare that porous carbon substrate is more environmentally friendly, and cost is relatively low using biomass, and biology
Matter has eucaryotic cell structure, can obtain the relatively uniform porous carbon substrate of pore size distribution$, and silicon particle progress decentralized processing is had
It is distributed in porous carbon substrate conducive to silicon particle is relatively uniform, reduces the generation of agglomeration, the silicon obtained using this method
Silicon particle is embedded in the hole of porous carbon substrate in carbon negative pole material, is conducive to the expansion for weakening silicon particle, and then effectively reduce silicon
The phenomenon that particle agglomeration or dusting, can also effectively slow down the growth of SEI film, significantly improve the electrochemistry of silicon-carbon cathode material
Performance so that the service life of silicon-carbon cathode material is longer, and then improves the battery being prepared using the silicon-carbon cathode material
First effect, specific capacity and cycle performance, higher battery capacity is able to maintain in longer use process.
According to an embodiment of the invention, being combined by first mixed liquor and second mixed liquor by described
One mixed liquor, which is added drop-wise to, to carry out in second mixed liquor.What the first mixed liquor was mixed with the second mixed liquor as a result, is more equal
Even, silicon particle can be more evenly dispersed in the hole of porous carbon substrate, the excellent electrochemical performance of silicon-carbon cathode material, so that
The head for the battery being prepared using the silicon-carbon cathode material is imitated, specific capacity and cycle performance are higher, and the service life is longer.
According to an embodiment of the invention, before the third mixed solution is dried further include: Xiang Suoshu
Covering material is added in third mixed solution.Covering material can be formed in the outer surface of porous carbon substrate and silicon particle as a result,
Silicon particle is advantageously allowed to be not easy to fall off from the hole of porous carbon substrate, so that the structure of silicon-carbon cathode material is more stable,
And a possibility that being more advantageous to the expansion for weakening silicon particle, further decreasing silicon particle reunion or dusting, slow down the life of SEI film
Long better effect, the excellent electrochemical performance of silicon-carbon cathode material, the battery being prepared using the silicon-carbon cathode material
Head effect, specific capacity or cycle performance are higher, and the service life is longer.
According to an embodiment of the invention, into the third mixed solution be added covering material include: by covering material with
It is added drop-wise in the third mixed liquor after the mixing of third solvent, then carries out ball-milling treatment.Be conducive to covering material, silicon as a result,
The uniform mixing of particle and porous carbon substrate is conducive to the specific capacity for improving silicon-carbon cathode material and first effect, and ball-milling treatment
So that the specific surface area of the silicon-carbon cathode material obtained is larger, it is more advantageous to the chemical property for improving silicon-carbon cathode material.
According to an embodiment of the invention, the time of the ball-milling treatment is 8-10h.It help to obtain granular size as a result,
More appropriate silicon-carbon cathode material, so that the tap density of silicon-carbon cathode material is higher, so that the appearance of the battery finally obtained
It measures higher.
According to an embodiment of the invention, the porous carbon substrate through the following steps that obtain: the biomass is set
The second roasting is carried out in the second inert atmosphere to obtain charcoal；The charcoal is placed in third inert atmosphere and is carried out
Third roasts to obtain the porous carbon substrate.The charcoal for first carrying out the second roasting acquisition using biomass as a result, has
Certain electric conductivity is conducive to the progress of third roasting, and the use of biomass is more environmentally friendly, and cost is relatively low, biomass tool
Standby eucaryotic cell structure is conducive to roasting and forms the charcoal for having porous structure, and third roasting carries out the pore structure in charcoal
Adjustment, so that the structure of the porous carbon substrate obtained is more stable, tap density is higher, and conductive capability is stronger, transmit electronics
Ability is stronger, is conducive to the first effect, specific capacity and the cycle performance that improve battery, so that the service performance of battery is preferable.
According to an embodiment of the invention, the biomass includes microalgae.The source of biomass is relatively broad as a result, cost
It is lower；Since microalgae has eucaryotic cell structure, porous structure is advantageously formed after being roasted.
According to an embodiment of the invention, the microalgae in Huang Sizao, chlorella, spirulina and brown alga at least it
One.As a result, by the better effect of the porous structure obtained after the roasting of above-mentioned microalgae, it is more advantageous to silicon particle insertion acquisition
In pore structure.
According to an embodiment of the invention, second maturing temperature is 600-1000 degrees Celsius, the third maturing temperature
It is 2000-2700 degrees Celsius.Second the preferable charcoal of electric conductivity that can be obtained is roasted as a result, had in charcoal more
Pore structure；Third roasts the better effect to the porosity in charcoal, so that the structure of the porous carbon substrate obtained is more
Stablize, tap density is higher, and conductive capability is stronger, is conducive to the first effect, specific capacity and the cycle performance that improve battery, so that electric
The service performance in pond is preferable.
According to an embodiment of the invention, first solvent in dehydrated alcohol, isopropanol and deionized water at least
One of.The selection of the first solvent is relatively broad as a result, and the effect for dispersing silicon particle is preferable, the electrochemistry of silicon-carbon cathode material
Can be excellent, be conducive to the first effect, specific capacity and the cycle performance that improve the battery being prepared using the silicon-carbon cathode material.
According to an embodiment of the invention, second solvent is selected from deionized water, dehydrated alcohol, isopropanol, in ethylene glycol
At least one of.The selection of the second solvent is relatively broad as a result, and the effect of dispersing cellular carbon substrate is preferable, so that silicon-carbon cathode
The chemical property of material is good, is conducive to the first effect, the specific capacity that improve the battery being prepared using the silicon-carbon cathode material
And cycle performance.
According to an embodiment of the invention, it is 1 that the speed in second mixed liquor, which is added dropwise, in first mixed liquor
It drips per second.The first mixed liquor can be sufficiently mixed with the second mixed liquor as a result, and mixing is more uniform, is conducive to silicon
Grain is uniformly dispersed in porous carbon substrate, and silicon particle there's almost no agglomeration, so that the electrochemistry of silicon-carbon cathode material
It is functional, and then improve the first effect of the battery being prepared using the silicon-carbon cathode material, specific capacity and cycle performance
Better effect.
According to an embodiment of the invention, the partial size of the silicon particle is 300-500 nanometers, the hole in the porous carbon substrate
Diameter size is 1-10 microns.Silicon particle can be relatively easy in the porous carbon substrate of insertion as a result, and the aperture of porous carbon substrate
Mutual cooperation between the particle size of silicon particle is conducive to inhibit the expansion of silicon particle, to effectively avoid the group of silicon particle
Poly- or powder phenomenon-tion, can also effectively slow down the growth of SEI film, so that the excellent electrochemical performance of silicon-carbon cathode material, into
And make the service life for the battery being prepared using the silicon-carbon cathode material longer, can in longer use process
Keep higher battery capacity.
According to an embodiment of the invention, the gross mass based on the silicon-carbon cathode material, the content of the silicon particle is 10-
20wt%.The content of silicon particle is more appropriate as a result, and what is be distributed in porous carbon substrate is relatively uniform, there's almost no reunion
Phenomenon is conducive to the chemical property for improving silicon-carbon cathode material.
According to an embodiment of the invention, the mass ratio of the covering material and the silicon particle is (1-2): 1.On as a result,
The covering material for stating content can effectively coat silicon particle and porous carbon substrate, the silicon-carbon cathode material obtained after roasting
Silicon particle hardly falls off from porous carbon substrate in material, and then improves the stability of the structure of silicon-carbon cathode material, and silicon
Particle is less susceptible to expand after being wrapped by, and powder phenomenon-tion hardly occurs, and the growth of SEI film is slower, silicon
The chemical property of carbon negative pole material is more preferably.
According to an embodiment of the invention, the covering material is selected from least one of organic gel materials, carbohydrate.By
This, material source is extensive, and price is lower, and that disperses in third mixed liquor is relatively uniform, coats silicon particle and porous carbon-based
The effect of material is preferable, and can obtain the carbon material for having porous structure after baking, and improving, silicon-carbon cathode material structure is steady
The chemical property of silicon-carbon cathode material is hardly influenced while qualitative.
According to an embodiment of the invention, first roasting carries out under inert atmosphere conditions, and first roasting
The temperature of burning is 500-1000 DEG C, calcining time 2-5h.The first roasting can be stronger embedded in porous by silicon particle as a result,
In the hole of carbon substrate, it is also possible that the coating function that covering material plays after firing is more preferably, and then silicon-carbon can be improved
The stability of negative electrode material structure is conducive to the chemical property for improving silicon-carbon cathode material, so that negative using the silicon-carbon
The cycle performance for the battery that pole material is prepared, first effect and specific capacity are higher.
In another aspect of this invention, the present invention provides a kind of silicon-carbon cathode materials.According to an embodiment of the invention, should
Silicon-carbon cathode material is prepared using mentioned-above method.Inventors have found that cost is relatively low for the silicon-carbon cathode material,
Structure is more stable, excellent electrochemical performance, the first effect of the battery being prepared using the silicon-carbon cathode material, specific capacity and
Cycle performance is preferable, and service life is longer, and higher specific capacity and cyclicity are able to maintain in longer use process
Can, the market competitiveness is stronger, the consumption experience for the consumer that is content with very little.
In another aspect of this invention, the present invention provides a kind of cathode.According to an embodiment of the invention, the cathode includes
Mentioned-above silicon-carbon cathode material.Inventors have found that the stability of the cathode is preferable, the ability of insertion or abjection lithium compared with
By force, so that the first effect of battery, specific capacity and cycle performance are preferable, service life is longer, and in longer use process
It is able to maintain higher specific capacity and cycle performance, the market competitiveness is stronger, the consumption experience for the consumer that is content with very little.
In another aspect of this invention, the present invention provides a kind of batteries.According to an embodiment of the invention, the battery pack
It includes: mentioned-above cathode；Anode；Diaphragm, wherein the diaphragm setting is between the cathode and the anode；Electrolyte,
At least part of at least part of the anode, at least part of the cathode and the diaphragm is immersed in the electrolysis
In liquid.Inventors have found that the battery structure is simple, is easily achieved, price is lower, and head effect, specific capacity and cycle performance are preferable,
Service life is longer, and higher specific capacity and cycle performance, the market competitiveness are able to maintain in longer use process
It is relatively strong, the consumption experience for the consumer that is content with very little.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram that silicon-carbon cathode material is prepared in one embodiment of the invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of Huang Sizao in one embodiment of the invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of the porous carbon substrate of embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of the porous carbon substrate of embodiment 2.
Fig. 5 is the scanning electron microscope (SEM) photograph of the silicon-carbon cathode material of embodiment 7.
Fig. 6 is the scanning electron microscope (SEM) photograph of the silicon-carbon cathode material of embodiment 8.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
The present invention is following understanding based on inventor and discovery and completes:
Currently, there are silicon particles to expand the phenomenon that leading to dusting, and the SEI film on silicon particle surface repeatedly for silicon based anode material
Sustainable growth, limited electrolyte and the lithium from anode in irreversible consumption battery, cause the capacity of battery rapid always
Decaying.In view of the above technical problems, inventor conducts in-depth research, and finds after research, silicon particle can be embedded in porous
In the hole of carbon substrate, so that the expansion of silicon particle is restricted, and then reduces the powder phenomenon-tion of silicon particle, it can also limit
The growth of SEI film, inventor has found after continuing research, in order to which silicon particle is uniformly dispersed in porous carbon substrate, Ke Yixian
Silicon particle is subjected to decentralized processing, to improve silicon-carbon cathode material chemical property.
In view of this, in one aspect of the invention, the present invention provides a kind of methods for preparing silicon-carbon cathode material.Root
According to the embodiment of the present invention, referring to Fig.1, this method comprises:
S100: silicon particle is dispersed in the first solvent to form the first mixed liquor.
According to an embodiment of the invention, by silicon particle progress decentralized processing be conducive to silicon particle it is relatively uniform be distributed in it is more
In the carbon substrate of hole, the generation of agglomeration is reduced, improves the structural stability of silicon-carbon cathode material, in favor of improving silicon-carbon cathode
The chemical property of material, so can be improved the first effect for the battery being prepared using the silicon-carbon cathode material, specific capacity with
And cycle performance.If not carrying out above-mentioned decentralized processing to silicon particle, silicon particle is easy to happen agglomeration, silicon-carbon cathode material
Structural stability it is lower, chemical property is bad.
According to an embodiment of the invention, first solvent in dehydrated alcohol, isopropanol and deionized water at least
One of.The selection of the first solvent is relatively broad as a result, and the effect for dispersing silicon particle is preferable, is conducive to improve silicon-carbon cathode material
Chemical property.
According to an embodiment of the invention, the partial size of the silicon particle be 300-500 nanometers (such as 300 nanometers, 350 nanometers,
400 nanometers, 450 nanometers, 500 nanometers etc.).The partial size of silicon particle is more appropriate as a result, and specific surface area is larger, so that silicon-carbon is negative
Pole material electrochemical performance is excellent, and the ability of insertion or abjection lithium is stronger, so that being prepared using the silicon-carbon cathode material
The head of obtained battery is imitated, specific capacity and cycle performance are higher.Relative to above-mentioned particle size range, when the partial size of silicon particle is too small
When, it cannot be effectively embedded into the hole of porous carbon substrate, so that the structural stability of silicon-carbon cathode material is relatively bad；When
When the partial size of silicon particle is excessive, the expansion of silicon particle can destroy the pore structure of porous carbon substrate in use, so that silicon-carbon
The structural stability of negative electrode material is relatively bad, and chemical property is relatively bad.
According to an embodiment of the invention, in the first mixed liquor silicon particle content be 20-40wt% (such as 20wt%,
25wt%, 30wt%, 35wt%, 40wt% etc.), be conducive to disperse silicon particle as a result, relatively uniform.
According to an embodiment of the invention, silicon particle is dispersed in the first solvent through the following steps that carrying out: by silicon
Particle is put into the first solvent, and ultrasonic disperse 30min-4h obtains the first mixed liquor.Dispersion effect is preferable as a result,.
S200: porous carbon substrate is dispersed in the second solvent to form the second mixed liquor.
According to an embodiment of the invention, pore size in the porous carbon substrate be 1-10 microns (such as 1 micron, it is 2 micro-
Rice, 3 microns, 4 microns, 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns etc.).Silicon particle can compare appearance as a result,
In the porous carbon substrate of easy insertion, and the mutual cooperation between the aperture of porous carbon substrate and the particle size of silicon particle is conducive to
The life of SEI film can also effectively be slowed down to effectively avoid reunion or the powder phenomenon-tion of silicon particle by inhibiting the expansion of silicon particle
It is long, so that the service life of silicon-carbon cathode material is longer, higher battery capacity is able to maintain in longer use process.
Relative to above-mentioned pore size, when the aperture in porous carbon substrate is excessive, silicon particle cannot be effectively embedded into wherein, so that silicon-carbon
The structural stability of negative electrode material is relatively bad；When the aperture in porous carbon substrate is too small, silicon particle in use
Expansion can destroy the pore structure of porous carbon substrate, so that the structural stability of silicon-carbon cathode material is relatively bad, service performance phase
To bad.
According to an embodiment of the invention, second solvent is selected from deionized water, dehydrated alcohol, isopropanol, in ethylene glycol
At least one of.The selection of the second solvent is relatively broad as a result, and the effect of dispersing cellular carbon substrate is preferable, is conducive to improve silicon
The chemical property of carbon negative pole material.
According to an embodiment of the invention, in the second mixed liquor porous carbon substrate content can for 5-40wt% (such as
5wt%, 10wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt% etc.), be conducive to as a result, by porous carbon substrate point
Cloth is uniform, and is conducive to the mixing of subsequent first mixed liquor and the second mixed liquor so that silicon particle be evenly distributed in it is more
In the carbon substrate of hole.
According to an embodiment of the invention, porous carbon substrate is dispersed in the second solvent through the following steps that carrying out:
Porous carbon substrate is slowly added in the second solvent under agitation, be added after the completion of continue stir 1-12h (such as 1h, 2h,
4h, 6h, 8h, 10h, 12h etc.), obtain the second mixed liquor.Be conducive to porous carbon substrate being uniformly dispersed in second as a result, molten
In agent.
According to an embodiment of the invention, the porous carbon substrate is prepared using biomass.Of the invention one
In a little embodiments, the porous carbon substrate is through the following steps that obtain: the biomass is placed in the second inert atmosphere (example
Such as argon atmosphere, nitrogen atmosphere) in carry out second roasting to obtain charcoal；The charcoal is placed in third indifferent gas
Third roasting is carried out in atmosphere (such as argon atmosphere, nitrogen atmosphere etc.) to obtain the porous carbon substrate.Biology is utilized as a result,
Matter carries out the charcoal that the second roasting obtains and has certain electric conductivity, is conducive to the progress of third roasting, and biomass
Using more environmentally friendly, cost is relatively low, and biomass has eucaryotic cell structure (specifically can refer to the scanning electron microscope (SEM) photograph of Huang Sizao in Fig. 2),
Being conducive to roasting and forms the charcoal for having porous structure, third roasting adjusts the pore structure in charcoal, so that
Obtain porous carbon substrate structure it is more stable, tap density is higher, and conductive capability is stronger, be conducive to improve battery capacity with
And first effect, so that the service performance of battery is preferable.
According to an embodiment of the invention, second maturing temperature is 600-1000 degrees Celsius of (such as 600 degrees Celsius, 650
Degree Celsius, 700 degrees Celsius, 750 degrees Celsius, 800 degrees Celsius, 850 degrees Celsius, 900 degrees Celsius, 950 degrees Celsius, 1000 degrees Celsius
Deng), the third maturing temperature be 2000-2700 degrees Celsius (such as 2000 degrees Celsius, 2050 degrees Celsius, 2100 degrees Celsius,
2150 degrees Celsius, 2200 degrees Celsius, 2250 degrees Celsius, 2300 degrees Celsius, 2350 degrees Celsius, 2400 degrees Celsius, 2450 degrees Celsius,
2500 degrees Celsius, 2550 degrees Celsius, 2600 degrees Celsius, 2650 degrees Celsius, 2700 degrees Celsius etc.).The second roasting can obtain as a result,
The preferable charcoal of electric conductivity, have porous structure in charcoal；Third is roasted to the porosity in charcoal
Better effect so that obtain porous carbon substrate structure it is more stable, tap density is higher, and conductive capability is stronger, is conducive to
First effect, specific capacity and the cycle performance for improving battery, so that the service performance of battery is preferable.Relative to above-mentioned maturing temperature model
It encloses, the impurity in Huang Sizao can not then be burnt up when the temperature of the second roasting is too low, other impurities ingredient is contained in Huang Sizao
Such as sulphur, nitrogen etc. cause the chemical property of silicon-carbon cathode material relatively bad, when then roasting when the temperature is excessively high for the second roasting
Cost is excessively high, belongs to the wasting of resources, and the effect of high temperature purification is also not achieved；When the temperature of third roasting is too low, then high temperature is pure
Change carry out opposite to be not thorough, and the electric conductivity and tap density of material can not be improved, when third roasting when the temperature is excessively high then
Belong to the wasting of resources, consuming cost is excessively high.
According to an embodiment of the invention, the biomass includes microalgae.The source of biomass is relatively broad as a result, cost
It is lower；Since microalgae has eucaryotic cell structure, the uniform porous structure of pore size distribution is advantageously formed after being roasted, and utilize
The tap density for the porous carbon substrate that microalgae is prepared is high, is conducive to the capacity for improving battery.It should be noted that microalgae can
To be provided in the form of microalgae cured leaf, microalgae cured leaf can be pre-processed (such as air-flow crushing etc.) before the use, with benefit
In subsequent dispersion.
According to an embodiment of the invention, the microalgae in Huang Sizao, chlorella, spirulina and brown alga at least it
One.As a result, by the better effect of the porous structure obtained after the roasting of above-mentioned microalgae, it is more advantageous to silicon particle insertion acquisition
In pore structure.
S300: first mixed liquor and second mixed liquor are mixed, to form third mixed liquor.
According to an embodiment of the invention, being combined by first mixed liquor and second mixed liquor by described
One mixed liquor, which is added drop-wise to, to carry out in second mixed liquor.What the first mixed liquor was mixed with the second mixed liquor as a result, is more equal
Even, silicon particle can be more evenly dispersed in the hole of porous carbon substrate, so that silicon-carbon cathode material chemical property is more preferable, it is embedding
The ability for entering or deviating from lithium is stronger, so that first effect, specific capacity and the cycle performance of battery are more preferably, service life is more
It is long.
According to an embodiment of the invention, it is 1- that the speed in second mixed liquor, which is added dropwise, in first mixed liquor
3 drops are (such as 1 drop is per second, 2 drip per second, 3 drops are per second etc.) per second.The first mixed liquor can be mixed sufficiently with the second mixed liquor as a result,
It closes, and mixing is more uniform, is conducive to be uniformly dispersed in silicon particle in porous carbon substrate, silicon particle there's almost no group
Poly- phenomenon, and then improve the chemical property of silicon-carbon cathode material, and make the first effect of battery, specific capacity and cycle performance
Better effect.
According to an embodiment of the invention, can also be stirred while the first mixed liquor is added drop-wise to the second mixed liquor
Processing, and after the first mixed liquor is added drop-wise to the second mixed liquor completely, can also continue to stirring 1-12h (such as 1h, 2h, 4h,
6h, 8h, 10h, 12h etc.), be conducive to for the first mixed liquor and the second mixed liquor being sufficiently mixed as a result, and mix more equal
It is even.
S400: carrying out the first roasting in the first inert atmosphere after the third mixed liquor is dried, with
Just the silicon-carbon cathode material is obtained.
According to an embodiment of the invention, above-mentioned drying process may include that stirring is evaporated, convection oven is dry, freeze-drying
And at least one of vacuum drying.Above-mentioned drying process is illustrated so that stirring is evaporated as an example: third mixed liquor is put into
In water-bath, in 50-100 DEG C of (such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100
DEG C etc.) under conditions of be stirred and be evaporated.It is simple, convenient as a result, it is easy to accomplish, and drying effect is preferable.
According to an embodiment of the invention, first roasting is at inert atmosphere (such as argon atmosphere, nitrogen atmosphere etc.)
Under the conditions of carry out, and the temperature of first roasting be 500-1000 DEG C (such as 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700
DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C etc.), calcining time be 2-5h (such as 2h, 2.5h, 3h,
3.5h, 4h, 4.5h, 5h etc.).The first roasting can be stronger in the hole of porous carbon substrate by silicon particle as a result, weakens
The expansion of silicon particle is conducive to improve the cycle performance of the battery obtained using silicon-carbon cathode material, first effect and specific capacity.
According to an embodiment of the invention, the gross mass based on the silicon-carbon cathode material, the content of the silicon particle is 10-
20wt% (such as the content of silicon particle can be 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt% etc.).By
This, the content of silicon particle is more appropriate, and what is be distributed in porous carbon substrate is relatively uniform, there's almost no agglomeration, favorably
In the service performance for improving silicon-carbon cathode material.Relative to above-mentioned content range, when the content of silicon particle is too low, then silicon is utilized
The specific capacity and high rate performance for the battery that carbon negative pole material obtains are relatively low；When the too high levels of silicon particle, then silicon
Grain is easy to happen agglomeration, so that the first effect of battery, specific capacity and cycle performance are relatively low.
According to an embodiment of the invention, before the third mixed solution is dried further include: Xiang Suoshu
Covering material is added in third mixed solution.Covering material can be formed in the outer surface of porous carbon substrate and silicon particle as a result,
So that silicon particle is not easy to fall off from the hole of porous carbon substrate, so that the structure of silicon-carbon cathode material is more stable, and more has
Conducive to the expansion for weakening silicon particle, further decreases silicon particle and reunite or a possibility that dusting, slow down the effect of the growth of SEI film
More preferably, the chemical property of silicon-carbon cathode material is more preferable for fruit, utilizes first effect, the specific capacity of the battery that the silicon-carbon cathode material obtains
And cycle performance is higher, the service life is longer.
According to an embodiment of the invention, into the third mixed solution be added covering material include: by covering material with
It is added drop-wise in the third mixed liquor after the mixing of third solvent, then carries out ball-milling treatment.It is equal to be conducive to covering material as a result,
The uniform mixing of even, silicon particle and porous carbon substrate is conducive to the specific capacity for improving battery and first effect, and ball-milling treatment makes
The specific surface area of the silicon-carbon cathode material of acquisition is larger, is more advantageous to the service performance for improving silicon-carbon cathode material.
According to an embodiment of the invention, the time of the ball-milling treatment is 8-10h (such as 8h, 8.5h, 9h, 9.5h, 10h
Deng).It help to obtain the more appropriate silicon-carbon cathode material of granular size as a result, so that the tap density of silicon-carbon cathode material
It is higher, so that the capacity of the battery finally obtained is higher.Relatively above-mentioned time range, when the time of ball-milling treatment is too short, then
Solute cannot be dispersed well, and aggregating state can reduce the capacity of battery and shorten the service life of battery, when ball-milling treatment
Between it is too long when then due to zirconium pearl long-time friction temperature raising make solute that chemical change can occur, property can change.
According to an embodiment of the invention, the mass ratio of the covering material and the silicon particle is (1-2): 1 (such as 1:1,
1.5:1,2:1 etc.).The covering material of above-mentioned content can effectively get up silicon particle and porous carbon substrate cladding as a result, so that
Silicon particle hardly falls off from porous carbon substrate, and then improves the stability of the structure of silicon-carbon cathode material, after roasting
Silicon particle is less susceptible to expand after being wrapped by the silicon-carbon cathode material of acquisition, powder phenomenon-tion hardly occurs,
And the growth of SEI film is slower, the service performance of silicon-carbon cathode material is more preferably.When the mass ratio of covering material and silicon particle is excessively high
When then silicone content significantly reduce, then the specific capacity and high rate performance of the battery finally obtained are relatively low, when covering material with
Then covering material cannot wrap up silicon particle well when the mass ratio of silicon particle is too low, so that the pole piece of preparation is carrying out battery survey
Dusting rupture quickly occurs when examination, the service life of battery is also very of short duration.
According to an embodiment of the invention, the covering material be selected from carbohydrate (such as can be for monosaccharide and disaccharide or polysaccharide etc.
At least one of Deng) and organic gel materials (such as can be pitch etc.).Material source is extensive as a result, and price is lower,
That disperses in third mixed liquor is relatively uniform, and the effect for coating silicon particle and porous carbon substrate is preferable, and after baking can
It is enough to obtain the carbon material for having porous structure, silicon-carbon is hardly influenced while improving silicon-carbon cathode material structural stability
The service performance of negative electrode material.In some embodiments of the invention, carbohydrate is selected from glucose, fructose, galactolipin, sucrose, wheat
At least one of bud sugar, lactose, starch, cellulose, glycogen, above-mentioned carbohydrate covered effect is more preferably as a result,.Of the invention one
In a little preferred embodiments, carbohydrate is selected from monosaccharide (such as glucose, fructose, galactolipin etc.).The dispersion of monosaccharide in a solvent as a result,
Effect is good, so that the clad in the silicon-carbon cathode material obtained is relatively uniform, is conducive to the electrification for improving silicon-carbon cathode material
Learn performance.According to an embodiment of the invention, covering material is added into the third mixed solution through the following steps that carrying out
: covering material is dissolved in solvent and obtains mixed liquor, mixed liquor is slowly added dropwise in third mixed liquor, celestial body of being expert at later
Ball milling 8-10h in grinding jar, uniformly to mix.
According to an embodiment of the invention, the third mixed solution containing covering material is carried out the laggard of above-mentioned drying process
Row first roasts, and covering material can be carbonized, and obtains silicon-carbon cathode material, the covering material being carbonized in the silicon-carbon cathode material
It is formed on at least partly surface of silicon particle and porous carbon substrate, so that the structure of silicon-carbon cathode material is relatively stable, benefit
The head for the battery being prepared with the silicon-carbon cathode material is imitated, specific capacity and cycle performance are preferable, and service life is longer, market
Competitiveness is stronger.
According to an embodiment of the invention, the above-mentioned method for preparing silicon-carbon cathode material is simple, convenient, it is easy to accomplish,
Silicon particle progress decentralized processing is conducive to that silicon particle is relatively uniform to be distributed in porous carbon substrate, reduces the hair of agglomeration
Raw, silicon particle is embedded in the hole of porous carbon substrate in the silicon-carbon cathode material obtained using this method, is conducive to weaken silicon particle
Expansion, and then effectively reduce silicon particle and reunite or the phenomenon that dusting, can also effectively slow down the growth of SEI film, significantly mention
The chemical property of high silicon-carbon negative electrode material so that the service life of silicon-carbon cathode material is longer, and then improves and utilizes the silicon-carbon
First effect, specific capacity and the cycle performance for the battery that negative electrode material is prepared, are able to maintain in longer use process
Higher battery capacity, and obtain the first effect up to 90% or more of silicon-carbon cathode material, 0.1C condition discharge capacity can
Up to 900mAh/g or more.
In another aspect of this invention, the present invention provides a kind of silicon-carbon cathode materials.According to an embodiment of the invention, should
Silicon-carbon cathode material is prepared using mentioned-above method.Inventors have found that cost is relatively low for the silicon-carbon cathode material,
Structure is more stable, and the ability of insertion or abjection lithium is strong, so that the head for the battery being prepared using the silicon-carbon cathode material
Effect, specific capacity and cycle performance are preferable, the first effect up to 90% or more of battery, reachable in 0.1C condition discharge capacity
900mAh/g or more, service life is longer, and higher specific capacity and cyclicity are able to maintain in longer use process
Can, the market competitiveness is stronger, the consumption experience for the consumer that is content with very little.
In another aspect of this invention, the present invention provides a kind of cathode.According to an embodiment of the invention, the cathode includes
Mentioned-above silicon-carbon cathode material.Inventors have found that the cathode stability is preferable, the ability of insertion or abjection lithium is strong, makes
First effect, specific capacity and the cycle performance for obtaining battery are preferable, and service life is longer, and is able to maintain in longer use process
Higher specific capacity and cycle performance, the market competitiveness is stronger, the consumption experience for the consumer that is content with very little.
It, can be with according to an embodiment of the invention, the processing of above-mentioned cathode includes except mentioned-above silicon-carbon cathode material
Including binder (such as butadiene-styrene rubber etc.), conductive agent (such as acetylene black etc.), thickener (such as carboxymethyl cellulose etc.) with
And collector (such as copper foil etc.) etc..According to an embodiment of the invention, when preparing cathode, by silicon-carbon cathode material, binder,
Slurry is formed after conductive agent and thickener etc. are uniformly mixed, slurry is coated on the surface of collector, and drying is simultaneously cut
It can be obtained required cathode later.
In another aspect of this invention, the present invention provides a kind of batteries.According to an embodiment of the invention, the battery pack
It includes: mentioned-above cathode；Anode；Diaphragm, wherein the diaphragm setting is between the cathode and the anode；Electrolyte,
At least part of at least part of the anode, at least part of the cathode and the diaphragm is immersed in the electrolysis
In liquid.Inventors have found that the battery structure is simple, is easily achieved, price is lower, and head effect, specific capacity and cycle performance are preferable,
Service life is longer, and higher specific capacity and cycle performance, the market competitiveness are able to maintain in longer use process
It is relatively strong, the consumption experience for the consumer that is content with very little.
According to an embodiment of the invention, the material for forming anode may include: positive electrode (such as cobalt acid lithium etc.), conduction
Agent (such as acetylene black etc.), binder (such as Kynoar etc.) and collector (such as aluminium foil etc.) etc..According to the present invention
Embodiment, the material for forming diaphragm may include polyethylene, polypropylene etc..According to an embodiment of the invention, electrolyte includes
Solute and solvent, wherein the material for forming solvent includes propene carbonate, ethylene carbonate etc., and the material for forming solute includes
Lithium hexafluoro phosphate, LiBF4 etc..
According to an embodiment of the invention, above-mentioned battery is other than including anode, cathode, electrolyte and diaphragm, it can be with
Including shell etc., no longer excessively repeat herein.According to an embodiment of the invention, above-mentioned battery can be lithium ion battery etc..
Embodiments herein is described below.
Embodiment
If without specified otherwise, in following embodiment and comparative example, by the lithium ion button containing silicon-carbon cathode material
Formula half-cell carries out electrochemical property test to study the performance of silicon-carbon cathode material.
The step of preparing lithium ion button-shaped half-cell is as follows: the model of the button-shaped half-cell of lithium ion is 2032 models,
Cathode of the lithium piece as half-cell, anode in contain silicon-carbon cathode material, specifically, anode prepare it is as follows: first, in accordance with silicon
Carbon negative pole material: conductive agent: the ratio of binder=8:1:1 (mass ratio) weighs silicon-carbon cathode material, conductive agent (such as acetylene
Black, Super P, KS-6 etc.) and binder (such as butadiene-styrene rubber, carboxymethyl cellulose, acrylic resin, polyimides etc.)
And be mixed uniformly to form slurry, then carry out coating sizing-agent on copper foil and obtain pole piece, the pole piece dried is cut
It cuts out, is cut into the disk that diameter is 12 millimeters, drying obtains anode again.Wherein, electrolyte model LBC3401A4, diaphragm type
Number be celgard 2320.
To the electrochemical property test method of battery: the chemical property for testing battery is to first pass through Shanghai Chen Hua
CHI660E electrochemical workstation carries out the test of CV curve and impedance, then is filled on blue electric battery test system CT2001A
Discharge test to carry out battery the test of high rate performance and cycle performance.
Embodiment 1:
The preparation of silicon-carbon cathode material:
(1) chlorella is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 900 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2000 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 5 microns, (specific structure can refer to Fig. 3)；
(4) 1g silicon particle (partial size 300nm) is dissolved in 5.07ml dehydrated alcohol, ultrasonic disperse 2h, forms solution A；
(5) the porous carbon substrate of 4g is weighed, is slowly added into 40ml water under agitation and stirs 3h formation solution B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 2h and forms solution C；
(7) solution C is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 5 DEG C/min rate
900 DEG C of roasting 3h.
In the present embodiment, the content of silicon is 20wt% in silicon-carbon cathode material, and the first effect of battery is 81%, is compared at 0.1C
Capacitor is 925mAh/g, and cycle performance is 50 circulation conservation rates 75%.
Embodiment 2:
The preparation of silicon-carbon cathode material:
(1) yellow silk algae is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 1000 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2000 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 3 microns (specific structure can refer to Fig. 4)；
(4) 1g silicon particle (partial size 350nm) is dissolved in 11.41ml dehydrated alcohol, ultrasonic disperse 30min, is formed molten
Liquid A；
(5) the porous carbon substrate of 9g is weighed, stirring 3h in 50ml deionized water is slowly added under agitation and is formed
Solution B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 2h and forms solution C；
(7) solution C is dried in vacuo, 900 DEG C of roasting 2h is then risen to 2 DEG C/min rate in a nitrogen atmosphere.
In the present embodiment, the content of silicon is 10wt% in silicon-carbon cathode material, and the first effect of battery is 88.3%, at 0.1C
Specific capacitance is 512mAh/g, and cycle performance is capacitor sustainment rate after 50 circulations 81%.
Embodiment 3
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 600 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2700 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 5 microns；
(4) 1g silicon particle (partial size 300nm) is dissolved in 11.41ml dehydrated alcohol, ultrasonic disperse 4h, forms solution A；
(5) the porous carbon substrate of 9g is weighed, is slowly added into 100ml water under agitation and stirs 3h formation solution B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 12h and forms solution C；
(7) solution C is freeze-dried, 1000 DEG C of roasting 5h is then risen to 2 DEG C/min rate in a nitrogen atmosphere.
In the present embodiment, the content of silicon is 10wt% in silicon-carbon cathode material, and the first effect of battery is 80.5%, at 0.1C
Specific capacitance is 498mAh/g, and cycle performance is that 50 capacitor sustainment rates of circulation are 83%.
Embodiment 4
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 600 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2500 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 1 micron；
(4) 1.5g silicon particle (partial size 500nm) is dissolved in 10.77ml dehydrated alcohol, ultrasonic disperse 4h, forms solution
A；
(5) weigh the porous carbon substrate of 8.5g, be slowly added under agitation in 100ml water stir 10h formed it is molten
Liquid B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 8h and forms solution C；
(7) solution C is put into drying in 75 DEG C of convection ovens, then rises to 800 in a nitrogen atmosphere with 2 DEG C/min rate
DEG C roasting 3h.
In the present embodiment, the content of silicon is 15wt% in silicon-carbon cathode material, and the first effect of battery is 82.7%, at 0.1C
Specific capacitance is 672mAh/g, and cycle performance is 50 capacitor sustainment rates of circulation 77%.
Embodiment 5
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 400 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 3000 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, forming porous carbon substrate, (pore size is
2.5 microns)；
(4) 0.5g silicon particle (partial size 350nm) is dissolved in 12.04ml dehydrated alcohol, ultrasonic disperse 4h, forms solution
A；
(5) weigh the porous carbon substrate of 9.5g, be slowly added under agitation in 100ml water stir 10h formed it is molten
Liquid B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 8h and forms solution C；
(7) solution C is put into stir in 75 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
1200 DEG C of roasting 6h.
In the present embodiment, the content of silicon is 5wt% in silicon-carbon cathode material, and the first effect of battery is 86.7%, at 0.1C
Specific capacitance is 327mAh/g, and cycle performance is capacitor sustainment rate after 50 circulations 79%.
Embodiment 6
The preparation of silicon-carbon cathode material:
(1) brown alga is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 1200 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 1800 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate (pore size 10
Micron)；
(4) 1g silicon particle (partial size 300nm) is dissolved in 3.8ml dehydrated alcohol, ultrasonic disperse 4h, forms solution A；
(5) the porous carbon substrate of 3g is weighed, is slowly added into 30ml water under agitation and stirs 10h formation solution B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 10 drops/sec), is added dropwise subsequent
Continuous stirring 8h forms solution C；
(7) solution C is put into stir in 75 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
400 DEG C of roasting 1h.
In the present embodiment, the content of silicon is 25wt% in silicon-carbon cathode material, and the first effect of battery is 70.6%, at 0.1C
The specific capacitance of battery is 1086mAh/g, and cycle performance is that 50 circulation capacity retentions are 66%.
Embodiment 7
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 600 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2500 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 1 micron；
(4) 1g silicon particle (partial size 300nm) is dissolved in 5.07ml dehydrated alcohol, ultrasonic disperse 4h, forms solution A；
(5) the porous carbon substrate of 3g is weighed, is slowly added into 30ml water under agitation and stirs 10h formation solution B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 8h and forms solution C；
(7) claim the DEXTROSE ANHYDROUS of 1g to be dissolved in 10ml water, be slowly added dropwise in solution C, ball milling in celestial body grinding jar of being expert at
8h forms solution D；
(8) solution D is put into stir in 75 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
800 DEG C of roasting 3h.
In the present embodiment, the scanning electron microscope (SEM) photograph of silicon-carbon cathode material can refer to Fig. 5, and the content of silicon particle is 20%, battery
First effect be 83.5%, the specific capacitance of battery is 910mAh/g at 0.1C, and cycle performance is recycle 50 capacitors under 0.1C to tie up
Holdup is 81%.
Embodiment 8
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 600 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2500 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 2 microns；
(4) 3g silicon particle (partial size 300nm) is dissolved in 21.55ml dehydrated alcohol, ultrasonic disperse 4h, forms solution A；
(5) the porous carbon substrate of 14g is weighed, is slowly added into 100ml water under agitation and stirs 10h formation solution
B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 8h and forms solution C；
(7) claim the DEXTROSE ANHYDROUS of 3g to be dissolved in 20ml water, be slowly added dropwise in solution C, ball milling in celestial body grinding jar of being expert at
10h forms solution D；
(8) solution D is put into stir in 75 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
800 DEG C of roasting 3h.
In the present embodiment, the scanning electron microscope (SEM) photograph of silicon-carbon cathode material can refer to Fig. 6, and the content of silicon particle is 15%, head effect
It is 80.7%, the specific capacitance of battery is 635mAh/g at 0.1C, and cycle performance is that the lower 50 circulations capacity retention of 0.1C exists
83%.
Embodiment 9
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 600 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2500 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 6 microns；
(4) 1g silicon particle (partial size 300nm) is dissolved in 11.41ml dehydrated alcohol, ultrasonic disperse 4h, forms solution A；
(5) the porous carbon substrate of 7g is weighed, is slowly added into 40ml water under agitation and stirs 10h formation solution B；
(6) under agitation, solution A is added in solution B dropwise (drop speed is 1 drop/sec), is continued after being added dropwise
It stirs 8h and forms solution C；
(7) claim the DEXTROSE ANHYDROUS of 2g to be dissolved in 20ml water, be slowly added dropwise in solution C, ball milling in celestial body grinding jar of being expert at
9h forms solution D；
(8) solution D is put into stir in 75 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
800 DEG C of roasting 3h.
It is 82% that the content of silicon particle, which is 10%, head effect, in the present embodiment, in silicon-carbon cathode material, the battery at 0.1C
Specific capacitance is 479mAh/g, and cycle performance is 50 capacity retentions of circulation 75.1%.
Embodiment 10
The preparation method is the same as that of Example 1 for the present embodiment silicon-carbon cathode material, the difference is that it is molten that solution A is added dropwise to B
The drop speed of liquid is 10 drops/sec.In the present embodiment, the content of silicon is 20wt% in silicon-carbon cathode material, and the first effect of battery is
67.9%, the specific capacitance of battery is 513mAh/g at 0.1C, and cycle performance is that 50 circulation capacitor sustainment rates are 58%.
Embodiment 11
The preparation of silicon-carbon cathode material:
(1) chlorella is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 900 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2000 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 5 microns；
(4) 1g silicon particle (partial size 400nm) is dissolved in 11.41ml dehydrated alcohol, ultrasonic disperse 2h, forms solution A；
(5) the porous carbon substrate of 4g is weighed, is slowly added into 40ml water under agitation and stirs 3h formation solution B；
(6) under agitation, solution A is poured slowly into solution B, continues to stir 2h formation solution C；
(7) solution C is put into stir in 70 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 5 DEG C/min rate
900 DEG C of roasting 3h.
In the present embodiment, the content of silicon particle is 20% in silicon-carbon cathode material, and the first effect of battery is 78%, at 0.1C
Specific capacitance is 287mAh/g, and cycle performance is that 50 capacitor sustainment rates of circulation are 68.2%.
Comparative example 1
The preparation of silicon-carbon cathode material:
(1) spirulina is subjected to air-flow crushing；
(2) smashed microalgae powder carries out 600 degrees Celsius of roastings under an inert atmosphere and forms microalgae charcoal；
(3) 2500 degrees Celsius of roastings are carried out under an inert atmosphere to microalgae charcoal, form porous carbon substrate, in porous carbon substrate
Pore size be 1 micron；
(4) by 1g silicon particle (partial size is 400 nanometers) and the porous carbon substrate of 4g, it is slowly added to 50ml water under agitation
Middle stirring 10h forms solution A；
(5) solution A is put into stir in 75 DEG C of water-baths and is evaporated, then risen in a nitrogen atmosphere with 2 DEG C/min rate
800 DEG C of roasting 5h.
In this comparative example, the first effect of battery is 71.7%, and specific capacitance is 583mAh/g under 0.1C, cycle performance at 0.1C
It is 62% for 50 capacity retention ratios of circulation.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include one or more of the features.In the description of the present invention, the meaning of " plurality " is two or more,
Unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing silicon-carbon cathode material characterized by comprising
Silicon particle is dispersed in the first solvent to form the first mixed liquor；
Porous carbon substrate is dispersed in the second solvent to form the second mixed liquor；
First mixed liquor and second mixed liquor are mixed, to form third mixed liquor；
The first roasting is carried out after the third mixed liquor is dried in the first inert atmosphere, it is described to obtain
Silicon-carbon cathode material,
Wherein, the porous carbon substrate is prepared using biomass.
2. the method according to claim 1, wherein first mixed liquor and second mixed liquor are mixed
It is to be carried out by the way that first mixed liquor to be added drop-wise in second mixed liquor；
Optional, it is that 1-3 drop is per second that the speed in second mixed liquor, which is added dropwise, in first mixed liquor.
3. the method according to claim 1, wherein before the third mixed solution is dried
Further include:
Covering material is added into the third mixed solution.
4. according to the method described in claim 3, it is characterized in that, covering material packet is added into the third mixed solution
It includes:
It is added drop-wise in the third mixed liquor after the covering material is mixed with third solvent, then carries out ball-milling treatment；
Optional, the time of the ball-milling treatment is 8-10h；
Optional, the mass ratio of the covering material and the silicon particle is (1-2): 1；
Optional, the covering material is selected from least one of organic gel materials, carbohydrate.
5. method according to claim 1 or 3, which is characterized in that the porous carbon substrate is through the following steps that obtain
:
Biomass is placed in the second inert atmosphere and carries out the second roasting to obtain charcoal；
The charcoal is placed in third inert atmosphere and carries out third roasting to obtain the porous carbon substrate；
Optional, the biomass includes microalgae；
Optional, second maturing temperature is 600-1000 degrees Celsius, and the third maturing temperature is that 2000-2700 is Celsius
Degree.
6. method according to claim 1 or 3, which is characterized in that the partial size of the silicon particle is 300-500 nanometers, institute
Stating the pore size in porous carbon substrate is 1-10 microns.
7. the method according to claim 1, wherein the gross mass based on the silicon-carbon cathode material, the silicon
The content of particle is 10-20wt%.
8. method according to claim 1 or 3, which is characterized in that the temperature of first roasting is 500-1000 DEG C, roasting
The burning time is 2-5h.
9. a kind of silicon-carbon cathode material, which is characterized in that be prepared using the described in any item methods of claim 1-8
's.
10. a kind of battery characterized by comprising
Cathode is made of silicon-carbon cathode material as claimed in claim 9；
Anode；
Diaphragm, wherein the diaphragm setting is between the cathode and the anode；
Electrolyte, at least part leaching of at least part of the anode, at least part of the cathode and the diaphragm
Bubble is in the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811261434.1A CN109449401A (en) | 2018-10-26 | 2018-10-26 | Silicon-carbon cathode material and preparation method thereof, cathode and battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982296A (en) * | 2019-12-04 | 2020-04-10 | 湖北三江航天红阳机电有限公司 | Preparation method of prepreg filaments |
| CN111016220A (en) * | 2019-12-04 | 2020-04-17 | 湖北三江航天红阳机电有限公司 | Structural member and forming method thereof |
| CN111540896A (en) * | 2020-05-07 | 2020-08-14 | 七台河万锂泰电材有限公司 | Preparation method of silicon-carbon composite negative electrode material |
| CN113488640A (en) * | 2021-07-07 | 2021-10-08 | 盐城工学院 | Preparation method of silicon-carbon negative electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509781A (en) * | 2011-10-27 | 2012-06-20 | 上海交通大学 | Silicon-carbon composite anode material and preparing method thereof |
| CN102694155A (en) * | 2012-05-31 | 2012-09-26 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same |
| CN103236560A (en) * | 2013-04-16 | 2013-08-07 | 浙江大学 | Lithium-sulfur battery sulfur/carbon composite positive electrode material, preparation method and applications thereof |
| CN106129362A (en) * | 2016-07-21 | 2016-11-16 | 天津巴莫科技股份有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN108565431A (en) * | 2018-04-24 | 2018-09-21 | 中国矿业大学 | A method of preparing lithium ion battery silicon-carbon compound cathode materials by carbon source of konjaku flour |
-
2018
- 2018-10-26 CN CN201811261434.1A patent/CN109449401A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509781A (en) * | 2011-10-27 | 2012-06-20 | 上海交通大学 | Silicon-carbon composite anode material and preparing method thereof |
| CN102694155A (en) * | 2012-05-31 | 2012-09-26 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same |
| CN103236560A (en) * | 2013-04-16 | 2013-08-07 | 浙江大学 | Lithium-sulfur battery sulfur/carbon composite positive electrode material, preparation method and applications thereof |
| CN106129362A (en) * | 2016-07-21 | 2016-11-16 | 天津巴莫科技股份有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN108565431A (en) * | 2018-04-24 | 2018-09-21 | 中国矿业大学 | A method of preparing lithium ion battery silicon-carbon compound cathode materials by carbon source of konjaku flour |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982296A (en) * | 2019-12-04 | 2020-04-10 | 湖北三江航天红阳机电有限公司 | Preparation method of prepreg filaments |
| CN111016220A (en) * | 2019-12-04 | 2020-04-17 | 湖北三江航天红阳机电有限公司 | Structural member and forming method thereof |
| CN111540896A (en) * | 2020-05-07 | 2020-08-14 | 七台河万锂泰电材有限公司 | Preparation method of silicon-carbon composite negative electrode material |
| CN113488640A (en) * | 2021-07-07 | 2021-10-08 | 盐城工学院 | Preparation method of silicon-carbon negative electrode material |
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