CN107086297A - A kind of preparation method of silicon-carbon cathode material and the silicon-carbon cathode material prepared using this method - Google Patents

A kind of preparation method of silicon-carbon cathode material and the silicon-carbon cathode material prepared using this method Download PDF

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Publication number
CN107086297A
CN107086297A CN201710271222.0A CN201710271222A CN107086297A CN 107086297 A CN107086297 A CN 107086297A CN 201710271222 A CN201710271222 A CN 201710271222A CN 107086297 A CN107086297 A CN 107086297A
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silicon
cathode material
carbon cathode
graphite
carbon
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毛方会
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Guangdong Candle Light New Energy Technology Co Ltd
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Guangdong Candle Light New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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Abstract

The invention belongs to energy storage research field, more particularly to a kind of silicon-carbon cathode material preparation method, methods described mainly includes step 1, and power source material 1, silicon nanoparticle, graphite particle is dry-mixed, until well mixed;Step 2, add and continue to mix after electrolyte 1, form ion channel, now in the presence of power source material, graphite particle will be peeled off, form graphite flake layer hatch frame;Under the active force of mixing, silicon nanoparticle constantly will be filled into the hatch frame of graphite flake layer;Or step 1 ', silicon nanoparticle, graphite particle, electrolyte 2 are well mixed stand-by;The product assembling paired electrode that step 2 ', by power source material 2 and step 1 ' is obtained, applies electric current, graphite particle is peeled off between electrodes, formation graphite flake layer hatch frame;Silicon nanoparticle constantly will be filled into the hatch frame of graphite flake layer afterwards;Step 3, after the completion of filling, electrolyte component is removed, is coated, is carbonized, obtain silicon-carbon cathode material.When preparing silicon-carbon cathode using this method simultaneously, it is possible to achieve graphite particle lamella opening is filled with nano silicon particles and carried out so that filling carries out more smooth, so that it is guaranteed that the silicon-carbon cathode material has excellent chemical property.

Description

A kind of preparation method of silicon-carbon cathode material and the silicon-carbon prepared using this method Negative material
Technical field
The invention belongs to energy storage material technical field, the preparation method of more particularly to a kind of silicon-carbon cathode material and use should The silicon-carbon cathode material that method is prepared.
Background technology
Lithium ion battery is so that its specific energy is big, operating voltage is high, self-discharge rate is small, small volume, the advantage such as lightweight, from it Since birth, revolutionary change just has been brought to energy storage field, is widely used in various portable electric appts and electronic In automobile.However as the improvement of people's living standards, higher Consumer's Experience proposes higher requirement to lithium ion battery: Quality is lighter, use time is longer etc.;The more excellent electrode material of new performance is had to look for solve the above problems.
Current commercialized lithium ion battery negative material is mainly graphite, but because its theoretical capacity is only 372mAhg-1, the active demand of user can not be met;Therefore, the exploitation of the negative material of more height ratio capacity is extremely urgent.It is used as lithium ion Cell negative electrode material, silicon materials receive much concern always.Its theoretical capacity is 4200mAhg-1, it is the graphite capacity having been commercialized More than 10 times, it is and relatively inexpensive, environment-friendly etc. excellent with low intercalation potential, low atomic wts, high-energy-density, price One of gesture, therefore be the optimal selection of high-capacity cathode material of new generation.
But be due to that silicon materials electric conductivity itself is poor and in charge and discharge process volumetric expansion it is big and easily cause material knot Structure is destroyed and mechanical crushing, causes the decay of its cycle performance fast, is limited it and is widely applied.In order to solve the above problems, Prior art mainly has silicon grain nanosizing, conductive material with excellent conductive capability etc. is added into silica-base material particle Deng the electric conductivity for improving silica-base material integral particle, while solving the mechanical powder of silica-base material in material charge and discharge process Broken the problems such as.
But the based particles of nanostructured are easily reunited, disperse difficulty big;And conventional conductive agent material, general size Smaller (nanoscale), and specific surface area is larger, scattered difficulty is bigger;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 preparation method of silicon-carbon cathode material and use what this method was prepared Silicon-carbon cathode material, it can be dispersed by the larger material (nano silicon-based particle, conductive agent) of two kinds of scattered difficulty, together When ensure to be closely joined together (i.e. silicon carbon material structural stability) between the two, so as to prepare the silicon-carbon of function admirable Negative material.
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 preparation method provided, Methods described mainly includes step 1, and power source material 1, silicon nanoparticle, graphite particle is dry-mixed, until well mixed;Step 2, add after electrolyte 1 and continue to mix, form ion channel, now in the presence of power source material, graphite particle will be entered Row is peeled off, and forms graphite flake layer hatch frame;Under the active force of mixing, silicon nanoparticle will constantly be filled into graphite flake layer Hatch frame in;
Or
Step 1 ', silicon nanoparticle, graphite particle, electrolyte 2 are well mixed stand-by;Step 2 ', by power source material 2 With step 1 ' obtained product assembling paired electrode, apply electric current between electrodes, graphite particle is peeled off, formation stone Ink sheet layer hatch frame;Silicon nanoparticle constantly will be filled into the hatch frame of graphite flake layer afterwards;
Step 3, after the completion of filling, electrolyte component is removed, is coated, is carbonized, obtain silicon-carbon cathode material.
When preparing silicon-carbon cathode using this method, it is possible to achieve graphite particle lamella opening is filled simultaneously with nano silicon particles Carry out so that filling carries out more smooth, 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 preparation method of silicon-carbon cathode material, mainly comprises the following steps:
Step 1, it is power source material 1, silicon nanoparticle, graphite particle is dry-mixed, until well mixed;
Step 2, add and continue to mix after electrolyte 1, form ion channel, will now in the presence of power source material Graphite particle is peeled off, graphite flake layer hatch frame is formed;Under the active force of mixing, silicon nanoparticle will be filled constantly Into in the hatch frame of graphite flake layer;
Or
Step 1 ', silicon nanoparticle, graphite particle, electrolyte 2 are well mixed stand-by;
The product assembling paired electrode that step 2 ', by power source material 2 and step 1 ' is obtained, applies electricity between electrodes Stream, is peeled off to graphite particle, forms graphite flake layer hatch frame;Silicon nanoparticle will constantly be filled into graphite flake afterwards In the hatch frame of layer;
Step 3, after the completion of filling, electrolyte component is removed, is coated, is carbonized, obtain silicon-carbon cathode material.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, power source material 1 is pre- described in step 1 Embedding lithium titanate cathode material (such as lithium intercalated graphite, embedding lithium silica-base material, rich lithium material) or/and metal lithium material.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, electrolyte 1 described in step 2 includes Solute and solvent, the solvent include graphite intercalation or/and peel off function ingredients;Step 1 ' described in electrolyte 2 include Solute and solvent, the solvent include graphite intercalation or/and peel off function ingredients.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the solute is electrolysed for lithium ion battery Liquid solute;Include alkali metal, alkali earth metal, metal chloride (such as ZrCl4, CrCl3, CoCl3 in the solvent Deng), chloride (such as MoF6, WF6 etc.), rare earth element (such as Sm, Eu, Tm, Yb etc.), halogens (such as F, Cl etc.), counterfeit halogen At least one of (such as Br2, ICl, IF5 etc.), strong acid (such as H2SO4, HNO3), propene carbonate.
Be used as a kind of improvement of silicon-carbon cathode material preparation method of the present invention, step 2 ' described in power source material 2 include rich lithium material or/and the metallics as electrode material;The rich lithium material includes LiM1O2、LiMn2-XM2xO4、 LiNixM31-xO2、Li3-xM4xN、LiFePO4、Li2FeO4、Li7-xMnxN4、Li3-xFexN2、Li2S、Li2S2And LiNixMnyCozO2 At least one of, wherein, M1 is at least one of Co, Ni, Mn, Cu, Cr and Fe, and M2 is in Ni, Co, Cu, Cr, Fe and V At least one, M3 is at least one of Co, Mn, Cu, Cr, Fe, V, La, Al, Mg, Ga and Zn, M4 be Co, Ni, Cu, Cr and At least one of V, x+y+z=1, x, y, z are not less than zero;The metallics as electrode material include lithium metal, At least one of metallic sodium, metallic potassium, magnesium metal, metallic aluminium, metallic zinc.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, can also be to step 1 or step 1 ' in Silane coupler, surface reactive material, conductive agent component, non-silicon-based negative pole nano particle are added (it is required that it is not by power source thing Matter is peeled off);
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, the surface reactive material includes;Institute Stating silane coupler described in silane coupler includes including VTES, methyl trimethoxy epoxide for silane coupler Silane, tetraethoxysilane, vinyltrimethoxy silane, methylvinyldimethoxysilane, γ-methacryloxy Propyl trimethoxy silicane, methacryloyloxypropyl methyl dimethoxysilane, γ aminopropyltriethoxy silane, γ mercaptopropyitrimethoxy silane, γ-cyanopropyl trimethoxy silane, γ-glycidoxypropyltrimethoxy base silicon Alkane, β-(3,4- epoxycyclohexyl) at least one of ethyl trimethoxy silane and γ-ureido-propyl trimethoxy silane; The surfactant includes at least one of wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent;It is described Conductive agent component includes at least one of super conductive carbon, acetylene black, CNT, Ketjen black, conductive carbon black;The non-silicon Base negative pole nano particle includes native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, pyrolysis At least one of resin carbon, lithium carbonate, non-silicon alloy material of cathode.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, can also be to step 1 or step 1 ' in Add polymer monomer;Now, it is necessary to trigger monomer to polymerize after completion is filled, step 3 is carried out again afterwards.
Improved as one kind of silicon-carbon cathode material preparation method of the present invention, polymer monomer includes acrylate Class, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol dimethacrylate, polyethylene glycol two Acrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl methacrylate, N, N- dimethyl allenes Acid amides, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate, positive Hexyl 2-propenoate, 2- acrylates Ester, dodecyl acrylate, GDMA, polyethylene glycol dimethacrylate, polyethylene glycol dimethyl propylene Olefin(e) acid ester, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol Diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythritol acrylate, double-Glycerin 4 third Olefin(e) acid ester, pentaerythritol triacrylate, trimethylol-propane trimethacrylate, glycerol propoxylate triacrylate, three (2- ethoxys) isocyanuric acid triacrylate trimethylolpropane trimethacrylate, propoxylation trimethylolpropane tris propylene Acid esters, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylation three At least one of hydroxymethyl-propane triacrylate, tetramethylol methane tetraacrylate;Initiator, institute are added in the initiation reaction State initiator 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.
Present invention additionally comprises a kind of silicon-carbon cathode material, the silicon-carbon cathode material, including nuclear structure and shell structure are described Nuclear structure is second particle structure, and including the leading electric network with loose structure and is filled in described porous leading Nanometer primary particle in electric network pore structure;The leading electric network is that graphite part stripping is obtained, between graphite flake layer Opening and the loose structure linked together between lamella and lamella;Between the leading electric network and the nanometer primary particle It is closely joined together.
The advantage of the invention is that:
1. being peeled off using electrochemical method to graphite particle, the porous graphite being open between lamella is obtained;Electrochemistry Stripping means is more gentle, is easily controlled extent of exfoliation (by controlling to peel off the progress such as electric current, splitting time accurately control), really Do not come off again by thorough stripping while stripping out opening between guarantor's graphite flake layer;
2. prepare silicon-carbon cathode using the inventive method, it is possible to achieve graphite particle lamella opening is filled out with nano silicon particles Fill and carry out simultaneously, i.e., graphite flake layer opening a bit, fill a bit by nano silicon particles;This fill method can prevent filling process Graphite flake layer is inwardly bent and folds into and cause hole channel blockage not to be sufficient filling with by middle nano particle;Therefore it is filled into It is capable more smoothly and to fill more abundant, so that it is guaranteed that the silicon-carbon cathode material has excellent chemical property;
3. the present invention can also use the low-down high polymer monomer of viscosity as the reactant of dispersed with stirring, can be very big Reduction disperse difficulty so that high polymer monomer is dispersed in a nanometer primary particle surface;
, can be by nanometer once 4. 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.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the embodiment party of the present invention Formula not limited to this.
Comparative example, prepares the silicon-carbon second particle material that particle diameter is 10 μm;
Step 1, mix:By elemental silicon, polymethyl methacrylate, conductive black, the tetraethoxy-silicane that particle diameter is 100nm Alkane, polyvinylpyrrolidone are so that (mass ratio is elemental silicon:Polymethyl methacrylate:Conductive black:Tetraethoxysilane:It is poly- Vinylpyrrolidone=90:4:4.9:1:0.1) and NMP (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, it is metallic lithium powder, a diameter of 100nm elemental silicon, particle diameter is dry-mixed for 6 μm of graphite particle, until It is even;
Step 2, selection lithium hexafluoro phosphate be salt, the electrolyte that PC is solvent, add said mixture in continue stir, this When in the presence of metallic lithium powder, PC will be peeled off to graphite particle, formed hatch frame, while simple substance silicon grain will fill Into in mouth structure;
Step 3, after the completion of filling, electrolyte component is removed, is coated, is carbonized, obtain silicon-carbon cathode material.
Remaining is identical with comparative example, repeats no more.
Embodiment 2, is that the present embodiment comprises the following steps with comparative example difference:
Step 1, it is that salt PC is molten by graphite particle that a diameter of 100nm elemental silicon, particle diameter are 6 μm, lithium hexafluoro phosphate The electrolyte mixer kneader of agent, until uniform;
Step 2, by power source material of LiFePO4, assembling is to electrode, and the material composition obtained afterwards with step 1 is to electricity Pole, connects external circuit, is charged using 1A electric current, graphite particle is peeled off, form graphite flake layer hatch frame;Receive afterwards Rice silicon grain constantly will be filled into the hatch frame of graphite flake layer;
Step 3, after the completion of filling, electrolyte component is removed, is coated, is carbonized, obtain silicon-carbon cathode material.
Remaining is identical with comparative example, repeats no more.
Embodiment 3, difference from Example 1 is, the present embodiment comprises the following steps:
Step 1, by metallic lithium powder, a diameter of 100nm elemental silicon, methyl methacrylate, tetraethoxysilane, particle diameter Mediated for 6 μm of graphite particles are dry-mixed, until uniform;
Step 2, selection lithium hexafluoro phosphate be salt, the electrolyte that PC is solvent, add said mixture in continue stir, this When in the presence of metallic lithium powder, PC will be peeled off to graphite particle, formed hatch frame, while simple substance silicon grain will fill Into in hatch frame;
Step 3, the special butyl ester of perbenzoic acid is dissolved in PC and forms initiator solution, treat the filling described in step 3 After the completion of, add initiator solution, improve temperature, promote polymer monomer occur polymerisation, simple substance silicon grain with it is porous Polymer network structure is formed between graphite skeleton;
Step 4, electrolyte component is removed, is coated, be carbonized (while also by polymer carbonization), obtains silicon-carbon cathode material Material.
Remaining is same as Example 1, repeats no more.
Embodiment 4, difference from Example 1 is, the present embodiment comprises the following steps:
Step 1, it is the sub- silicon grain of the oxidation of metallic lithium powder, a diameter of 100nm, a diameter of 100nm Delanium is (artificial Graphite surface is handled by cladding, and mass ratio is the sub- silicon of oxidation:Delanium=1:9), methyl methacrylate, PVP, tetrem TMOS, particle diameter are 6 μm of the dry-mixed kneading of graphite particle, until uniform;
Step 2, selection lithium hexafluoro phosphate be salt, the electrolyte that PC is solvent, add said mixture in continue stir, this When in the presence of metallic lithium powder, PC will be peeled off to graphite particle, formed hatch frame, while simple substance silicon grain will fill Into in hatch frame;
Step 3, the special butyl ester of perbenzoic acid is dissolved in PC and forms initiator solution, treat the filling described in step 3 After the completion of, add initiator solution, improve temperature, promote polymer monomer occur polymerisation, simple substance silicon grain with it is porous Polymer network structure is formed between graphite skeleton;
Step 4, electrolyte component is removed, is coated, be carbonized (while also by polymer carbonization), obtains silicon-carbon cathode material Material.Remaining is same as Example 1, repeats no more.
Battery is assembled:It is the silicon-carbon cathode material that comparative example, embodiment 1- embodiments 10 are prepared and conductive agent, Nian Jie Agent, stirring solvent obtain electrode slurry, apply form negative electrode on a current collector afterwards;By negative electrode and anode electrode The assembling of (cobalt acid lithium is active material), barrier film obtains naked battery core, and bag is entered afterwards and carries out top side seal, drying, fluid injection, standing, change Resultant battery is obtained into, shaping, degasification.
Material properties test:
Gram volume is tested:Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment Battery core carries out gram volume test:Stand 3min;0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C;Stand 3min; 0.2C constant-current discharges obtain discharge capacity D1 to 3.0V;Stand 3min;0.2C constant-current discharges are to 3.85V;It is complete after standing 3min Into volume test, the weight of silicon carbon material, that is, obtain negative pole gram volume, acquired results are shown in Table 1 in D1 divided by negative electricity pole piece.
High rate performance is tested:Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment Battery core carry out high rate performance test:Stand 3min;0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C;Stand 3min;0.2C constant-current discharges obtain discharge capacity D1 to 3.0V;Stand 3min;0.2C constant-current charges to 4.2V, 4.2V constant pressures is filled Electricity is to 0.05C;Stand 3min;2C constant-current discharges obtain discharge capacity D21 to 3.0V;Stand 3min;High rate performance is completed afterwards Test, battery high rate performance=D2/D1*100%, acquired results are shown in Table 1.
Loop test:The electricity prepared in 25 DEG C of environment by following flow to each embodiment and comparative example silicon carbon material Core carries out loop test:Stand 3min;0.2C constant-current charges are to 4.2V, 4.2V constant-voltage charges to 0.05C;Stand 3min;0.2C Constant-current discharge obtains discharge capacity D1 to 3.0V;3min is stood, " 0.2C constant-current charges to 4.2V, 4.2V constant-voltage charges are extremely 0.05C;Stand 3min;0.2C constant-current discharges obtain discharge capacity Di to 3.0V;3min " is stood to repeat to obtain D300 299 times, Loop test is completed afterwards, and calculating capability retention is D300/D1*100%, and acquired results are shown in Table 1.
The chemical property of the battery core of silicon-carbon cathode material system assembling prepared by table 1, different comparative examples and embodiment
Can be obtained by table 1, the present invention can prepare the silicon-carbon cathode material of function admirable, using the silicon-carbon cathode material as The battery core that negative electrode active material assembling is obtained has excellent chemical property.
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 preparation method of silicon-carbon cathode material, it is characterised in that mainly comprise the following steps:
Step 1, it is power source material 1, silicon nanoparticle, graphite particle is dry-mixed, until well mixed;
Step 2, add and continue to mix after electrolyte 1, form ion channel, now in the presence of power source material, electrolyte Component will be peeled off to graphite particle, form graphite flake layer hatch frame;Under the active force of mixing, silicon nanoparticle will not It is disconnected to be filled into the hatch frame of graphite flake layer;
Or
Step 1 ', silicon nanoparticle, graphite particle, electrolyte 2 are well mixed stand-by;
The product assembling paired electrode that step 2 ', by power source material 2 and step 1 ' is obtained, applies electric current between electrodes, Graphite particle is peeled off, graphite flake layer hatch frame is formed;Silicon nanoparticle will constantly be filled into graphite flake layer afterwards Hatch frame in;
Step 3, after the completion of filling, electrolyte component is removed, is coated, is carbonized, obtain silicon-carbon cathode material.
2. a kind of preparation method of the silicon-carbon cathode material described in claim 1, it is characterised in that power source thing described in step 1 Matter 1 is pre- embedding lithium titanate cathode material or/and metal lithium material.
3. a kind of preparation method of the silicon-carbon cathode material described in claim 1, it is characterised in that electrolyte 1 described in step 2 Include solute and solvent, the solvent includes graphite intercalation or/and peels off function ingredients;Step 1 ' described in electrolyte 2 Include solute and solvent, the solvent includes graphite intercalation or/and peels off function ingredients.
4. the preparation method of the silicon-carbon cathode material described in a kind of claim 3, it is characterised in that the solute is lithium-ion electric Pond electrolyte solute;Include alkali metal, alkali earth metal, metal chloride, chloride, rare earth member in the solvent At least one of element, halogens, counterfeit halogen, strong acid, propene carbonate.
5. a kind of preparation method of the silicon-carbon cathode material described in claim 1, it is characterised in that step 2 ' described in power Source material 2 includes rich lithium material or/and the metallics as electrode material;The rich lithium material includes LiM1O2、LiMn2- XM2xO4、LiNixM31-xO2、Li3-xM4xN、LiFePO4、Li2FeO4、Li7-xMnxN4、Li3-xFexN2、Li2S、Li2S2With LiNixMnyCozO2At least one of, wherein, M1 is at least one of Co, Ni, Mn, Cu, Cr and Fe, M2 be Ni, Co, At least one of Cu, Cr, Fe and V, M3 are at least one of Co, Mn, Cu, Cr, Fe, V, La, Al, Mg, Ga and Zn, and M4 is At least one of Co, Ni, Cu, Cr and V, x+y+z=1;The metallics as electrode material includes lithium metal, metal At least one of sodium, metallic potassium, magnesium metal, metallic aluminium, metallic zinc.
6. the preparation method of the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that step 1 or step 1 ' in also Added with silane coupler, surface reactive material, conductive agent component, non-silicon-based negative pole nano particle.
7. the preparation method of the silicon-carbon cathode material described in a kind of claim 6, it is characterised in that the silane coupler includes VTES, MTMS, tetraethoxysilane, vinyltrimethoxy silane, ethylene methacrylic Base dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, methacryloyloxypropyl methyl dimethoxy Base silane, γ aminopropyltriethoxy silane, γ mercaptopropyitrimethoxy silane, γ-cyanopropyl trimethoxy silicon Alkane, γ-glycidoxypropyltrimethoxy base silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane and γ- At least one of ureido-propyl trimethoxy silane;The surfactant includes wetting agent, dispersant, bleeding agent, solubilising At least one of agent, cosolvent, cosolvent;The conductive agent component includes super conductive carbon, acetylene black, CNT, section Qin is black, at least one of conductive carbon black;The non-silicon-based negative pole nano particle includes native graphite, Delanium, interphase At least one in carbosphere, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, non-silicon alloy material of cathode Kind.
8. the preparation method of the silicon-carbon cathode material described in a kind of claim 1, it is characterised in that step 1 or step 1 ' in also Added with polymer monomer;Now, it is necessary to trigger polymer monomer to polymerize after completion is filled, step 3 is carried out again afterwards.
9. the preparation method of the silicon-carbon cathode material described in a kind of claim 8, it is characterised in that polymer monomer 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;The initiation reaction addition is drawn Send out agent, the initiator isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, di-tert-butyl peroxide, mistake Aoxidize the special butyl ester of dibenzoyl, dilauroyl peroxide, perbenzoic acid, peroxide tert pivalate ester, dicetyl peroxydicarbonate At least one of diisopropyl ester, di-cyclohexylperoxy di-carbonate.
10. the silicon-carbon cathode material that a kind of preparation method of the silicon-carbon cathode material described in claim 1 is prepared, its feature It is, the silicon-carbon cathode material, including nuclear structure and shell structure, the nuclear structure is second particle structure, and including Leading electric network with loose structure and the nanometer primary particle being filled in the pore structure of the leading electric network;It is described Leading electric network be graphite part peel off lamella and lamella in coccolith ink obtain, same at least a portion link together, Form the loose structure of opening between lamella and lamella again simultaneously;It is tight between the leading electric network and the nanometer primary particle It is close to link together.
CN201710271222.0A 2017-04-24 2017-04-24 A kind of preparation method of silicon-carbon cathode material and the silicon-carbon cathode material prepared using this method Pending CN107086297A (en)

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CN109873197A (en) * 2019-02-20 2019-06-11 苏州大学 A kind of solid lithium ion battery polymer dielectric and preparation method thereof
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