CN106920949A - Silicon-carbon cathode material and preparation method thereof - Google Patents
Silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- CN106920949A CN106920949A CN201710270902.0A CN201710270902A CN106920949A CN 106920949 A CN106920949 A CN 106920949A CN 201710270902 A CN201710270902 A CN 201710270902A CN 106920949 A CN106920949 A CN 106920949A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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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- H—ELECTRICITY
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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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- 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
- H01—ELECTRIC ELEMENTS
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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, 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；There is stronger chemical bond between the leading network structure and power is acted on；Closely be locked in the nanometer primary particle in the pore structure of the leading electric network by the chemical bond.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 with its specific energy it 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 is brought to energy storage field, be widely used in various portable electric appts and electronic
In automobile.However as the improvement of people's living standards, Consumer's Experience higher proposes requirement higher 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.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 due to silicon materials electric conductivity is poor in itself and charge and discharge process in volumetric expansion it is big and easily cause material knot
Structure is destroyed and mechanical crushing, causes its cycle performance to be decayed fast, limits its wider application.In order to solve the above problems,
Prior art mainly has silicon grain nanosizing, has conductive material of excellent conductive capability etc. to addition in silica-base material particle
Deng the electric conductivity for improving silica-base material integral particle, while solving silica-base material machinery powder in material charge and discharge process
Broken the problems such as.
But the based particles of nanostructured are easily reunited, dispersion difficulty is big；And conventional conductive agent material, general size
Smaller (nanoscale), and specific surface area is larger, dispersion difficulty is bigger；Simultaneously in charge and discharge process, the huge body of based particles
Product change, huge impact is produced to silicon-carbon cathode grain structure stability.But when, to maximize the conductive effect of conductive agent with
And the more excellent silicon substrate second particle material of processability, it is necessary to ensure that nano silicon-based particle and conductive agent be dispersed, with
And the stability of silicon carbon material structure.Meanwhile, the bonding force between nanostructured silica-base material and conductive agent is weaker, swollen in volume
Two kinds separated is easily lead to during swollen, 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 difficult by two kinds of dispersions
The larger material (nano silicon-based particle, conductive agent) of degree is dispersed, while ensuring to be closely joined together between the two (i.e.
Silicon carbon material structural stability), so as to 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 for providing, 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；There is stronger change between the leading network structure
Learn key and power effect；The nanometer primary particle is closely locked in the chemical bond pore structure of the leading electric network
In.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；
There is stronger chemical bond between the leading network structure and power is acted on；The chemical bond is tight by the nanometer primary particle
Be locked in the pore structure of the leading electric network.Shell structure refers to the general clad of negative material, predominantly pitch etc.
Material cladding, carbonization are obtained, therefore the present invention is not set forth in detail.
As silicon-carbon cathode material of the present invention one kind improve, there is provided the key classification that the strong bond is made a concerted effort be hydrogen bond or/and
Chemical bond；Constitute the hydrogen bond or/and chemical bond oxygen-containing functional group quality account for whole leading electric network architecture quality 1%~
40%.
Improved as one kind of silicon-carbon cathode material of the present invention, the leading electric network has pliability, dominate electric network
Contain functional group in inside；The hydrogen bond or/and chemical bond are obtained by the leading electric network inside oxygen-containing functional group reaction.
As silicon-carbon cathode material of the present invention one kind improve, the leading electric network structure be opening graphene-structured,
At least one in opening intumesced graphite structure, quasiflake graphite alkene structure；The primary particle includes nano silicon-based negative pole
Particle；Between the leading electric network and the primary particle, guidance electric network can also be distributed with, the guidance electric network will
The leading electric network is closely joined together with the nanometer primary particle.
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 primary particle can also include non-nano silicon-based anode particle；The non-nano silicon-based anode
Grain for native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate,
In tin base cathode material, transition metal nitride, kamash alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy
It is at least one；The guidance electric network is obtained by macromolecular material carbonization；The macromolecular material is by high molecular polymer monomer
In-situ polymerization and obtain；In the guidance electric network, conductive black, super conductive carbon, Ketjen black, carbon nanometer can also be included
At least one in pipe, Graphene, acetylene black；
Present invention additionally comprises a kind of preparation method of silicon-carbon cathode material, it is characterised in that mainly comprise the following steps：
It is prepared by step 1, presoma：Primary particle is uniformly scattered in solvent, presoma is obtained；
It is prepared by step 2, the leading electric network structure that is modified：Leading electric network structure with loose structure is placed in oxidation ring
In border, grafted functional group obtains modified leading electric network structure；
Step 3, filling：Presoma obtained in step 1 is filled into modified leading electric network structure；
Step 4, remains silent：It is placed under reducing atmosphere, promotes the functional group being grafted in leading electric network structure to react,
Generation strong bond is made a concerted effort, and the pore structure sealing in porous leading electric network structure or part are sealed；
Step 5, the product of step 4 is coated, is carbonized the finished silicon carbon negative pole material that obtain.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the primary particle surface described in step 1 is passed through
It is modified, it is function dough primary particle, the functional group is carboxyl or/and hydroxyl；The functional group being grafted described in step 2 includes carboxylic
At least one in base, hydroxyl, epoxy radicals, carbonyl, nitro, amino；Reducing environment described in step 4 include addition reducing agent or/
Reduced with Direct Hydrothermal.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, polymer monomer can also be added in step 1,
Will be mediated after primary particle, polymer monomer mixing, obtain polymer monomer and be uniformly scattered in a nanometer primary particle surface
Presoma；At this time, it may be necessary to carry out polymerisation after step 3, the polymerisation is, by the product of step 3, to be placed in and draw
In the environment that hair agent is present, promote the polymer monomer for being scattered in primary particle surface to be polymerized, obtain high molecular polymer.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, included in nanometer primary particle described in step 1
There is nano silicon-based particle；Non-nano silicon-based anode particle can also be included in the nanometer primary particle；May be used also when mediating reaction
To add high molecular polymer, carbon source component, conductive agent component, solvent composition；Now kneading process described in step 1 is：To receive
Rice primary particle, silane coupler, polymer monomer, solvent 1 are mediated, and obtain mixture 1；By conductive agent component, surface-active
Agent, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and is obtained precursor pulp.
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 is vacuumized, in exclusion 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, 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 in 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
Lauroyl, perbenzoic acid spy butyl ester, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate, the carbon of peroxidating two
At least one in sour dicyclohexyl maleate.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, included in nanometer primary particle described in step 1
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 in 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, the described carbon source component in sodium carboxymethylcellulose (CMC), polypropylene fine (PAN) includes 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 in acetylene black, water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, two
At least one in ethyl-formamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran.
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 opening graphene-structured, opening intumesced graphite structure and quasiflake graphite alkene structure：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 for linking together), it is heat-treated afterwards expanded, you can
Obtain the loose structure that lamella between same coccolith ink links together, is open between lamella and lamella；Afterwards again as oxidation
Grafted functional group in environment, obtains modified leading electric network structure
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the silane coupler is coupled for alkyl silane
The coupling of agent, amino silicane coupling agent, alkenyl silane coupling agent, epoxyalkylsilane coupling agent and alkyl acyloxy silane
At least one in agent；The solvent 1 is water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethyl
At least one in acid amides, DEF, dimethyl sulfoxide (DMSO) and tetrahydrofuran.The surfactant is surfactant
Comprising at least one in wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent；The solvent 2 be water, alcohols,
Ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethylformamide, DEF, dimethyl sulfoxide (DMSO) and tetrahydrochysene
At least one in furans.
The advantage of the invention is that：
1. it is modified and dominates between electric network structure and modified primary particle, with similar functional group, is more beneficial for once
Granuloplastic presoma enters in the pore structure of leading electric network；Being sufficient filling with for pore structure is realized, primary particle is improved and is existed
Proportion in Si-C composite material；
2. bonding action power stronger between leading electric network inside configuration lamella, effectively can seal primary particle
In leading electric network inside configuration, it is ensured that in charge and discharge process, primary particle is without departing from leading electric network structure；It is simultaneously stronger
Bonding force also ensure that the stability of leading electric network structure self structure, so that it is guaranteed that dominating electric network in cyclic process
Structure itself will not avalanche；
3. teach electric network structure that leading electric network structure is closely connected 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；
4. in preparation process, kneading dispersion is carried out using the low polymer monomer of viscosity and nanometer primary particle, can be true
Protect nanometer primary particle dispersed, and polymer monomer is uniformly distributed in a nanometer primary particle surface；
5. there is the presoma of more low viscosity (because polymer monomer viscosity is low), it is easier to be filled into leading electric network
Pore structure in, it is ensured that fill up a nanometer primary particle in the hole of the loose structure of leading electric network.
Specific embodiment
The present invention and its advantage are described in detail with reference to specific embodiment, but embodiment party of the invention
Formula not limited to this.
Comparative example, prepares the silicon-carbon second particle material that particle diameter is 10 μm；
Step 1, mixing：It is elemental silicon, polymethyl methacrylate, conductive black, the tetraethoxy-silicane of 100nm by particle diameter
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 (solid content is 0.5%) mix 10h, obtain slurry.
It is prepared by step 2, 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：
It is prepared by step 1, presoma：It is elemental silicon, methyl methacrylate, the tetraethoxysilane (matter of 100nm by particle diameter
Amount is than being elemental silicon:Methyl methacrylate：Tetraethoxysilane=95:4:1), (solid content is 10%) pinches after NMP mixing
Close, it is 30 turns/min to revolve round the sun, and 300 turns/min is switched to certainly；Mediate 4h and obtain elemental silicon, methyl methacrylate, tetraethoxy-silicane
The dispersed presoma of alkane；
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 1% functional group
Modified quasiflake graphite alkene is stand-by；
Step 3, filling：The modified quasiflake graphite alkene that step 2 is obtained is vacuumized, the presoma of step 1 is placed in afterwards
In, apply pressure in drive body further along, while ultrasonic vibration so that presoma is inserted in the pore structure of quasiflake graphite alkene, point
From the modified quasiflake graphite alkene for obtaining filling full presoma；
Step 4, polymerisation：Dispersion obtains solution during perbenzoic acid spy's butyl ester is dissolved in into NMP, and step is sprayed onto afterwards
The modified quasiflake graphite alkene surface of the rapid 3 full presomas of the filling for obtaining, heating promotes to be scattered in the first of elemental silicon particle surface
Base methyl acrylate is polymerized, together with simple substance silicon grain is closely bonded with modified quasiflake graphite alkene lamella；
Step 5, remains silent：The product that step 4 is obtained, carries out solvent thermal reaction, promotes to be grafted on quasiflake graphite alkene piece
Functional group on layer (between adjacent sheets) reacts, and generates new chemical bond, will be sealed at quasiflake graphite alkene lamella opening
Firmly；
Step 6, the product of step 5 is coated, is carbonized (while by clad and polymer carbonization) and is obtained finished product
Silicon-carbon cathode material.
Embodiment 2, difference from Example 1 is that the present embodiment comprises the following steps：
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 5% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 3, difference from Example 1 is that the present embodiment comprises the following steps：
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 15% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 4, difference from Example 1 is that the present embodiment comprises the following steps：
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 20% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 5, difference from Example 1 is that the present embodiment comprises the following steps：
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 25% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 6, difference from Example 1 is that the present embodiment comprises the following steps：
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 40% functional group
Modified quasiflake graphite alkene is stand-by；
Remaining is same as Example 1, repeats no more.
Embodiment 7, difference from Example 1 is that the present embodiment comprises the following steps：
It is prepared by step 1, presoma：Be the modified elemental silicon (surface hydroxylation) of 100nm by particle diameter, NMP mix after (Gu
Content is 10%) to mediate, and it is 30 turns/min to revolve round the sun, and 300 turns/min is switched to certainly；It is dispersed that kneading 4h obtains nano simple substance silicon
Precursor pulp；
It is prepared by step 2, the leading electric network structure of the quasiflake graphite alkene that is modified：Selection micro crystal graphite is raw material, is added afterwards
The concentrated sulfuric acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and quasiflake graphite alkene is thermally treated resulting in afterwards；By vermiform
Graphene is placed in the mixture of the concentrated sulfuric acid, potassium permanganate, sodium nitrate and it is modified, and obtains being grafted with 20% functional group
Modified quasiflake graphite alkene is stand-by；
Step 3, filling：The modified quasiflake graphite alkene that step 2 is obtained is vacuumized, the presoma of step 1 is placed in afterwards
In, apply pressure in drive body further along, while ultrasonic vibration so that presoma is inserted in quasiflake graphite alkene pore structure, separate
Obtain filling the modified quasiflake graphite alkene of full presoma；
Step 4, remains silent：The product that step 3 is obtained, carries out solvent thermal reaction, promotes to be grafted on quasiflake graphite alkene piece
Functional group on layer (between adjacent sheets) reacts, and generates new chemical bond, will be sealed at quasiflake graphite alkene lamella opening
Firmly；
Step 5, the product of step 4 is coated, is carbonized (while by clad and polymer carbonization) and is obtained finished product
Silicon-carbon cathode material.
Remaining is same as Example 1, repeats no more.
Embodiment 8, difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, mediates：By particle diameter, for the sub- silicon+Delanium of the oxidation of 100nm, (mass ratio is the sub- silicon of oxidation: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 it is 5 turns/min to revolve round the sun, and 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, it is 5 turns/min to revolve round the sun, and 10 turns/min is switched to certainly；Polymer monomer is obtained after kneading 6h to be uniformly wrapped on once
Particle (the sub- silicon of oxidation and Delanium) surface, polymer monomer and graphene uniform dispersion, Graphene and primary particle are uniform
Scattered presoma；
It is prepared by step 2, the leading electric network structure of modified expanded graphite：Selection crystalline flake graphite is raw material, and dense sulphur is added afterwards
Acid, potassium permanganate carry out oxidation intercalation, obtain graphite oxide, and expanded graphite is thermally treated resulting in afterwards；Expanded graphite is placed in dense
It is modified in sulfuric acid, potassium permanganate, the mixture of sodium nitrate, obtains being grafted with the modified expanded graphite of 20% functional group
Leading electric network structure is stand-by；
Step 3, filling：The leading electric network structure of modified expanded graphite that step 2 is obtained is vacuumized, and step is placed in afterwards
In 1 presoma, apply pressure in drive body further along, while ultrasonic vibration so that presoma is inserted modified expanded graphite and dominated
In electric network pore structure, the leading electric network structure of modified expanded graphite of the isolated full presoma of filling；
Rapid 4, polymerisation：Dispersion obtains solution during perbenzoic acid spy's butyl ester is dissolved in into NMP, and step is sprayed onto afterwards
The modified expanded graphite surface of the 3 full presomas of the filling for obtaining, heating promotes to be scattered in the methacrylic acid on primary particle surface
Methyl esters is polymerized, together with primary particle is closely bonded with modified expanded graphite lamella；
Step 5, remains silent：To reducing agent is added in the product that step 4 is obtained, promote to be grafted on modified expanded graphite lamella
Functional group in (between adjacent sheets) reacts, and generates new chemical bond, will be sealed at modified expanded graphite lamella opening；
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 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, D1 obtains negative pole gram volume divided by the weight of silicon carbon material in negative electricity pole piece, and acquired results are shown in Table 1.
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 to each embodiment and comparative example silicon carbon material by following flow in 25 DEG C of environment
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；Stand 3min " 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, be with the silicon-carbon cathode material
The battery core that negative electrode active material assembling is obtained has excellent chemical property.Specifically, comparative examples and embodiment 1- realities
Applying example 6 can obtain, and with the increase of the oxygen-containing functional group on modified leading electric network frame sheet, material capacity first keeps constant,
Sharp-decay, keeps constant after the first gradually lifting of cycle performance afterwards, and high rate performance first keeps constant rear sharp-decay；There is this
The reason for planting phenomenon is that, when oxygen-containing functional group is very few, can only remain silent reaction seldom, therefore cannot be played effectively
Leading electric network Stability Analysis of Structures effect；When oxygen-containing functional group is excessive, remain silent when reacting, the aperture of loose structure will be more
Be closed until block, so as to influence the transmission of ion；The dynamic performance of material is caused to be decayed.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 specific embodiment, every those skilled in the art exist
On the basis of of the invention it is done it is any conspicuously improved, replace or modification belongs to protection scope of the present invention.This
Outward, 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；There is stronger bonding force between the leading electric network to act on；And by the bonding force by the nanometer
Primary particle is closely locked in the pore structure of the leading electric network.
2. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the classification for providing the key that strong bond is made a concerted effort is hydrogen bond
Or/and chemical bond；The quality for constituting the oxygen-containing functional group of the hydrogen bond or/and chemical bond accounts for the whole quality for dominating electric network
1%~40%.
3. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the leading electric network has pliability, and
Contain functional group inside the leading electric network；The hydrogen bond or/and chemical bond are by the oxygen-containing official inside the leading electric network
Reaction can be rolled into a ball and obtained.
4. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the leading electric network is opening Graphene knot
At least one in structure, opening intumesced graphite structure, quasiflake graphite alkene structure；The nanometer primary particle includes nano-silicon
Base negative pole particle；Guidance electric network, the guidance electric network are also distributed between the leading electric network and the primary particle
The leading electric network is closely joined together with the nanometer primary particle.
5. the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that the nano silicon-based negative pole particle is nano-silicon
Particle or/and nanometer silicon oxide particles；The primary particle also includes non-nano silicon-based anode particle；The non-nano silicon substrate
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 in gold；The guidance electric network is obtained by macromolecular material carbonization；The macromolecular material is by high polymer monomer
In-situ polymerization is obtained；In the guidance electric network, also including conductive black, super conductive carbon, Ketjen black, CNT, graphite
At least one in alkene, acetylene black.
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：
It is prepared by step 1, presoma：Primary particle is uniformly scattered in solvent, presoma is obtained；
It is prepared by step 2, the leading electric network structure that is modified：Leading electric network structure with loose structure is placed in oxidation environment
In, grafted functional group obtains modified leading electric network structure；
Step 3, filling：Presoma obtained in step 1 is filled into modified leading electric network structure；
Step 4, remains silent：It is placed under reducing atmosphere, promotes the functional group being grafted in leading electric network structure to react, generates
Strong bond is made a concerted effort, and the pore structure sealing in porous leading electric network structure or part are sealed；
Step 5, the product of step 4 is coated, is carbonized the finished silicon carbon negative pole material that obtain.
7. the preparation method of the silicon-carbon cathode material described in a kind of claim 6, it is characterised in that described in step 1 once
Grain surface turns into functional group's primary particle by modified, and the functional group is carboxyl or/and hydroxyl；It is grafted described in step 2
Functional group includes at least one in carboxyl, hydroxyl, epoxy radicals, carbonyl, nitro, amino；Reducing environment described in step 4 includes adding
Plus reducing agent or/and Direct Hydrothermal reduction.
8. the preparation method of the silicon-carbon cathode material described in a kind of claim 6, it is characterised in that be also added with step 1 poly-
Monomer adduct, will mediate after primary particle, polymer monomer mixing, obtain polymer monomer and be uniformly scattered in nanometer once
The presoma of particle surface；At this time, it may be necessary to carry out polymerisation after step 3, the polymerisation is by the product of step 3
Thing, is placed in the environment of initiator presence, promotes the polymer monomer for being scattered in primary particle surface to be polymerized, and obtains polyphosphazene polymer
Compound.
9. the preparation method of the silicon-carbon cathode material described in a kind of claim 8, 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；Now kneading process described in step 1 is：
Nanometer primary particle, silane coupler, polymer monomer, solvent 1 are mediated, mixture 1 is obtained；By conductive agent component, surface
Activating agent, solvent 2 are mediated, and obtain mixture 2；Mixture 1 is blended with mixture 2 again, is uniformly dispersed and is obtained precursor pulp.
10. a kind of preparation method of the silicon-carbon cathode material described in claim 6, it is characterised in that the filling described in step 3
Cheng Wei：
Porous leading electric network structural material is pre-processed, the pretreatment includes surface active or/and addition surface-active
Agent；
Before filling, porous leading electric network structural material is placed in vacuum environment and is vacuumized, the air in discharge pore structure,
It 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, opens hole mouthful.
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