CN106941169A - A kind of silicon-carbon cathode material and preparation method thereof - Google Patents
A kind of silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to energy storage research field, more particularly to a kind of silicon-carbon cathode material, the particle diameter D1 of the silicon-carbon cathode material is 1 μm 200 μm, the silicon-carbon cathode material is second particle structure, the second particle is made up of primary particle and electronics conductive components, the primary particle particle diameter is D2, D2≤0.5D1；The electronics conductive components include graphene sheet layer, and the primary particle and the graphene sheet layer are dispersed；The graphene is porous graphene；The width of continuous part is d1, d1≤0.5D1 between the porous graphene lamellar spacing h1≤100nm, bore dia D3, holes.I.e. selection porous graphene is easy to ion free shuttling in radius of the width no more than second particle structure of two continuous parts between surface, and holes of graphene so that two-dimensional graphene lamella has relatively low inhibition to ion diffusion.
Description
Technical field
The invention belongs to field of material technology, more particularly to a kind of silicon-carbon cathode material and preparation method thereof.
Background technology
Lithium ion battery is so that its specific energy is big, operating voltage is high, self-discharge rate is small, small volume, the advantage such as lightweight, from it
Since birth, revolutionary change just has been brought to energy storage field, is widely used in various portable electric appts and electronic
In automobile.However as the improvement of people's living standards, higher Consumer's Experience proposes higher requirement to lithium ion battery：
Quality is lighter, use time is longer etc.；The more excellent electrode material of new performance is had to look for solve the above problems.
Current commercialized lithium ion battery negative material is mainly graphite, but because its theoretical capacity is only 372mAhg-1, the active demand of user can not be met；Therefore, the exploitation of the negative material of more height ratio capacity is extremely urgent.It is used as lithium ion
Cell negative electrode material, silicon materials receive much concern always.Its theoretical capacity is 4200mAhg-1, it is the graphite capacity having been commercialized
More than 10 times, it is and relatively inexpensive, environment-friendly etc. excellent with low intercalation potential, low atomic wts, high-energy-density, price
One of gesture, therefore be the optimal selection of high-capacity cathode material of new generation.
But be due to that silicon materials electric conductivity itself is poor and in charge and discharge process volumetric expansion it is big and easily cause material knot
Structure is destroyed and mechanical crushing, is caused the decay of its cycle performance fast, is limited it and widely apply.In order to solve the above problems,
Prior art mainly has silicon grain nanosizing, grapheme material with excellent conductive capability etc. is added into silica-base material particle
Deng the electric conductivity for improving silica-base material integral particle, while solving the mechanical powder of silica-base material in material charge and discharge process
Broken the problems such as.
There is unique flexible two-dimension plane structure yet with grapheme material, its lamella is very easy to nanosizing
Based particles are coated on inside it, so as to hinder the Qian He in charge and discharge process between lithium ion and nano silica-base material, are influenceed
The performance of silica-base material capacity.
In view of this, it is necessory to propose a kind of silicon-carbon cathode material and preparation method thereof, it can both give play to graphene
Sharpest edges, the obstruction transmitted to ion that its cladding to nano particle is avoided that again and is caused.
The content of the invention
It is an object of the invention to：In view of the shortcomings of the prior art, a kind of silicon-carbon cathode material provided, the silicon-carbon
The particle diameter D1 of negative material be 1 μm -200 μm, the silicon-carbon cathode material be second particle structure, the second particle by
Primary particle and electronics conductive components composition, the primary particle particle diameter is D2, D2≤0.5D1；In the electronics conductive components
Including graphene sheet layer, the primary particle and the graphene sheet layer are dispersed；The graphene is porous graphene；Institute
Porous graphene lamellar spacing h1≤100nm is stated, bore dia D3, D3 are no more than continuous part between particle diameter D1, holes
Width is d1, d1≤0.5D1.That is selection porous graphene is easy to ion free shuttling in two surfaces of graphene, and holes it
Between continuous part width be no more than second particle structure radius so that two-dimensional graphene lamella to ion diffusion have it is relatively low
Inhibition.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of silicon-carbon cathode material, the particle diameter D1 of the silicon-carbon cathode material is 1 μm -200 μm, grain diameter mistake
Small, poor processability when subsequently preparing electrode slurry, grain diameter is excessive, and the high rate performance of silicon-carbon cathode is poor；The silicon-carbon is born
Pole material is second particle structure, and the second particle is made up of primary particle and electronics conductive components, the primary particle grain
Footpath is that D2, D2≤0.5D1, i.e. second particle are at least made up of 8 primary particles, so that it is guaranteed that second particle has more preferable knot
Structure stability；The electronics conductive components include graphene sheet layer, and the primary particle uniformly divides with the graphene sheet layer
Dissipate；The graphene is porous graphene；Connect between the porous graphene lamellar spacing h1≤100nm, bore dia D3, holes
The width of continuous part is d1, d1≤0.5D1.That is selection porous graphene is easy to ion free shuttling in two surfaces of graphene,
And the width of continuous part is no more than the radius of second particle structure between holes so that two-dimensional graphene lamella spreads to ion
With relatively low inhibition.
Improved as one kind of silicon-carbon cathode material of the present invention, silicon containing component particle is contained in the primary particle, may be used also
With including non-silicon containing component particle.There is high power capacity, the silicon containing component of high volumetric expansion with having relatively low capacity, relatively low
The primary particle mixture that the material blending of volumetric expansion is obtained, with more structural stability.
Improved as one kind of silicon-carbon cathode material of the present invention, the silicon containing component is pure silicon, Si oxide, silicon substrate are combined
At least one in material, modified silica-base material；The non-silicon containing component particle includes native graphite, Delanium, interphase
At least one in carbosphere, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, non-silicon alloy material of cathode
Kind.I.e. the present invention has universality：It is suitable for high power capacity, high volumetric expansion active component to expand with relative low capacity, low volume
The mixture of active component, obtains capacity height and constitutionally stable composite.
Improved as one kind of silicon-carbon cathode material of the present invention, the primary particle is uniformly scattered in the graphene film
Layer surface, and good electron channel is formed between the two；1≤40nm of the graphene sheet layer thickness h；The silicon-carbon cathode material
In material, the part by weight of graphite olefinic constituent is x%, x%≤5%, because graphene ability has excellent electric conductivity, therefore
In the case where ensuring finely dispersed situation, it need to only add and can reach excellent conductive effect on a small quantity；And addition is excessive, it will cause
Whole material intermediate ion diffusional resistance is increased.
Improve, in the electronics conductive components, can also be led containing super as one kind of silicon-carbon cathode material of the present invention
At least one in electrical carbon, acetylene black, CNT, Ketjen black, conductive carbon black；Continuous portion between the porous graphene holes
The width divided is d1≤D2；Combined conductive agent component can be with the maximized conductive effect for playing various conductive agents, and porous stone
The width of continuous part is no more than the size of primary particle between black alkene holes, it can be ensured that the continuum on graphene sheet layer
Part will not envelope primary particle, insertion and abjection of the barrier ion in primary particle completely.
Present invention additionally comprises a kind of preparation method of silicon-carbon cathode material, mainly comprise the following steps：
Step 1, prepared by presoma：Electronics conductive components are well mixed with primary particle and obtain presoma；
Step 2, presoma is granulated, obtains second particle presoma；
Step 3, coat, being carbonized obtains finished product second particle；
Improved as a kind of the of preparation method of silicon-carbon cathode material of the present invention, the electronics conductive components include graphite
The width d1 of continuous part between alkene, the porous graphene thickness degree h1≤100nm, the porous graphene lamella holes≤
0.5D1；Contain silicon containing component particle in the primary particle, non-silicon containing component particle can also be included.
Improved as a kind of the of preparation method of silicon-carbon cathode material of the present invention, the silicon containing component is pure silicon, silicon oxidation
At least one in thing, silicon based composite material, modified silica-base material；The non-silicon containing component particle includes native graphite, artificial
Graphite, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, non-silicon alloy material of cathode
In at least one；In the electronics conductive components, can also containing super conductive carbon, acetylene black, CNT, Ketjen black,
At least one in conductive carbon black；The graphene sheet layer planar diameter d1≤D2.
Improved as a kind of the of preparation method of silicon-carbon cathode material of the present invention, by electronics conductive components, solvent 1, auxiliary
Component 1 is uniformly mixed；Primary particle, solvent 2, helper component 2 are uniformly mixed；Two kinds of blending ingredients are mixed into traveling afterwards
Disperseing for one step, obtains electronics conductive components and the equally distributed presoma of primary particle.Hybrid mode includes kneading, ball
The means such as mill, husky mill, high-pressure homogeneous；It is to add a small amount of solvent to be stirred slowly to mediate, and is reduced while can improving dispersion effect
Solvent load, so as to reduce energy consumption when solvent volatilizees in balling process；The solvent 1 is selected from water, alcohols, ketone, alkanes, ester
In class, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran at least
It is a kind of；It is anion surfactant, cationic surfactant, two that the helper component 1, which is selected from ionic surfactant,
At least one of property ionic surface active agent；The anion surfactant is lauryl sodium sulfate, enuatrol, dodecane
Base benzene sulfonic acid sodium salt or Aerosol OT.The cationic surfactant be cetyl trimethylammonium bromide,
Hexadecyldimethyl benzyl ammonium allyl ammonium chloride or polyacrylamide；The zwitterionic surfactant is dodecyl dimethyl
At least one in glycine betaine, Cocoamidopropyl betaine or dodecylamino dipropionic acid；The solvent 2 be selected from water,
Alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO)
With at least one in tetrahydrofuran；The VTES of helper component 2, MTMS, tetrem
TMOS, vinyltrimethoxy silane, methylvinyldimethoxysilane, γ-methacryloxypropyl front three
TMOS, methacryloyloxypropyl methyl dimethoxysilane, γ aminopropyltriethoxy silane, γ-sulfydryl third
Base trimethoxy silane, γ-cyanopropyl trimethoxy silane, γ-glycidoxypropyltrimethoxy base silane, β-(3,
4- epoxycyclohexyls) at least one in ethyl trimethoxy silane and γ-ureido-propyl trimethoxy silane.
Improved as a kind of the of preparation method of silicon-carbon cathode material of the present invention, the granulation process described in step 2, for spraying
Dry；Cladding described in step 3, for cladding indefinite form carbon-coating；The clad includes phenolic resin, melamine resin, crosses chloroethene
Alkene, pitch, polyethylene, stearic acid, PVC, polyacrylonitrile, natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers, poly- second
At least one in alkene, polypropylene, polyamide, polyethylene terephthalate.
The advantage of the invention is that：
1. prepare pre- presoma, electronics conductive components and primary particle component are first prepared respectively, can be sufficiently by tool
The electronics conductive components and primary particle subpackage for having nanostructured, which are covered with after helper component, to be dissipated in solvent, obtains mixing more equal
Even presoma；
2. ensure between conductive agent component and nano particle it is dispersed after, can be with maximized performance conductive component
Conductive effect, so as to reduce the consumption (i.e. graphene content is not higher than 5%) of graphite olefinic constituent, reduces graphite flake layer planar
The inhibition that structure is transmitted to ion；
The second particle of 3.D2≤0.5D1, i.e., one is made up of at least eight primary particles, and primary particle particle diameter is smaller, fills
In discharge process, its structure is more stable, and the dynamic performance of particle is better；
The width of continuous part is no more than the radius of second particle between holes on 4.d1≤0.5D1, i.e. graphene sheet layer,
Because the graphene of planar structure has inhibition to ion diffusion, but when using porous graphene of the present invention,
Ion can freely be passed through in the hole of porous graphene, therefore ion is around row distance (distance of second particle radius length)
It is smaller, therefore inhibition is faint, battery has excellent chemical property.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the embodiment party of the present invention
Formula not limited to this.
Comparative example 1, prepares the silicon-carbon cathode material that particle diameter is 10 μm；
It is prepared by presoma：The silicon grain that particle diameter is 100nm is selected, lamellar spacing is 3nm, a diameter of 10 μm of slice plane
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 94 to conductive agent component:6), N, N- dimethyl pyrrolidone is
Solvent, is sufficiently stirred for, and obtains precursor pulp；Because size disparity is larger between graphene sheet layer and silicon nanoparticle, graphite
Alkene is easy to be coated on a nanometer silicon face, and it is big to disperse difficulty between the two；
Step 2, using spray drying process, the presoma that step 1 is obtained is granulated, and is controlled granulation conditions, is obtained particle straight
Footpath is 10 μm of silicon-carbon cathode nuclear material；
Step 3, using pitch as carbon source, the silicon-carbon cathode nuclear material obtained to step 2 carries out Surface coating, is carbonized afterwards
To finished product silicon-carbon cathode material；
Embodiment 1, is that the present embodiment comprises the following steps with the difference of comparative example 1：
Step 1, selection particle diameter be 100nm silicon grain, lamellar spacing be 3nm, a diameter of 50 μm of slice plane it is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 99 to conductive agent component:1)；The Kong Zhi of the porous graphene
Footpath is 1 μm, and the width d1 of continuous part is 5 μm or so between holes；
It is other identical with comparative example 1, it is not repeated herein.
Embodiment 2, difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, selection particle diameter be 100nm silicon grain, lamellar spacing be 3nm, a diameter of 50 μm of slice plane it is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 99 to conductive agent component:1)；The Kong Zhi of the porous graphene
Footpath is 1 μm, and the width d1 of continuous part is 1 μm or so between holes；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 3, difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, selection particle diameter be 100nm silicon grain, lamellar spacing be 3nm, a diameter of 50 μm of slice plane it is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 99 to conductive agent component:1)；The Kong Zhi of the porous graphene
Footpath is 1 μm, and the width d1 of continuous part is 0.5 μm or so between holes；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 4, difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, selection particle diameter be 100nm silicon grain, lamellar spacing be 3nm, a diameter of 50 μm of slice plane it is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 99 to conductive agent component:1)；The Kong Zhi of the porous graphene
Footpath is 0.1 μm, and the width d1 of continuous part is 0.1 μm or so between holes；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 5, difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, selection particle diameter be 100nm silicon grain, lamellar spacing be 3nm, a diameter of 50 μm of slice plane it is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 99 to conductive agent component:1)；The Kong Zhi of the porous graphene
Footpath is 0.1 μm, and the width d1 of continuous part is 0.05 μm or so between holes；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 6, difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, selection particle diameter be 100nm silicon grain, lamellar spacing be 3nm, a diameter of 50 μm of slice plane it is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 99 to conductive agent component:1)；The Kong Zhi of the porous graphene
Footpath is 0.1 μm, and the width d1 of continuous part is 0.02 μm or so between holes；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 7, is that the present embodiment comprises the following steps with comparative example difference：
Particle diameter is 100 μm of silicon-carbon cathode material；
Step 1, the silicon grain that selection particle diameter is 1000nm, lamellar spacing is 100nm, a diameter of 10 μm of slice plane is porous
Graphene sheet layer is that (mass ratio between silicon grain and graphene is 95 to conductive agent component:5)；The Kong Zhi of the porous graphene
Footpath is 1 μm, and the width d1 of continuous part is 0.5 μm or so between holes；
It is other identical with comparative example 1, it is not repeated herein.
Embodiment 8, is that the present embodiment comprises the following steps with comparative example difference：
Particle diameter is 1 μm of silicon-carbon cathode material；
Step 1, the silicon grain that selection particle diameter is 500nm, lamellar spacing is 5nm, a diameter of 10 μm of porous stones of slice plane
Black alkene lamella is that (mass ratio between silicon grain and graphene is 97 to conductive agent component:3)；The bore dia of the porous graphene
For 1 μm, the width d1 of continuous part is 0.5 μm or so between holes；
It is other identical with comparative example 1, it is not repeated herein.
Embodiment 9, prepares the silicon-carbon cathode material that particle diameter is 12 μm；
It is prepared by presoma：Select the silicon grain that particle diameter is 200nm, lamellar spacing is that 1nm, slice plane are a diameter of more than 10 μm
Hole graphene sheet layer is conductive agent component, and the bore dia of the porous graphene is 0.1 μm, the width of continuous part between holes
For 0.1 μm, (mass ratio between silicon grain and graphene is 99.6：0.4)；By silane coupler (alkyl silane coupling agent), silicon
Particle is mixed, and a small amount of N is added afterwards, N- dimethyl pyrrolidone solution is mediated, and obtains the dispersed slurry of nano-silicon；
Graphene, PVP are mixed, a small amount of N is added afterwards, N- dimethyl pyrrolidone solution is mediated, graphene uniform point is obtained
Scattered slurry；Two kinds of slurries are uniformly mixed, graphene and the mixed uniformly presoma of silicon nanoparticle is obtained；
Step 2, using spray drying process, the presoma that step 1 is obtained is granulated, and is controlled granulation conditions, is obtained particle straight
Footpath is 12 μm of silicon-carbon cathode nuclear material；
Step 3, using phenolic resin as carbon source, the silicon-carbon cathode nuclear material obtained to step 2 carries out Surface coating, afterwards carbon
Change obtains finished product silicon-carbon cathode material (silane coupler, PVP are carbonized in carbonisation and obtain agraphitic carbon).
Embodiment 10, prepares the silicon-carbon cathode material that particle diameter is 12 μm；
It is prepared by presoma：It is the 200nm sub- silicon of oxidation, Delanium hybrid particles as primary particle to select particle diameter, its
The middle sub- silicone content of oxidation is 10%；(lamellar spacing is 1nm, a diameter of 10 μm of porous graphene pieces of slice plane to porous graphene
Layer be conductive agent component, the porous graphene aperture be 0.1 μm, between holes the width of continuous part be 0.1 μm), it is super
Conductive carbon is conductive agent component, and wherein the content of graphene is 20%, and (mass ratio of primary particle and electronics conductive components is
99：1)；Silane coupler (alkyl silane coupling agent), silicon grain are mixed, a small amount of N, N- dimethyl pyrrolidones are added afterwards
Solution is mediated, and obtains the dispersed slurry of nano-silicon；Graphene, PVP are mixed, a small amount of N, N- dimethyl are added afterwards
Pyrrolidone solution is mediated, and obtains the scattered slurry of graphene uniform；Two kinds of slurries are uniformly mixed, graphite is obtained
Alkene and the mixed uniformly presoma of silicon nanoparticle；
Step 2, using spray drying process, the presoma that step 1 is obtained is granulated, and is controlled granulation conditions, is obtained particle straight
Footpath is 12 μm of silicon-carbon cathode nuclear material；
Step 3, using phenolic resin as carbon source, the silicon-carbon cathode nuclear material obtained to step 2 carries out Surface coating, afterwards carbon
Change obtains finished product silicon-carbon cathode material (silane coupler, PVP are carbonized in carbonisation and obtain agraphitic carbon).
Battery is assembled：It is the silicon-carbon cathode material that comparative example, embodiment 1- embodiments 10 are prepared and conductive agent, Nian Jie
Agent, stirring solvent obtain electrode slurry, apply form negative electrode on a current collector afterwards；By negative electrode and anode electrode
The assembling of (cobalt acid lithium is active material), barrier film obtains naked battery core, and bag is entered afterwards and carries out top side seal, drying, fluid injection, standing, change
Resultant battery is obtained into, shaping, degasification.
Material properties test：
Gram volume is tested：Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment
Battery core carries out gram volume test：Stand 3min；0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C；Stand 3min；
0.2C constant-current discharges obtain discharge capacity D1 to 3.0V；Stand 3min；0.2C constant-current discharges are to 3.85V；It is complete after standing 3min
Into volume test, the weight of silicon carbon material, that is, obtain negative pole gram volume, acquired results are shown in Table 1 in D1 divided by negative electricity pole piece.
High rate performance is tested：Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment
Battery core carry out high rate performance test：Stand 3min；0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C；Stand
3min；0.2C constant-current discharges obtain discharge capacity D1 to 3.0V；Stand 3min；0.2C constant-current charges to 4.2V, 4.2V constant pressures is filled
Electricity is to 0.05C；Stand 3min；2C constant-current discharges obtain discharge capacity D21 to 3.0V；Stand 3min；High rate performance is completed afterwards
Test, battery high rate performance=D2/D1*100%, acquired results are shown in Table 1.
Loop test:The electricity prepared in 25 DEG C of environment by following flow to each embodiment and comparative example silicon carbon material
Core is circulated test：Stand 3min；0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C；Stand 3min；0.2C
Constant-current discharge obtains discharge capacity D1 to 3.0V；3min is stood, " 0.2C constant-current charges to 4.2V, 4.2V constant-voltage charges are extremely
0.05C；Stand 3min；0.2C constant-current discharges obtain discharge capacity Di to 3.0V；3min " is stood to repeat to obtain D300 299 times,
Loop test is completed afterwards, and calculating capability retention is D300/D1*100%, and acquired results are shown in Table 1.
Battery core gram volume, circulation volume conservation rate and high rate performance that table 1, different silicon-carbon cathode materials are prepared
It can be obtained by table 1, silicon-carbon cathode material prepared by the present invention, with more outstanding chemical property：It is i.e. higher
Gram volume, more preferable circulation volume conservation rate and higher high rate performance.Specifically, comparative examples are implemented with embodiment 1-
Example 6 can be obtained, with d1/D2 reduction, and the chemical property of material is gradually stepped up, and this is due to continuous part between lamella holes
The smaller porous graphenes of width d1, the inhibition spread to ion is lower；It can be obtained by embodiment 9, more preferably disperse side
Presoma prepared by method, silicon-carbon cathode has more preferable chemical property, and this is due to that more preferably dispersing technology can be divided
More preferably uniform presoma is dissipated, therefore the consumption of graphene will further decrease, its diffusional resistance to ion is smaller.By each reality
Applying example can obtain, and the present invention has universality, be adapted to various silicon-carbon cathode materials and preparation method thereof.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art exist
Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of the present invention.This
Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Constitute any limitation.
Claims (10)
1. a kind of silicon-carbon cathode material, it is characterised in that the particle diameter D1 of the silicon-carbon cathode material is 1 μm -200 μm, institute
Silicon-carbon cathode material is stated for second particle structure, the second particle is made up of primary particle and electronics conductive components, it is described once
The particle diameter of particle is D2, and D2≤0.5D1；
The electronics conductive components include graphene sheet layer, and the primary particle and the graphene sheet layer are dispersed；Stone
Black alkene is porous graphene；
Lamellar spacing h1≤100nm of the porous graphene, the bore dia of the porous graphene is continuous part between D3, holes
Width be d1, and d1≤0.5D1.
2. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that contain silicon containing component in the primary particle
Grain.
3. the silicon-carbon cathode material described in a kind of claim 2, it is characterised in that the silicon containing component be pure silicon, Si oxide,
At least one in silicon based composite material, modified silica-base material；Also contain non-silicon containing component particle in the primary particle, it is described
Non- silicon containing component particle includes native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, pyrolysis
At least one in resin carbon, lithium carbonate, non-silicon alloy material of cathode.
4. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the primary particle is uniformly scattered in described
The sheet surfaces of porous graphene, and good electron channel is formed between the two；The lamellar spacing h1 of the porous graphene
≤40nm；In the silicon-carbon cathode material, the part by weight of graphite olefinic constituent is x%, and x≤5.
5. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that also containing super in the electronics conductive components
At least one in conductive carbon, acetylene black, CNT, Ketjen black, conductive carbon black；Connect between the holes of the porous graphene
Width d1≤D2 of continuous part.
6. the preparation method of the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that mainly comprise the following steps：
Step 1, prepared by presoma：Electronics conductive components are well mixed with primary particle and obtain presoma；
Step 2, presoma is granulated, obtains second particle presoma；
Step 3, coat, being carbonized obtains finished product second particle.
7. the preparation method of the silicon-carbon cathode material described in a kind of claim 6, it is characterised in that in the electronics conductive components
Including porous graphene, thickness degree h1≤100nm of the porous graphene is continuous between the porous graphene lamella holes
Partial width d1≤0.5D1；Contain silicon containing component particle and non-silicon containing component particle in the primary particle.
8. the preparation method of the silicon-carbon cathode material described in a kind of claim 7, it is characterised in that the silicon containing component is pure
At least one in silicon, Si oxide, silicon based composite material, modified silica-base material；The non-silicon containing component particle includes natural
Graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, non-silicon alloy
At least one in negative material；Also contain super conductive carbon, acetylene black, CNT, section's qin in the electronics conductive components
At least one in black, conductive carbon black；On the porous graphene lamella between holes continuous part width d1≤D2.
9. a kind of preparation method of the silicon-carbon cathode material described in claim 6, it is characterised in that step 1 is specially：By electronics
Conductive components, solvent 1, helper component 1 are uniformly mixed；Primary particle, solvent 2, helper component 2 are uniformly mixed；Afterwards by two
Kind blending ingredients, which are mixed into row, further to be disperseed, and obtains electronics conductive components and the equally distributed presoma of primary particle.
10. a kind of preparation method of the silicon-carbon cathode material described in claim 6, it is characterised in that the granulation described in step 2
Journey is spray drying；Cladding described in step 3 is cladding indefinite form carbon-coating；The clad include phenolic resin, melamine resin,
Vinylidene Chloride, pitch, polyethylene, stearic acid, PVC, polyacrylonitrile, natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers,
At least one in polyethylene, polypropylene, polyamide, polyethylene terephthalate.
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