CN107069016A - 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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- CN107069016A CN107069016A CN201710270679.XA CN201710270679A CN107069016A CN 107069016 A CN107069016 A CN 107069016A CN 201710270679 A CN201710270679 A CN 201710270679A CN 107069016 A CN107069016 A CN 107069016A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
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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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- 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 silicon-carbon cathode material includes nuclear structure and shell structure, the nuclear structure, which has, is dispersed in second particle structure tightly packed after conductive agent by nanometer primary particle, and the nanometer primary particle includes nano silicon-based particle；And it is distributed with conductive network between the nano silicon-based particle, between the conductive agent and between the nano silicon-based particle and the conductive agent, and the conductive network is closely connected with the nano silicon-based particle and the conductive agent, 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 to improve the electric conductivity of silica-base material integral particle, while solving silica-base material mechanical crushing in material charge and discharge process
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, easilys lead to break between the two 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
An object of the present invention is：In view of the shortcomings of the prior art, a kind of silicon-carbon cathode material provided, its energy
It is enough that the larger material (nano silicon-based particle, conductive agent) of two kinds of scattered difficulty is dispersed, while ensuring tight between the two
It is close to link together, so as to prepare the silicon-carbon cathode material of function admirable, so that it is guaranteed that the silicon-carbon cathode material have it is excellent
Good chemical property.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of silicon-carbon cathode material, the silicon-carbon cathode material is the tightly packed obtained second particle knot of primary particle
Primary particle and conductive agent component are included in structure, the second particle, the primary particle includes nano silicon-based particle；It is described
Conduction is distributed between nano silicon-based particle, between the conductive agent and between the nano silicon-based particle and the conductive agent
Closely connected between network, and the conductive network and the nano silicon-based particle and the conductive agent component.
Improved as one kind of silicon-carbon cathode material of the present invention, the conductive network is obtained by high polymer material carbonization；Institute
High polymer material is stated before carbonization, is uniformly distributed between the nano silicon-based particle and the conductive agent, and will be described
Closely bonded between nano silicon-based particle, between the conductive agent and between the nano silicon-based particle and the conductive agent
Together.
Improved as one kind of silicon-carbon cathode material of the present invention, the macromolecule is obtained by high polymer monomer in-situ polymerization
Arrive.
Improved as one kind of silicon-carbon cathode material of the present invention, the nano silicon-based particle is simple substance silicon grain or/and silicon
Oxide particle；The conductive agent component includes conductive black, super conductive what is said or talked about, Ketjen black, CNT, graphene, acetylene
At least one of conductive network that black, high polymer material carbonization is obtained；The primary particle can also include non-nano silicon substrate
Negative pole particle；The non-nano silicon-based anode particle is native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, stone
Oil coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, tin base cathode material, transition metal nitride, kamash alloy, germanium-base alloy,
At least one of 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, mediate：Mediated after nanometer primary particle, polymer monomer are mixed so that polymer monomer uniformly divides
Dissipate in nanometer primary particle surface；
Step 2, polymerisation：Initiator is added into the product of step 1, promotes polymerized monomer to occur polymerisation, it is raw
Into polymer network structure be coated on a nanometer primary particle surface；
Step 3, pelletizing：The product that step 2 to a certain extent is obtained occurs for selective polymerization reaction, carries out pelletizing, obtains
Second particle；
Step 4, prepared by silicon-carbon cathode：The product that step 3 is obtained is coated, is carbonized, that is, obtains finished silicon Carbon anode
Material.
Shell structure refers to the general clad of negative material, and predominantly the material such as pitch cladding, carbonization are obtained, therefore this hair
It is bright to be not set forth in detail.
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 described in step 2 is different
Cumene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, peroxide
Change the special butyl ester of lauroyl, perbenzoic acid, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, peroxidating two
At least one of dicyclohexyl carbonate.
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 what is said or talked about, 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, polymerisation described in step 3 occurs to certain
Degree refers to that polymerisation has carried out 10%~90%.
Improve, can occur with exchange step 2 and step 3 as one kind of silicon-carbon cathode material preparation method of the present invention
Sequentially, i.e.,：
Step 2, pelletizing：The precursor pulp obtained using step 1, is carried out pelletizing, obtains second particle；
Step 3, polymerisation：In the environment that the second particle that step 2 is obtained exists as initiator, promote polymerization single
Polymerisation occurs for body, and the polymer network structure of generation is coated on a nanometer primary particle surface；Now require selected poly-
The boiling point of monomer adduct is not less than used drying temperature during pelletizing.
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 present invention uses the low-down high polymer monomer of viscosity as the reactant of dispersed with stirring, can greatly it reduce
Scattered difficulty so that high polymer monomer is dispersed in a nanometer primary particle surface；
, can be by nanometer once 2. the present invention is using high polymer monomer in-situ polymerization, carbonization afterwards builds conductive network
Each component closely bonds together inside the second particles such as grain, conductive agent component, so that it is guaranteed that the electrification of each primary particle
Learn performance can fully play out in cyclic process；
3. in kneading process, high polymer monomer, silane coupler can be uniformly wrapped on to a nanometer primary particle surface, more had
Beneficial to scattered between nanometer primary particle；Similarly, surfactant can be also uniformly wrapped on to conductive agent surface, be more beneficial for
It is scattered between conductive agent particle；Simultaneously as first individually scattering in advance, silane coupler and surface-active can be maximized
The performance of agent, both consumptions of reduction；
4. using kneading process, in the case where guarantee is dispersed, moreover it is possible to the consumption of minimumization solvent 1 and solvent 2, make
The solid content for the slurry that must be obtained is improved as far as possible；Energy consumption during spray drying can be now reduced, production efficiency, drop is improved
Low production cost；Simultaneously as solid content is high, during spray drying, the quantity of solvent evaporated from mist particles will reduce (molten
Agent volatilization process often by along with the relatively low conductive agent component of density from inside generation from particle to particle surface transport phenomena,
The phenomenon for ultimately resulting in conductive agent skewness in second particle occurs), therefore its influence being distributed to conductive agent is lower, obtains
To second particle in conductive agent distribution it is more uniform；Therefore second particle active material there is higher capacity, it is lower interior
Resistance；
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 using (mass ratio as:Elemental silicon:Polymethyl methacrylate:Conductive black:Tetraethoxysilane:It is poly-
Vinylpyrrolidone=90:4:4.9:1:0.1) and NMP (solid content is 0.5%) mix 10h, 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, mediate：By elemental silicon, methyl methacrylate, the tetraethoxysilane (mass ratio that particle diameter is 100nm
For:Elemental silicon:Methyl methacrylate:Tetraethoxysilane=90:4:1), mediated after NMP (solid content is 1%) mixing,
Revolve round the sun as 60 turns/min, 500 turns/min is switched to certainly；Mediate 2h and obtain mixture 1；By conductive black, polyvinylpyrrolidone (matter
Amount is than being conductive black:Polyvinylpyrrolidone=4.9:0.1) and after NMP (solid content is 0.5%) mixing mediate, revolving round the sun is
60 turns/min, 500 turns/min is switched to certainly；Mediate 2h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:
Conductive black=90:4.9) mix, continue to mediate, revolve round the sun as 20 turns/min, 300 turns/min is switched to certainly；Mediate after 2h
Obtain the dispersed mixed slurry of polymer monomer, nano silica-base material, conductive black；
Step 2, polymerisation：The special butyl ester of initiator perbenzoic acid is added into the product of step 1, promotes polymer
Polymerisation occurs for monomer, and the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 50% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
Step 4, prepared by silicon-carbon cathode：The product that step 3 is obtained is coated, is carbonized, that is, obtains finished silicon Carbon anode
Material.
It is other identical with comparative example, it is not repeated herein.
Embodiment 2, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：By elemental silicon, methyl methacrylate, the tetraethoxysilane (mass ratio that particle diameter is 100nm
For：Elemental silicon:Methyl methacrylate：Tetraethoxysilane=90:4:1), (solid content is 5%) mediates after NMP mixing,
Revolve round the sun as 20 turns/min, 300 turns/min is switched to certainly；Mediate 2h and obtain mixture 1；By conductive black, polyvinylpyrrolidone (matter
Amount is than being conductive black:Polyvinylpyrrolidone=4.9:0.1) and after NMP mixing (solid content is 2%) mediates, and revolves round the sun as 20
Turn/min, 300 turns/min is switched to certainly；Mediate 2h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Lead
Electric carbon black=90:4.9) mix, continue to mediate, revolve round the sun as 20 turns/min, 300 turns/min is switched to certainly；Mediate and obtained after 2h
To the mixed slurry that polymer monomer, nano silica-base material, conductive black are dispersed；
Step 2, polymerisation：The special butyl ester of initiator perbenzoic acid is added into the product of step 1, promotes polymer
Polymerisation occurs for monomer, and the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 50% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 3, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：By elemental silicon, methyl methacrylate, the tetraethoxysilane (mass ratio that particle diameter is 100nm
For：Elemental silicon:Methyl methacrylate：Tetraethoxysilane=90:4:1), (solid content is 10%) mediates after NMP mixing,
Revolve round the sun as 10 turns/min, 100 turns/min is switched to certainly；Mediate 4h and obtain mixture 1；By conductive black, polyvinylpyrrolidone (matter
Amount is than being conductive black:Polyvinylpyrrolidone=4.9:0.1) and after NMP mixing (solid content is 5%) mediates, and revolves round the sun as 10
Turn/min, 100 turns/min is switched to certainly；Mediate 4h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Lead
Electric carbon black=90:4.9) mix, continue to mediate, revolve round the sun as 20 turns/min, 100 turns/min is switched to certainly；Mediate and obtained after 4h
To the mixed slurry that polymer monomer, nano silica-base material, conductive black are dispersed；
Step 2, polymerisation：The special butyl ester of initiator perbenzoic acid is added into the product of step 1, promotes polymer
Polymerisation occurs for monomer, and the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 50% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 4, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：By elemental silicon, methyl methacrylate, the tetraethoxysilane (mass ratio that particle diameter is 100nm
For：Elemental silicon:Methyl methacrylate：Tetraethoxysilane=90:4:1), (solid content is 20%) mediates after NMP mixing,
Revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By conductive black, polyvinylpyrrolidone (quality
Than for conductive black:Polyvinylpyrrolidone=4.9:0.1) and NMP mixing after (solid content is 10%) mediate, revolve round the sun for 5 turns/
Min, switchs to 10 turns/min certainly；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Conductive charcoal
Black=90:4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；It is polymerize after mediating 6h
The dispersed mixed slurry of thing monomer, nano silica-base material, conductive black；
Step 2, polymerisation：The special butyl ester of initiator perbenzoic acid is added into the product of step 1, promotes polymer
Polymerisation occurs for monomer, and the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 50% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 5, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：By elemental silicon, methyl methacrylate, the tetraethoxysilane (mass ratio that particle diameter is 100nm
For：Elemental silicon:Methyl methacrylate：Tetraethoxysilane=90:4:1), (solid content is 40%) mediates after NMP mixing,
Revolve round the sun as 1 turn/min, 0 turn/min is switched to certainly；Mediate 20h and obtain mixture 1；By conductive black, polyvinylpyrrolidone (quality
Than for conductive black:Polyvinylpyrrolidone=4.9:0.1) and NMP mixing after (solid content is 15%) mediate, revolve round the sun for 1 turn/
Min, switchs to 0 turn/min certainly；Mediate 20h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Conductive charcoal
Black=90:4.9) mix, continue to mediate, revolve round the sun as 2 turns/min, 10 turns/min is switched to certainly；It is polymerize after mediating 20h
The dispersed mixed slurry of thing monomer, nano silica-base material, conductive black；
Step 2, polymerisation：The special butyl ester of initiator perbenzoic acid is added into the product of step 1, promotes polymer
Polymerisation occurs for monomer, and the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 50% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 6, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：(mass ratio is for the elemental silicon, divinylbenzene, tetraethoxysilane that are 100nm by particle diameter：It is single
Matter silicon:Divinylbenzene：Tetraethoxysilane=90:4:1), (solid content is 20%) mediates after NMP mixing, revolves round the sun as 5
Turn/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By conductive black, polyvinylpyrrolidone, (mass ratio is to lead
Electric carbon black:Polyvinylpyrrolidone=4.9:0.1) and after NMP mixing (solid content is 10%) mediates, and revolves round the sun as 5 turns/min, from
Switch to 10 turns/min；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Conductive black=90:
4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 6h after obtain polymer monomer,
The dispersed mixed slurry of nano silica-base material, conductive black；
Step 2, polymerisation：Initiator isopropyl benzene hydroperoxide is added into the product of step 1, promotes polymer monomer
Generation polymerisation, the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 10% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 7, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：(mass ratio is for the elemental silicon, divinylbenzene, tetraethoxysilane that are 100nm by particle diameter：It is single
Matter silicon:Divinylbenzene：Tetraethoxysilane=90:4:1), (solid content is 20%) mediates after NMP mixing, revolves round the sun as 5
Turn/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By conductive black, polyvinylpyrrolidone, (mass ratio is to lead
Electric carbon black:Polyvinylpyrrolidone=4.9:0.1) and after NMP mixing (solid content is 10%) mediates, and revolves round the sun as 5 turns/min, from
Switch to 10 turns/min；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Conductive black=90:
4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 6h after obtain polymer monomer,
The dispersed mixed slurry of nano silica-base material, conductive black；
Step 2, polymerisation：Initiator cumyl peroxide is added into the product of step 1, promotes polymer monomer
Generation polymerisation, the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 90% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 8, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, mediate：(mass ratio is simple substance to the elemental silicon, divinylbenzene, tetraethoxysilane for being 100nm by particle diameter
Silicon:Divinylbenzene：Tetraethoxysilane=90:4:1), acetone mixing after (solid content is 20%) mediate, revolve round the sun for 5 turns/
Min, switchs to 10 turns/min certainly；Mediate 8h and obtain mixture 1；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive charcoal
It is black:Polyvinylpyrrolidone=4.9:0.1) and after acetone mixing (solid content is 10%) mediates, and revolves round the sun as 5 turns/min, rotation
For 10 turns/min；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is elemental silicon:Conductive black=90:
4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate 6h after obtain polymer monomer,
The dispersed mixed slurry of nano silica-base material, conductive black；
Step 2, pelletizing：(drying temperature is 60 DEG C to adjustable spraying drying condition, and now drying temperature is higher than acetone boiling point；
Less than divinylbenzene boiling point, in balling process, solvent will be vapored away, and polymer monomer is still distributed in nanometer once
Grain, conductive agent component surface), prepare the silicon-carbon second particle that particle diameter is 10 μm；
Step 3, polymerisation：The second particle that step 2 is obtained is placed in initiator dibenzoyl peroxide atmosphere, is promoted
Polymer monomer is set to occur polymerisation, the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 9, 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 20%) mediates after NMP mixing, revolution
For 5 turns/min, 10 turns/min is switched to certainly；Mediate 8h and obtain mixture 1；By graphene, polyoxyethylated alkyl phenol, (mass ratio is
Graphene:Polyoxyethylated alkyl phenol=4.9:0.1) and after NMP mixing (solid content is 5%) mediates, and revolves round the sun as 5 turns/min,
From switching to 10 turns/min；Mediate 8h and obtain mixture 2；By mixture 1, mixture 2, (mass ratio is the (sub- silicon+artificial stone of oxidation
Ink):Graphene=90:4.9) mix, continue to mediate, revolve round the sun as 5 turns/min, 10 turns/min is switched to certainly；Mediate after 6h
Obtain the scattered mixed slurry of polymer monomer, nano silica-base material, graphene uniform；
Step 2, polymerisation：The special butyl ester of initiator perbenzoic acid is added into the product of step 1, promotes polymer
Polymerisation occurs for monomer, and the polymer network structure of generation is coated on a nanometer primary particle, conductive black surface；
Step 3, pelletizing：Reaction to be polymerized there occurs after 50% that adjustable spraying drying condition prepares particle diameter
For 10 μm of silicon-carbon second particle；
It is other identical with embodiment 1, it is not repeated herein.
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 solid content, and matching is suitable to mediate stirring technique, can prepare the nanometer of premium properties
Silicon substrate second particle (worth battery core has excellent chemical property).But when solid content is too high, dispersion effect will be also influenceed,
So that material property declines.It can be obtained by embodiment 4, embodiment 6 and embodiment 7, the progress of polymerisation is too low during granulation
Or it is too high, will all it influence the chemical property of final material.Because when the degree of polymerization is excessive, polymer also has mobility, and
When the degree of polymerization is too high, by the viscosity of great increase slurry；Granule-morphology and structure when these situations all granulate influence, finally
Cause the degradation of material.It can be obtained by each embodiment, the present 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, it is characterised in that the silicon-carbon cathode material includes nuclear structure and shell structure, the core knot
Structure, which has, is dispersed in second particle structure tightly packed after conductive agent by nanometer primary particle, and the nanometer is once
Particle includes nano silicon-based particle；And between the nano silicon-based particle, it is between the conductive agent and described nano silicon-based
It is distributed with conductive network between particle and the conductive agent, and the conductive network and the nano silicon-based particle and described leads
Electric agent is closely connected.
2. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the conductive network is carbonized by high polymer material
Obtain；The high polymer material is distributed in before carbonization, uniformly between the nano silicon-based particle and the conductive agent, and
Together with the nano silicon-based particle is closely bonded with the conductive agent.
3. the silicon-carbon cathode material described in a kind of claim 2, it is characterised in that the high polymer material is former by high polymer monomer
Position polymerize and obtained.
4. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the nano silicon-based particle is simple substance silicon grain
Or/and silicon oxide particles；The conductive agent includes conductive black, super conductive carbon, Ketjen black, CNT, graphene, second
At least one of conductive network that acetylene black, high polymer material carbonization are obtained；The primary particle also includes non-nano silicon substrate and born
Pole particle；The non-nano silicon-based anode particle is native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, oil
Jiao, carbon fiber, thermal decomposed resins carbon, lithium carbonate, tin base cathode material, transition metal nitride, kamash alloy, germanium-base alloy, aluminium
At least one of based alloy, 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, mediate：Mediated after component at least containing nanometer primary particle and polymer monomer is mixed so that polymer
Monomer is uniformly scattered in a nanometer primary particle surface, obtains precursor pulp；
Step 2, polymerisation：Initiator is added into the product of step 1, promotes polymer monomer to occur polymerisation, generation
Polymer network structure be coated on the surface of nanometer primary particle；
Step 3, pelletizing：The product that step 2 to a certain extent is obtained occurs for selective polymerization reaction, carries out pelletizing, obtains secondary
Particle；
Step 4, prepared by silicon-carbon cathode：The product that step 3 is obtained is coated, is carbonized, that is, 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 2
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
Nano silicon-based particle is included in particle；Also include non-nano silicon-based anode particle in the nanometer primary particle；Mediated in step 1
At least one of high molecular polymer, carbon source component, conductive agent component and solvent composition have been additionally added during reaction.
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；Conductive agent, surface are lived
Property agent, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and obtains precursor pulp.
9. a kind of preparation method of the silicon-carbon cathode material described in claim 5, it is characterised in that polymerisation described in step 3
Generation refers to that polymerisation has carried out 10%~90% to a certain extent.
10. the preparation method of the silicon-carbon cathode material described in a kind of claim 5, it is characterised in that first carried out after mediating reaction
Pelletizing, then polymerisation is carried out, silicon-carbon cathode preparation is finally carried out again, i.e.,：
Step 2, pelletizing：The precursor pulp obtained using step 1, is carried out pelletizing, obtains second particle；
Step 3, polymerisation：The second particle that step 2 is obtained is placed in the environment of initiator presence, promotes polymer monomer
Generation polymerisation, the polymer network structure of generation is coated on a nanometer primary particle surface.
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| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN109817962A (en) * | 2019-04-02 | 2019-05-28 | 福建蓝海黑石新材料科技有限公司 | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method of phenolic resin modification |
| CN111342021A (en) * | 2020-03-12 | 2020-06-26 | 谈益 | Preparation method of carbon cathode slurry |
| CN111740090A (en) * | 2020-07-06 | 2020-10-02 | 江西理工大学 | Synthetic method for improving conductivity of silicon-based negative electrode material |
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| CN104362300A (en) * | 2014-12-02 | 2015-02-18 | 南京工业大学 | Preparation method of silicon-carbon composite negative electrode material of lithium ion battery and application of silicon-carbon composite negative electrode material |
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| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN109728281B (en) * | 2018-12-31 | 2021-10-12 | 青岛农业大学 | Preparation method of surface modified SiOx electrode material |
| CN109817962A (en) * | 2019-04-02 | 2019-05-28 | 福建蓝海黑石新材料科技有限公司 | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method of phenolic resin modification |
| CN111342021A (en) * | 2020-03-12 | 2020-06-26 | 谈益 | Preparation method of carbon cathode slurry |
| CN111342021B (en) * | 2020-03-12 | 2021-04-02 | 宇恒电池有限公司 | Preparation method of carbon cathode slurry |
| CN111740090A (en) * | 2020-07-06 | 2020-10-02 | 江西理工大学 | Synthetic method for improving conductivity of silicon-based negative electrode material |
| CN111740090B (en) * | 2020-07-06 | 2022-09-16 | 江西理工大学 | Synthetic method for improving conductivity of silicon-based negative electrode material |
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