CN107134567A - Silicon-carbon cathode material and preparation method thereof - Google Patents
Silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- CN107134567A CN107134567A CN201710271172.6A CN201710271172A CN107134567A CN 107134567 A CN107134567 A CN 107134567A CN 201710271172 A CN201710271172 A CN 201710271172A CN 107134567 A CN107134567 A CN 107134567A
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 invention belongs to energy storage material technical field, more particularly to a kind of silicon-carbon cathode material, including nuclear structure and shell structure, the nuclear structure is second particle structure, and including the leading electric network with loose structure and the nanometer primary particle being filled in the porous leading electric network pore structure；Between the leading electric network and the nanometer primary particle, guidance electric network is distributed with, the leading electric network is closely joined together by the guidance electric network with the nanometer primary particle, so that it is guaranteed that the silicon-carbon cathode material has excellent chemical property.
Description
Technical field
The invention belongs to energy storage material technical field, 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, causes the decay of its cycle performance fast, is limited it and is widely applied.In order to solve the above problems,
Prior art mainly has silicon grain nanosizing, conductive 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.
But the based particles of nanostructured are easily reunited, disperse difficulty big；And conventional conductive agent material, general size
Smaller (nanoscale), and specific surface area is larger, scattered difficulty is bigger.But when, to maximize conductive agent conductive effect and
The more excellent silicon substrate second particle material of processability, it is necessary to ensure that nano silicon-based particle and conductive agent are dispersed.Meanwhile,
Bonding force between nanostructured silica-base material and conductive agent is weaker, and two kinds of interruption is easily lead to during volumetric expansion
Open, so as to influence the chemical property of silicon carbon material.
In view of this, it is necessory to propose a kind of silicon-carbon cathode material and preparation method thereof, it can be by two kinds of scattered hardly possiblies
Spend larger material (nano silicon-based particle, conductive agent) dispersed, while ensure to be closely joined together between the two, from
And prepare the silicon-carbon cathode material of function admirable.
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, including core knot
Structure and shell structure, the nuclear structure are second particle structure, and including the leading electric network with loose structure and are filled out
The nanometer primary particle filled in the porous leading electric network pore structure；The leading electric network and the nanometer primary particle
Between, guidance electric network is distributed with, the guidance electric network closely connects the leading electric network with the nanometer primary particle
It is connected together.So that it is guaranteed that the silicon-carbon cathode material has excellent chemical property.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of silicon-carbon cathode material, including nuclear structure and shell structure, the nuclear structure are second particle structure, and are wherein wrapped
Include the leading electric network with loose structure and the nanometer primary particle being filled in the porous leading electric network pore structure；
Between the leading electric network and the nanometer primary particle, guidance electric network is distributed with, the guidance electric network is by the master
Conductive network is closely joined together with the nanometer primary particle.Shell structure refers to the general clad of negative material, mainly
Obtained for the materials such as pitch cladding, carbonization, therefore the present invention is not set forth in detail.
Improved as one kind of silicon-carbon cathode material of the present invention, the leading electric network structure is porous agraphitic carbon network
In structure, porous hard carbon network structure, opening graphene-structured, opening intumesced graphite structure, quasiflake graphite alkene structure extremely
Few one kind；The primary particle includes nano silicon-based negative pole particle；The guidance electric network conductive network is by high polymer material
Carbonization is obtained.
As silicon-carbon cathode material of the present invention one kind improve, the nano silicon-based negative pole particle be silicon nanoparticle or/
With nano-silicon oxidationization；The high polymer material is obtained by high polymer monomer in-situ polymerization.
As silicon-carbon cathode material of the present invention one kind improve, it is described guidance electric network in, can also include conductive black,
At least one of super conductive carbon, Ketjen black, CNT, graphene, acetylene black；The primary particle can also include non-
Nano silicon-based negative pole particle；The non-nano silicon-based anode particle be native graphite, Delanium, carbonaceous mesophase spherules, soft carbon,
Hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, tin base cathode material, transition metal nitride, kamash alloy, germanium
At least one of based alloy, acieral, antimony-containing alloy, magnesium base alloy；
Present invention additionally comprises a kind of preparation method of silicon-carbon cathode material, it is characterised in that mainly comprises the following steps：
Step 1, prepared by presoma：Mediated after primary particle, polymer monomer are mixed, obtain polymer monomer uniform
It is scattered in nanometer presoma on primary particle surface；
Step 2, electric network structure is dominated to prepare：Prepare the leading electric network structure with loose structure stand-by；
Step 3, fill：Presoma made from step 1 is filled into leading electric network structure；
Step 4, polymerisation：By the product of step 3, in the environment for being placed in initiator presence, promote to be scattered in once
The high polymer monomer polymerization on grain surface, obtains high molecular polymer；The polymer now generated will be primary particle and leading electricity
Network closely bonds together；
Step 5, the product of step 4 is coated, being carbonized obtains finished silicon carbon negative pole material.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, polymer monomer described in step 1 includes propylene
Esters of gallic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol dimethacrylate, poly- second two
Alcohol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl methacrylate, N, N- dimethyl
Acrylamide, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate, positive Hexyl 2-propenoate, 2- acrylic acid
Cyclohexyl, dodecyl acrylate, GDMA, polyethylene glycol dimethacrylate, polyethylene glycol diformazan
Base acrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, tetraethylene glycol diacrylate, two contractings 3 third
Omega-diol diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythritol acrylate, double-Glycerin
Tetraacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate, the acrylic acid of glycerol propoxylate three
Ester, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylates, propoxylation trimethylolpropane
Triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxy
At least one of base trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate；Initiator isopropyl described in step 4
Benzene hydrogen peroxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, peroxidating
The special butyl ester of lauroyl, perbenzoic acid, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, the carbon of peroxidating two
At least one of sour dicyclohexyl maleate.
Improve, included in nanometer primary particle described in step 1 as one kind of silicon-carbon cathode material preparation method of the present invention
There is nano silicon-based particle；Non-nano silicon-based anode particle, the non-nano silicon substrate can also be included in the nanometer primary particle
Negative pole particle be native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon,
Lithium carbonate, tin base cathode material, transition metal nitride, kamash alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium-based are closed
At least one of gold；High molecular polymer, carbon source component, conductive agent component or/and solvent can also be added when mediating reaction
Component, the high molecular polymer includes polymethyl methacrylate (PMMA), Kynoar (PVDF), butadiene-styrene rubber
(SBR), at least one of sodium carboxymethylcellulose (CMC), polypropylene fine (PAN), the carbon source component include glucose, sugarcane
Sugar, soluble starch, cyclodextrin, furfural, sucrose, glucose, cornstarch, tapioca, wheaten starch, cellulose, poly- second
Enol, polyethylene glycol, Tissuemat E, phenolic resin, vinyl pyrrolidone, epoxy resin, polyvinyl chloride, glycan alcohol, furans
Resin, Lauxite, polymethyl methacrylate, Kynoar or polyacrylonitrile, petroleum coke, oil system needle coke, coal measures pin
At least one of shape Jiao, the conductive agent component include conductive black, super conductive carbon, Ketjen black, CNT, graphene,
At least one of acetylene black, water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, two
At least one of ethyl-formamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, kneading process described in step 1 is：By nanometer one
Secondary particle, silane coupler, polymer monomer, solvent 1 are mediated, and obtain mixture 1；By conductive agent component, surfactant, molten
Agent 2 is mediated, and obtains mixture 2；Mixture 1 is blended with mixture 2 again, the blending method include kneadings, ball milling, it is husky grind,
At least one of high-pressure homogeneous, high speed shear, is uniformly dispersed and obtains precursor pulp.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, electric network structure is dominated described in step 2 and is prepared
Process includes：
It is prepared by porous agraphitic carbon network structure and porous hard carbon network structure：Carbon source component and carbon after foaming agent reaction
The directly reaction of change, template, polymer obtains being carbonized after loose structure；
It is prepared by graphene-structured, opening intumesced graphite structure and the quasiflake graphite alkene structure of being open：With crystalline flake graphite or micro-
Spar ink (can prepare quasiflake graphite alkene, change and be closely joined together between graphene sheet layer, while between lamella point
There is the gap structure of prosperity in portion, is easy to the filling of primary particle；Micro crystal graphite alkene particle size is smaller simultaneously, and what is prepared is compacted
Worm shape graphene particle diameter is 10 μm or so, is matched very much with final finished silicon-carbon cathode particle diameter) it is raw material, control oxidation is inserted
(main oxygenerating degree is moderate, and degree of oxidation is too low, it is impossible to form loose structure for layer degree；Degree of oxidation is too high, reduces
Graphite flake layer will be completely exfoliated and come in journey, it is impossible to form the loose structure linked together), reduce afterwards, you can obtain same
The loose structure that lamella links together, is open between lamella and lamella between one coccolith ink.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the filling process described in step 3 is：
Porous leading electric network structural material is pre-processed, the pretreatment includes surface active or/and addition surface
Activating agent；
Before filling, porous leading electric network structural material is placed in vacuum environment and vacuumized, excluded in pore structure
Air, is the filling vacating space of presoma, is placed in afterwards in precursor pulp and starts filling；
In filling process, apply pressure, presoma is squeezed into hole；Temperature is improved, the viscosity of presoma is reduced；
Increase mechanical disturbance, open hole mouthful.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the silane coupler accounts for nano silicon-based quality
0.01-10%, slurry solid content is not less than 1%；The surfactant accounts for the 0.01-10% of conductive agent quality, and slurry is solid
Content is not less than 0.5%.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the silane coupler is coupled for alkyl silane
Agent, amino silicane coupling agent, alkenyl silane coupling agent, epoxyalkylsilane coupling agent and the coupling of alkyl acyloxy silane
At least one of agent；The solvent 1 is water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethyl
At least one of acid amides, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.The surfactant is surfactant
Include at least one of wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent；The solvent 2 be water, alcohols,
Ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrochysene
At least one of furans.
The advantage of the invention is that：
1. the leading electric network structure of the present invention can play electronics conduction with limiting the double of primary particle charging volumetric expansion
Recast is used, while excellent conductive capability inside silicon-carbon cathode material particle is ensured, silicon-carbon material in stabilized charge and discharge process
Expect the macrostructure of particle；
2. teach electric network structure to be closely connected leading electric network structure with primary particle, it is ensured that to come in discharge and recharge volume
Return during dilation, all primary particles effectively can be connected with leading electric network close structure, form electronics path；
So that it is guaranteed that the chemical property of each primary particle can fully play out in cyclic process；
3. in preparation process, using the low high polymer monomer of viscosity and primary particle mediate and disperse, it can be ensured that receive
Rice primary particle is dispersed, and high polymer monomer is uniformly distributed in a nanometer primary particle surface；
4. the presoma with more low viscosity (because high polymer monomer viscosity is low), it is easier to be filled into leading electric network
Pore structure in, it is ensured that fill up primary particle in the hole of leading electric network loose structure.
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, prepares the silicon-carbon second particle material that particle diameter is 10 μm；
Step 1, mix：By elemental silicon, polymethyl methacrylate, conductive black, the tetraethoxy-silicane that particle diameter is 100nm
Alkane, polyvinylpyrrolidone are so that (mass ratio is elemental silicon:Polymethyl methacrylate:Conductive black:Tetraethoxysilane:It is poly-
Vinylpyrrolidone=90:4:4.9:1:0.1) and NMP mix 10h (solid content is 0.5%), obtain slurry.
Step 2, prepared by second particle：Adjustable spraying drying condition, prepares the silicon-carbon that particle diameter is 10 μm secondary
Particle；Coated afterwards, being carbonized obtains finished product silicon-carbon cathode material.
Embodiment 1, is that the present embodiment comprises the following steps with comparative example difference：
Step 1, prepared by presoma：By elemental silicon, methyl methacrylate, tetraethoxysilane (matter of the particle diameter for 100nm
Amount is than being elemental silicon:Methyl methacrylate：Tetraethoxysilane=95:4:1), (solid content is 10%) pinches after NMP mixing
Close, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain elemental silicon, methyl methacrylate, tetraethoxy-silicane
The dispersed presoma of alkane；
Step 2, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 15%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Step 3, fill：The quasiflake graphite alkene that step 2 is obtained is vacuumized, and is placed in afterwards in the presoma of step 1, then
Apply pressure into presoma, while ultrasonic vibration so that presoma is inserted in quasiflake graphite alkene pore structure, isolated to fill out
Quasiflake graphite alkene full of presoma；
Step 4, polymerisation：The special butyl ester of perbenzoic acid is dissolved in NMP and disperses to obtain solution, step is sprayed onto afterwards
The quasiflake graphite alkene surface of the rapid 3 full presomas of obtained filling, heating promotes to be scattered in the metering system on primary particle surface
Sour methyl esters polymerization, so that together with primary particle is closely bonded with quasiflake graphite alkene lamella.
Step 5, the product of step 4 is coated to, is carbonized (while by clad and polymer carbonization) and obtains finished product
Silicon-carbon cathode material.
Embodiment 2, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 5%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 3, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 20%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 4, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 25%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 5, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, quasiflake graphite alkene is dominated electric network structure and prepared：Selection micro crystal graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 40%, it
After to be thermally treated resulting in quasiflake graphite alkene stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 6, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, prepared by presoma：By elemental silicon, methyl methacrylate, tetraethoxysilane (matter of the particle diameter for 100nm
Amount is than being elemental silicon:Methyl methacrylate：Tetraethoxysilane=95:4:1), (solid content is 10%) pinches after NMP mixing
Close, revolve round the sun as 30 turns/min, 300 turns/min is switched to certainly；Mediate 4h and obtain elemental silicon, methyl methacrylate, tetraethoxy-silicane
The dispersed mixture 1 of alkane；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive black:Polyvinylpyrrolidone
=90:1) and after NMP mixing (solid content is 5%) mediates, and revolves round the sun as 20 turns/min, 200 turns/min is switched to certainly；4h is mediated to obtain
Mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Conductive black=95:5) mix, continue to mediate,
Revolve round the sun as 20 turns/min, 300 turns/min is switched to certainly；Mediate the nano silica-base material that polymer monomer cladding is obtained after 4h, conduction
The dispersed precursor pulp of carbon black；
Step 2, expanded graphite is dominated electric network structure and prepared：Selection crystalline flake graphite is raw material, and the concentrated sulfuric acid, height are added afterwards
Potassium manganate carries out oxidation intercalation, obtains the graphite oxide that oxygen-containing functional group quality accounts for whole graphite oxide quality 20%, Zhi Houre
The leading electric network of expanded graphite that processing obtains graphite flake layer opening is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 7, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：By the sub- silicon+Delanium of oxidation that particle diameter is 100nm, (mass ratio be oxidation Asia silicon:Delanium
=1：9), (mass ratio is (the sub- silicon+Delanium of oxidation) for methyl methacrylate, methylvinyldimethoxysilane:Methyl
Methyl acrylate：Methylvinyldimethoxysilane=90:4:1), (solid content is 10%) mediates after ethanol mixing, public
Switch to 5 turns/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By methylvinyldimethoxysilane, graphene,
(mass ratio is methylvinyldimethoxysilane to polyoxyethylated alkyl phenol:Graphene:Polyoxyethylated alkyl phenol=5:
4.9:0.1) and after ethanol mixing (solid content is 4%) mediates, and revolves round the sun as 5 turns/min, 10 turns/min is switched to certainly；8h is mediated to obtain
Mixture 2；By mixture 1, mixture 2, (mass ratio is (the sub- silicon+Delanium of oxidation):Graphene=90:4.9) it is blended in one
Rise, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Polymer monomer is obtained after kneading 6h to be uniformly wrapped on once
Particle surface, scattered polymer monomer and graphene uniform, graphene and the dispersed presoma of primary particle；
Step 2, agraphitic carbon is dominated electric network structure and prepared：Selection pitch is mixed with foaming agent, carries out foaming instead afterwards
It should again be carbonized, obtain agraphitic carbon and dominate electric network structure.
Remaining is same as Example 1, repeats no more.
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 carries out loop 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.
The chemical property of the battery core of silicon-carbon cathode material system assembling prepared by table 1, different comparative examples and embodiment
Can be obtained by table 1, the present invention can prepare the silicon-carbon cathode material of function admirable, using the silicon-carbon cathode material as
The battery core that negative electrode active material assembling is obtained has excellent chemical property.Specifically, comparative examples are real with embodiment 1-
Applying example 5 can obtain, with the increase of oxygen-containing functional group, battery capacity first increase keep afterwards it is constant (functional group very little, due to space too
Few, the primary particle amount of filling is less), cycle performance can first keep constant rear sharp-decay, and (functional group is too many, causes graphene
Adhesion is very low between lamella, therefore to the bad stability of material result), high rate performance, which has, first increases the trend reduced afterwards
(graphene sheet layer more dispersed then there is inhibition, influence battery high rate performance to ion transmission).It can be obtained by each embodiment, this
Invention has universality.
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, including nuclear structure and shell structure, it is characterised in that the nuclear structure is second particle knot
Structure, and including the leading electric network with loose structure and the nanometer being filled in the pore structure of the leading electric network
Primary particle；Guidance electric network, the guidance electric network are distributed between the leading electric network and the nanometer primary particle
The leading electric network is closely joined together with the nanometer primary particle.
2. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the leading electric network is porous agraphitic carbon
In network structure, porous hard carbon network structure, opening graphene-structured, opening intumesced graphite structure, quasiflake graphite alkene structure
At least one；The primary particle includes nano silicon-based negative pole particle；The guidance electric network is carbonized by high polymer material
Obtain.
3. the silicon-carbon cathode material described in a kind of claim 2, it is characterised in that the nano silicon-based negative pole particle is nano-silicon
Particle or/and nanometer silicon oxide particles；The high polymer material is obtained by high polymer monomer in-situ polymerization.
4. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that in the guidance electric network, in addition to conduction
At least one of carbon black, super conductive carbon, Ketjen black, CNT, graphene, acetylene black；The primary particle also includes
Non-nano silicon-based anode particle；The non-nano silicon-based anode particle is native graphite, Delanium, carbonaceous mesophase spherules, soft
Carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, tin base cathode material, transition metal nitride, kamash alloy,
At least one of germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy.
5. 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：Mediated after primary particle, polymer monomer are mixed, obtain polymer monomer and uniformly disperse
Presoma in nanometer primary particle surface；
Step 2, electric network structure is dominated to prepare：Prepare the leading electric network structure with loose structure stand-by；
Step 3, fill：Presoma made from step 1 is filled into leading electric network structure；
Step 4, polymerisation：By the product of step 3, in the environment for being placed in initiator presence, promote to be scattered in primary particle table
The high polymer monomer polymerization in face, obtains high molecular polymer；
Step 5, the product of step 4 is coated, being carbonized obtains finished silicon carbon negative pole material.
6. a kind of preparation method of the silicon-carbon cathode material described in claim 5, it is characterised in that polymer list described in step 1
Body includes esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, glycol dimethacrylates
Ester, polyethyleneglycol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl methacrylate, N,
N- DMAAs, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate, positive Hexyl 2-propenoate,
2- cyclohexyl acrylates, dodecyl acrylate, GDMA, polyethylene glycol dimethacrylate, poly- second
Diol dimethacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, tetraethylene glycol diacrylate,
Tri (propylene glycol) diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythritol acrylate, double-three
Hydroxy propane tetraacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate, glycerol propoxylate three
Acrylate, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylates, the hydroxyl first of propoxylation three
Base propane triacrylate, ethoxylated trimethylolpropane triacrylate, the acrylic acid of ethoxylated trimethylolpropane three
At least one of ester, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate；Draw described in step 4
Sending out agent includes isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, peroxidating two
The special butyl ester of benzoyl, dilauroyl peroxide, perbenzoic acid, peroxide tert pivalate ester, dicetyl peroxydicarbonate diisopropyl
At least one of ester, di-cyclohexylperoxy di-carbonate.
7. the preparation method of the silicon-carbon cathode material described in a kind of claim 5, it is characterised in that nanometer described in step 1 is once
Include nano silicon-based particle in particle；Also include non-nano silicon-based anode particle in the nanometer primary particle；Mediate reaction
When be additionally added high molecular polymer, carbon source component, conductive agent component, solvent composition.
8. a kind of preparation method of the silicon-carbon cathode material described in claim 5, it is characterised in that kneading process described in step 1
For：Nanometer primary particle, silane coupler, polymer monomer, solvent 1 are mediated, mixture 1 is obtained；By conductive agent component, table
Face activating agent, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and obtains forerunner's somaplasm
Material.
9. the preparation method of the silicon-carbon cathode material described in a kind of claim 5, it is characterised in that power network is dominated described in step 2
Electric network is dominated described in network swollen for porous agraphitic carbon network structure, porous hard carbon network structure, opening graphene-structured, opening
At least one of swollen graphite-structure, quasiflake graphite alkene structure, wherein, porous agraphitic carbon network structure and porous hard carbon net
The preparation method of network structure includes：The directly reaction of carbonization, template, polymer obtains porous after carbon source component is reacted with foaming agent
It is carbonized after structure；
Opening graphene-structured, opening intumesced graphite structure and the preparation method of quasiflake graphite alkene structure are：With crystalline flake graphite
Or micro crystal graphite is raw material, control oxidation intercalation degree is reduced afterwards, you can obtain the same interior lamella of coccolith ink and lamella extremely
A few part links together, while forming the loose structure of opening between lamella and lamella again.
10. a kind of preparation method of the silicon-carbon cathode material described in claim 5, it is characterised in that the filling described in step 3
Cheng Wei：
Leading electric network structural material is pre-processed, the pretreatment includes surface active or/and addition surfactant；
Before filling, leading electric network structural material is placed in vacuum environment and vacuumized, the air in discharge pore structure, before being
The filling vacating space of body is driven, is placed in afterwards in precursor pulp and starts filling；
In filling process, apply pressure, presoma is squeezed into hole；Temperature is improved, the viscosity of presoma is reduced；Increase
Mechanical disturbance, opens hole mouthful.
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