CN109244401A - A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation - Google Patents

A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation Download PDF

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CN109244401A
CN109244401A CN201811047837.6A CN201811047837A CN109244401A CN 109244401 A CN109244401 A CN 109244401A CN 201811047837 A CN201811047837 A CN 201811047837A CN 109244401 A CN109244401 A CN 109244401A
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silicon
weight
parts
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刘祥
王奥宁
王金培
徐晨
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Nanjing Tech University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of negative electrode of lithium ion battery porous nano Si-C composite materials and preparation method thereof, this first prepares polystyrene microsphere lotion, add template, ethyl alcohol, ammonium hydroxide and ethyl orthosilicate are reacted, obtain polystyrene/silica dioxide core-shell structure compound, then high-temperature calcination obtains carbon/silicon dioxide nanocomposite of hollow structure, it is subsequently added into magnesium powder progress reduction reaction and obtains porous carbon/silicon nano-complex of hollow structure, most followed by graphite mixes, spray drying, high-temperature heat treatment, it crushes, sieving, obtain porous nano Si-C composite material.Negative electrode of lithium ion battery porous nano Si-C composite material reversible capacity using this method preparation is high, and good conductivity, energy density is high, has extended cycle life.

Description

A kind of porous nano Si-C composite material and its preparation using magnesium reduction process preparation Method
Technical field
The invention belongs to lithium ion battery negative materials and preparation method thereof, are related to negative electrode of lithium ion battery porous nano silicon Carbon composite and preparation method thereof.
Background technique
In lithium ion battery negative material research application, the theoretical specific capacity highest of silica-base material, the alloy formed For LixSi, the range of x is 0-4.4, and the theoretical specific capacity of pure silicon is 4200mAh/g, and commercial negative electrode material natural graphite at present Theoretical capacity there was only 372mAh/g, and silicon does not have solvation, and raw material storage is abundant, and more other metal materials have Higher stability, it is considered to be the cathode material for high capacity lithium ion battery most expected.However, silicium cathode is since it is in lithium Embedding, de- cyclic process in undergo serious volume expansion and contraction, destruction and the pulverization of material structure are caused, to lead The decline for sending a telegraph pole cycle performance limits its commercial applications.
Stress cracking is easy to happen in charge and discharge process in order to solve silicium cathode material causes volume expansion to cause to recycle The problem of performance deteriorates mainly has following ameliorative way at present: reducing the partial size of active silicon particle, prepares nanometer materials to subtract The internal stress of few volume change；Using the compound of nano silicon material and other materials, such as Si-C composite material, to alleviate silicon Volume expansion, to improve its cycle life.
Chinese patent CN201710437168.2 discloses a kind of method that low temperature synthesizes high-specific-surface mesoporous silicon carbide, with Triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) is template, positive silicic acid Ethyl ester is silicon source, and furfuryl alcohol is that carbon source prepares C/SiO2Presoma；Under an inert gas, by C/SiO2Presoma is through magnesiothermic reduction With washing drying, carbofrax material is obtained.Persursor material has chosen the C/SiO of support, intergrowth each other in the method2Make For presoma, skeleton structure is retained to the greatest extent during the reaction, material prepared specific surface area up to 600~ 800m2/g.But the carbon in the material is all from high-molecular compound carbonisation, uses 500-700 DEG C of low temperature synthesis road Line, the carbon conductive that high-molecular compound obtains after low-temperature carbonization is poor, therefore the material can not be used as lithium ion battery material Material uses；Secondly, this method uses triblock copolymer P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide three block Copolymer) it is template, high molecular polymer is difficult to substantially remove at high temperature, and remaining carbon is high, due to triblock copolymer P123 Pintsch process carbon only exists as conductive agent in lithium cell cathode material, the active material of non-participating reaction, therefore residual The excessively high energy density for leading to the material of carbon amounts is smaller；Again, this method does not control the shapes and sizes of carbon source, shape Shape is irregular, and carbon source covers SiO2Particle or the excessive composite material granular resulted in of carbon source particle are excessive, separate SiO existing for inside the particle on surface2It is difficult to participate in magnesiothermic reduction, becomes non-active region, reduce Si-C composite material can Inverse capacity；Finally, the material does not control the structure of porous carbon and silicon particle compound, porous carbon and silicon particle are compound If object stacking volume is excessive, the deeper silicon in stacking volume inner distance surface can not participate in battery charging and discharging reaction, therefore drop The low reversible capacity of the Si-C composite material.
It is unformed with mesoporous crystal type Si- that Chinese patent CN201710703399.3 discloses a kind of sodium-ion battery SiO2The preparation method and application of ordered mesoporous carbon composite material are in situ multiple first using ordered mesoporous silica dioxide as self-template Ordered mesopore structure silica-mesoporous carbon complex that co-continuous is made in carbon source is closed, etching removal part SiO is then passed through2 The synthesising mesoporous SiO of method2Ordered mesoporous carbon complex；Magnesium reduction process is finally utilized, the ratio of magnesium powder and compound is controlled The mesoporous unformed SiO of crystal type Si- is made in example, reduction2Ordered mesoporous carbon composite material, anode material of lithium-ion battery tool There is excellent storage sodium performance, the preparation process is simple, and strong operability, raw material sources are extensive, and it is low in cost, it can give birth on a large scale It produces, meets environmental requirement.But the material does not control the structure of mesoporous carbon and silicon particle compound, porous carbon and If silicon particle compound stacking volume is excessive, it is anti-that the deeper silicon in stacking volume inner distance surface can not participate in battery charging and discharging It answers, therefore reduces the reversible capacity of the Si-C composite material；Secondly, the material does not control the partial size of silicon particle, If silicon particle is excessive, volume expansion can be very big in battery charging and discharging cyclic process, causes negative electrode active material from cathode collection Fluid falls off, and reduces cycle life.
Summary of the invention
It is obtained after 500-700 DEG C of low-temperature carbonization for above-mentioned existing Si-C composite material there are high-molecular compound Carbon conductive is poor；It is difficult to substantially remove at high temperature using high molecular polymer, remaining carbon is high, leads to the energy density of the material It is smaller；The shapes and sizes of carbon source are not controlled, far from surface particle inside existing for SiO2It is difficult to participate in magnesium Thermal reduction, becomes non-active region, reduces the reversible capacity of Si-C composite material；Not to mesoporous carbon and silicon particle compound Structure is controlled, if porous carbon and silicon particle compound stacking volume are excessive, stacking volume inner distance surface is deeper Silicon can not participate in battery charging and discharging reaction, therefore reduce the reversible capacity of the Si-C composite material；Not to the grain of silicon particle Diameter is controlled, if silicon particle is excessive, volume expansion can be very big in battery charging and discharging cyclic process, leads to negative electrode active material The disadvantages of material falls off from negative current collector, reduces cycle life, by studying demonstration repeatedly, the present invention proposes a kind of using magnesium heat The porous nano Si-C composite material and preparation method thereof of reduction method preparation solves the above problems, the technical solution adopted by the present invention Include step in detail below:
(1) preparation of polystyrene (PS) microballoon lotion:
1-10 weight account polyethylene pyrrolidones is dissolved in 180 parts by weight water, 5-15 parts by weight of styrene, stirring is added 70 DEG C are heated to, then 0.1-1 parts by weight initiator azo diisobutyl amidine hydrochloride salt is added in 30 parts by weight water It is reacted 12-30 hours in reaction system, obtains polystyrene (PS) microballoon lotion, microspherulite diameter range is 50-400nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 3.0-10.0 parts by weight polystyrene microsphere emulsion dispersion in 100 parts by weight water, stirs 5-20 minutes, continue It is added and contains the agent of 0.2-5 parts by weight of template, 30-60 parts by weight of ethanol, the mixed solution of 1 parts by weight ammonium hydroxide stirs 30 minutes, will 1.0-10.0 parts by weight ethyl orthosilicate (TEOS) is slowly added dropwise that 3-10 is persistently stirred at above-mentioned mixed solution, 25-35 DEG C is small When, centrifuge separation is dried to obtain polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size exists Between 200-600nm, wherein SiO2Layer is with a thickness of 10-100nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) 600-900 DEG C high-temperature calcination 2-6 hours, Under nitrogen atmosphere protection, carbon/silicon dioxide nanocomposite (C/SiO of hollow structure is obtained2), partial size 200-600nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
0.25-0.35 parts by weight carbon/silicon dioxide nanocomposite is taken, 0.25-0.35 parts by weight magnesium powder is in glove box Ground and mixed is uniform, and obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, under argon atmosphere 600-800 DEG C reaction 2-6 hours, the obtained product salt acid elution of 1mol/L removes oxidation magnesium addition, finally in vacuum It is 10-18 hours dry in 70-90 DEG C in drying box, porous carbon/silicon nano-complex (C/Si) of hollow structure is obtained, partial size is 200-600nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
It is slowly added to graphite composite powder into deionized water, stirs and graphite dispersing solution is made, then porous carbon/silicon nanometer is answered Object (C/Si) is closed to be added in graphite dispersing solution while stirring, graphite and silicon in mass ratio: 80~97 parts by weight of graphite, it is porous Carbon/20~296 parts by weight of silicon nano-complex (C/Si), adjustment dispersion fluid solid content is 15~25wt%, obtains porous carbon/silicon Nano-complex (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid into Row spray drying, is heat-treated for 300-800 DEG C under lazy gas shield, crushes, is sieved, obtain hollow knot for reaction 2-12 hours The porous nano Si-C composite material (C/Si/C) of structure, structural model are shown in attached drawing 1.
Step (2) template is one kind of cetyl trimethylammonium bromide (CTAB), polyethylene oxide.
Step (2) ethyl orthosilicate (TEOS) preferably 1.0-2.0 parts by weight.
Preferred 600-680 DEG C of reaction temperature in step (4) described tube furnace, the reaction time is 3-4 hours preferred, obtains hollow The porous carbon of structure/silicon nano-complex (C/Si), partial size is preferably 200-400nm.
One or two kinds of mixtures of step (5) the graphite preferred natural graphite, artificial graphite.
Step (5) porous carbon/silicon nano-complex (C/Si) is 20~40 parts by weight.
The present invention compared with the prior art, has the advantages that
(1) graphite in the porous nano Si-C composite material (C/Si/C) of the method for the present invention preparation, good conductivity are suitble to It is used as lithium ion battery material.
(2) the method for the present invention uses CTAB or polyethylene oxide as template, compared to high molecular polymer, CTAB Or polyethylene oxide molecules amount is small, is easily removed at high temperature, and few, the porous nano of the method for the present invention preparation is remained after sintering Si-C composite material (C/Si/C) energy density is higher.
(3) the method for the present invention synthetic polystyrene microballoon, polystyrene microsphere and SiO2200- is prepared by processing 600nm polystyrene/silica dioxide core-shell structure (PS/SiO2), carbon/dioxy of 200-600nm hollow structure is generated after carbonization SiClx nano-complex (C/SiO2), hollow carbon structure avoids carbon source covering SiO2Particle and the excessive problem of carbon source particle, SiO2Distribution of particles is easy to participate in magnesium thermit and generates Si particle, the porous nano silicon-carbon of preparation on the surface of hollow carbon structure Composite material reversible capacity is big.
(4) silicon particle and porous carbon structure are located at hollow carbon structure in the porous nano Si-C composite material of this method preparation Outer layer, ensure that silicon materials and electrolyte and negative current collector contact area in lithium ion battery, improve porous nano The reversible capacity of Si-C composite material (C/Si/C).
(5) this method is by ethyl orthosilicate (TEOS) fabricated in situ SiO2, item is chemically reacted by generated time, temperature etc. The control of part prepares the SiO of 10-100nm size2Particle passes through reaction temperature and time then by the method for magnesiothermic reduction Come control generate Si particle size, by SiO2It is reduced into the Si particle of 10-100nm size, it is excessive to solve silicon particle, in lithium Volume expansion can be very big in battery charging and discharging cyclic process, causes negative electrode active material to fall off from negative current collector, influences to recycle The problem of service life, improves the cycle life of porous nano Si-C composite material (C/Si/C).
Detailed description of the invention
Fig. 1 is the structural model of the porous nano Si-C composite material (C/Si/C) of hollow structure of the present invention.1, silicon；2, Carbon；3, graphite.
Fig. 2 is carbon/silicon dioxide nanocomposite (C/SiO of hollow structure prepared by embodiment 12) transmission electron microscope photograph Piece.
Fig. 3 is the discharge curve that 1 simulated battery of embodiment is tested with 0.1C multiplying power.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and examples.
Embodiment 1
(1) preparation of polystyrene (PS) microballoon lotion:
3g polyvinylpyrrolidone is dissolved in 180g water, 8.5g styrene is added, is stirred and heated to 70 DEG C, then will 0.18g initiator azo diisobutyl amidine hydrochloride salt is added in glass reactor and reacts 24 hours, obtain in 30g water To polystyrene (PS) microballoon lotion, microspherulite diameter range is 200nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 6g polystyrene microsphere emulsion dispersion in 100g water, stirs 10 minutes, continuously add containing 0.6g template Cetyl trimethylammonium bromide (CTAB), 39.5g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by the positive silicic acid of 1.4g Ethyl ester (TEOS), which is slowly added dropwise at above-mentioned mixed solution, 30 DEG C, persistently to be stirred 6 hours, centrifuge separation, in a vacuum drying oven 110 DEG C drying 5 hours, obtain polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size exists Between 300nm, wherein SiO2Layer is with a thickness of 50nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 800 DEG C of high temperature are forged It burns 3 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 300nm, transmission electron microscope photo is shown in attached drawing 2；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
0.3g carbon/silicon dioxide nanocomposite is taken, 0.3g magnesium powder ground and mixed in the glove box of applying argon gas is uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 650 DEG C of argon atmosphere are reacted 4 hours, The obtained product salt acid elution of 1mol/L removes oxidation magnesium addition, 12 hours dry in 70 DEG C in a vacuum drying oven, Obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 300nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
It is slowly added to natural graphite powder into deionized water, stirs natural graphite dispersion liquid, then porous carbon/silicon is received Rice compound (C/Si) is added to while stirring in natural graphite dispersion liquid, graphite and silicon in mass ratio: natural graphite 85g, it is more Hole carbon/silicon nano-complex (C/Si) 30g, adjustment dispersion fluid solid content is 20wt%, obtains porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid spray dryer It is spray-dried, obtained powder is put into atmosphere batch-type furnace, under inert gas protection 700 DEG C of reactions progress in 8 hours heat Processing, is crushed with pulverizer, is sieved with 200 mesh screens, is obtained the porous nano Si-C composite material (C/ of hollow structure Si/C)。
Simulated battery production:
For the porous nano Si-C composite material (C/Si/C) for using embodiment to prepare respectively as active material, production simulation is electric Pond, making step are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g, 5% Kynoar PVDF 8g and N- The ratio of methyl pyrrolidone NMP 0.8g weigh graphite silicon material activity substance, conductive agent, 5% PVDF and NMP, then use Mechanical stirring mode be configured to solid content be 32.26% slurry, stir about 15 minutes, slurry in honey paste preferably.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6(volume ratio Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd. The data in pond, voltage range are 0.005~2V, according to the reversible capacity and first charge discharge efficiency that charging and discharging currents are 0.1C, are held within 25 weeks The chemical property of conservation rate, 0.5C rate charge-discharge reversible capacity evaluation material is measured, the energy that tap density evaluates material is close Degree.
Simulated battery, tap density 1.0g/cm are made according to the above method3, battery is with the reversible appearance of 0.1C rate charge-discharge Amount is 507mAh/g, and discharge curve is shown in attached drawing 3, and first charge discharge efficiency 92.1%, circulation is after 25 weeks, capacity retention ratio 96.5%, 0.5C rate charge-discharge reversible capacity is 471mAh/g.
Embodiment 2
(1) preparation of polystyrene (PS) microballoon lotion:
6g polyvinylpyrrolidone is dissolved in 180g water, 12g styrene is added, is stirred and heated to 70 DEG C, then by 0.7g Initiator azo diisobutyl amidine hydrochloride salt is added in reaction system and reacts 18 hours, obtain polyphenyl second in 30g water Alkene (PS) microballoon lotion, microspherulite diameter range are 100nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 8.0g polystyrene microsphere emulsion dispersion in 100g water, stirs 15 minutes, continuously add containing 3g template Cetyl trimethylammonium bromide (CTAB), 50g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by the positive silicic acid second of 7.0g Ester (TEOS), which is slowly added dropwise at above-mentioned mixed solution, 35 DEG C, persistently to be stirred 4 hours, centrifuge separation, be dried to obtain polystyrene/ Silicon dixoide nucleocapsid structure compound (PS/SiO2) product, whole partial size is between 200nm, wherein SiO2Layer is with a thickness of 30nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) 700 DEG C high-temperature calcination 5 hours, nitrogen gas Under atmosphere protection, carbon/silicon dioxide nanocomposite (C/SiO of hollow structure is obtained2), partial size 200nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.32g carbon/silicon dioxide nanocomposite 0.32g magnesium powder ground and mixed in glove box uniform, it is obtained Mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 700 DEG C of argon atmosphere are reacted 3 hours, acquired Product remove oxidation magnesium addition with the salt acid elution of 1mol/L, it is finally 16 hours dry in 80 DEG C in a vacuum drying oven, obtain To porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 200nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 90g, porous carbon/silicon nano-complex (C/Si) 25g, adjustment dispersion fluid solid content is 15wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；Porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid is sprayed Mist is dry, and 600 DEG C of reactions are heat-treated for 10 hours under lazy gas shield, crushes, is sieved, obtains the porous of hollow structure and receive Rice Si-C composite material (C/Si/C).
Performance, tap density 1.0g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 485mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 93.6%, after 25 weeks, capacity retention ratio is circulation 97.1%, 0.5C rate charge-discharge reversible capacity are 466mAh/g.
Embodiment 3
(1) preparation of polystyrene (PS) microballoon lotion:
1g polyvinylpyrrolidone is dissolved in 180g water, 5g styrene is added, is stirred and heated to 70 DEG C, then 0.1g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 12 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 50nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 3.0g polystyrene microsphere emulsion dispersion in 100g water, stirs 12 minutes, continuously add containing 1g template Cetyl trimethylammonium bromide (CTAB), 30g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by 1g ethyl orthosilicate (TEOS) it is slowly added dropwise at above-mentioned mixed solution, 25 DEG C and persistently stirs 9 hours, be centrifugated, 110 DEG C in a vacuum drying oven Dry 5h, obtains polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size between 200nm, Wherein SiO2Layer is with a thickness of 70nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 700 DEG C of high temperature are forged It burns 2 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 200nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.25g carbon/silicon dioxide nanocomposite 0.25g magnesium powder ground and mixed in the glove box of applying argon gas uniform, Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and the lower 600 DEG C of reactions 3 of argon atmosphere are small When, obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally in a vacuum drying oven in 80 DEG C of dryings 10 hours, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 200nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 90g, porous carbon/silicon nano-complex (C/Si) 40g, adjustment dispersion fluid solid content is 18wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid with by spraying Drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, is reacted 10 hours for 650 DEG C under inert gas protection It is heat-treated, is crushed with pulverizer, be sieved with 200 mesh screens, obtain the porous nano silicon-carbon composite wood of hollow structure Expect (C/Si/C).
Performance, tap density 0.8g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 547mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 85.2%, after 25 weeks, capacity retention ratio is circulation 89.5%, 0.5C rate charge-discharge reversible capacity are 461mAh/g.
Embodiment 4
(1) preparation of polystyrene (PS) microballoon lotion:
10g polyvinylpyrrolidone is dissolved in 180g water, 15g styrene is added, is stirred and heated to 70 DEG C, then 1g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 30 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 400nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 10.0g polystyrene microsphere emulsion dispersion in 100g water, stirs 20 minutes, continuously add containing 5g template Cetyl trimethylammonium bromide (CTAB), 60g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by the positive silicic acid of 10.0g Ethyl ester (TEOS), which is slowly added dropwise at above-mentioned mixed solution, 35 DEG C, persistently to be stirred 10 hours, centrifuge separation, in a vacuum drying oven 110 DEG C of dry 5h, obtain polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size is in 600nm Between, wherein SiO2Layer is with a thickness of 100nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 900 DEG C of high temperature are forged It burns 4 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 600nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.35g carbon/silicon dioxide nanocomposite 0.35g magnesium powder ground and mixed in the glove box of applying argon gas uniform, Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and the lower 800 DEG C of reactions 2 of argon atmosphere are small When, obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally in a vacuum drying oven in 90 DEG C of dryings 12 hours, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 600nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 97g, porous carbon/silicon nano-complex (C/Si) 20g, adjustment dispersion fluid solid content is 15wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid with by spraying Drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, is reacted 12 hours for 600 DEG C under inert gas protection It is heat-treated, is crushed with pulverizer, be sieved with 200 mesh screens, obtain the porous nano silicon-carbon composite wood of hollow structure Expect (C/Si/C).
Performance, tap density 0.9g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 535mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 92.1%, after 25 weeks, capacity retention ratio is circulation 95.6%, 0.5C rate charge-discharge reversible capacity are 503mAh/g.
Embodiment 5
(1) preparation of polystyrene (PS) microballoon lotion:
4g polyvinylpyrrolidone is dissolved in 180g water, 9g styrene is added, is stirred and heated to 70 DEG C, then 0.2g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 20 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 200nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 5g polystyrene microsphere emulsion dispersion in 100g water, stirs 8 minutes, continuously add containing 0.5g template ten Six alkyl trimethyl ammonium bromides (CTAB), 35g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by 2g ethyl orthosilicate (TEOS) it is slowly added dropwise at above-mentioned mixed solution, 28 DEG C and persistently stirs 8 hours, be centrifugated, 110 DEG C in a vacuum drying oven Dry 5h, obtains polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size between 250nm, Wherein SiO2Layer is with a thickness of 20nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 800 DEG C of high temperature are forged It burns 3 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 250nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.3g carbon/silicon dioxide nanocomposite 0.3g magnesium powder ground and mixed in the glove box of applying argon gas uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 680 DEG C of argon atmosphere are reacted 4 hours, Obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally small in 70 DEG C of dryings 12 in a vacuum drying oven When, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 250nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 88g, porous carbon/silicon nano-complex (C/Si) 25g, adjustment dispersion fluid solid content is 20wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid with by spraying Drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, is reacted 8 hours for 750 DEG C under inert gas protection It is heat-treated, is crushed with pulverizer, be sieved with 200 mesh screens, obtain the porous nano silicon-carbon composite wood of hollow structure Expect (C/Si/C).
Performance, tap density 1.0g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 511mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 93.2%, after 25 weeks, capacity retention ratio is circulation 96.8%, 0.5C rate charge-discharge reversible capacity are 497mAh/g.
Embodiment 6
(1) preparation of polystyrene (PS) microballoon lotion:
4g polyvinylpyrrolidone is dissolved in 180g water, 9g styrene is added, is stirred and heated to 70 DEG C, then 0.2g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 28 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 300nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 5.0g polystyrene microsphere emulsion dispersion in 100g water, stirs 5 minutes, continuously add containing 0.2g template Cetyl trimethylammonium bromide (CTAB), 35g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by the positive silicic acid second of 2.0g Ester (TEOS), which is slowly added dropwise at above-mentioned mixed solution, 35 DEG C, persistently to be stirred 3 hours, centrifuge separation, and in a vacuum drying oven 110 DEG C dry 5h, obtains polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size 320nm it Between, wherein SiO2Layer is with a thickness of 10nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 600 DEG C of high temperature are forged It burns 6 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 320nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.3g carbon/silicon dioxide nanocomposite 0.3g magnesium powder ground and mixed in the glove box of applying argon gas uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 750 DEG C of argon atmosphere are reacted 5 hours, Obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally small in 80 DEG C of dryings 15 in a vacuum drying oven When, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 320nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 88g, porous carbon/silicon nano-complex (C/Si) 25g, adjustment dispersion fluid solid content is 25wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid with by spraying Drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, is reacted 8 hours for 750 DEG C under inert gas protection It is heat-treated, is crushed with pulverizer, be sieved with 200 mesh screens, obtain the porous nano silicon-carbon composite wood of hollow structure Expect (C/Si/C).
Performance, tap density 1.0g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 506mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 90.7%, after 25 weeks, capacity retention ratio is circulation 95.2%, 0.5C rate charge-discharge reversible capacity are 477mAh/g.
Embodiment 7
(1) preparation of polystyrene (PS) microballoon lotion:
4g polyvinylpyrrolidone is dissolved in 180g water, 9g styrene is added, is stirred and heated to 70 DEG C, then 0.2g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 20 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 200nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 5g polystyrene microsphere emulsion dispersion in 100g water, stirs 8 minutes, continuously add containing 0.5g template ten Six alkyl trimethyl ammonium bromides (CTAB), 35g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by 2g ethyl orthosilicate (TEOS) it is slowly added dropwise at above-mentioned mixed solution, 28 DEG C and persistently stirs 8 hours, be centrifugated, 110 DEG C in a vacuum drying oven Dry 5h, obtains polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size between 250nm, Wherein SiO2Layer is with a thickness of 20nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 800 DEG C of high temperature are forged It burns 3 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 250nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.3g carbon/silicon dioxide nanocomposite 0.3g magnesium powder ground and mixed in the glove box of applying argon gas uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 700 DEG C of argon atmosphere are reacted 4 hours, Obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally small in 70 DEG C of dryings 12 in a vacuum drying oven When, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 250nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 97g, porous carbon/silicon nano-complex (C/Si) 296g, adjustment dispersion fluid solid content is 15wt%, obtains porous carbon/silicon and receives Rice compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid spray Mist drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, and 800 DEG C of reactions 2 are small under inert gas protection Shi Jinhang heat treatment, is crushed with pulverizer, is sieved with 200 mesh screens, and the porous nano silicon-carbon for obtaining hollow structure is compound Material (C/Si/C).
Performance, tap density 0.7g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 769mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 77.3%, after 25 weeks, capacity retention ratio is circulation 61.8%, 0.5C rate charge-discharge reversible capacity are 332mAh/g.
Embodiment 8
(1) preparation of polystyrene (PS) microballoon lotion:
4g polyvinylpyrrolidone is dissolved in 180g water, 9g styrene is added, is stirred and heated to 70 DEG C, then 0.2g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 20 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 200nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 5g polystyrene microsphere emulsion dispersion in 100g water, stirs 8 minutes, continuously add poly- containing 0.5g template Ethylene oxide, 35g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, 2g ethyl orthosilicate (TEOS) are slowly added dropwise in upper Mixed solution is stated, is persistently stirred at 28 DEG C 8 hours, is centrifugated, 110 DEG C of dry 5h, obtain polyphenyl second in a vacuum drying oven Alkene/silicon dixoide nucleocapsid structure compound (PS/SiO2) product, whole partial size is between 250nm, wherein SiO2Layer with a thickness of 20nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 800 DEG C of high temperature are forged It burns 3 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 250nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.3g carbon/silicon dioxide nanocomposite 0.3g magnesium powder ground and mixed in the glove box of applying argon gas uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 700 DEG C of argon atmosphere are reacted 4 hours, Obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally small in 70 DEG C of dryings 12 in a vacuum drying oven When, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 250nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to natural graphite powder into deionized water, stir and natural graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in natural graphite dispersion liquid, natural graphite and silicon in mass ratio: natural stone Black 88g, porous carbon/silicon nano-complex (C/Si) 200g, adjustment dispersion fluid solid content is 20wt%, obtains porous carbon/silicon and receives Rice compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid spray Mist drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, and 300 DEG C of reactions 12 are small under inert gas protection Shi Jinhang heat treatment, is crushed with pulverizer, is sieved with 200 mesh screens, and the porous nano silicon-carbon for obtaining hollow structure is compound Material (C/Si/C).
Performance, tap density 0.7g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 681mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 81%, after 25 weeks, capacity retention ratio is circulation 65.7%, 0.5C rate charge-discharge reversible capacity are 346mAh/g.
Embodiment 9
(1) preparation of polystyrene (PS) microballoon lotion:
4g polyvinylpyrrolidone is dissolved in 180g water, 9g styrene is added, is stirred and heated to 70 DEG C, then 0.2g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 28 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 300nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 5g polystyrene microsphere emulsion dispersion in 100g water, stirs 8 minutes, continuously add poly- containing 0.5g template Ethylene oxide, 35g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, 2g ethyl orthosilicate (TEOS) are slowly added dropwise in upper Mixed solution is stated, is persistently stirred at 35 DEG C 8 hours, is centrifugated, 110 DEG C of dry 5h, obtain polyphenyl second in a vacuum drying oven Alkene/silicon dixoide nucleocapsid structure compound (PS/SiO2) product, whole partial size is between 400nm, wherein SiO2Layer with a thickness of 50nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 800 DEG C of high temperature are forged It burns 3 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 400nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.3g carbon/silicon dioxide nanocomposite 0.3g magnesium powder ground and mixed in the glove box of applying argon gas uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 700 DEG C of argon atmosphere are reacted 4 hours, Obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally small in 70 DEG C of dryings 12 in a vacuum drying oven When, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 400nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to artificial graphite powder into deionized water, stir and artificial graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in artificial graphite dispersion liquid, artificial graphite and silicon in mass ratio: artificial stone Black 95g, porous carbon/silicon nano-complex (C/Si) 25g, adjustment dispersion fluid solid content is 20wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid with by spraying Drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, is reacted 8 hours for 750 DEG C under inert gas protection It is heat-treated, is crushed with pulverizer, be sieved with 200 mesh screens, obtain the porous nano silicon-carbon composite wood of hollow structure Expect (C/Si/C).
Performance, tap density 0.8g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 465mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 88.1%, after 25 weeks, capacity retention ratio is circulation 83%, 0.5C rate charge-discharge reversible capacity are 406mAh/g.
Embodiment 10
(1) preparation of polystyrene (PS) microballoon lotion:
4g polyvinylpyrrolidone is dissolved in 180g water, 9g styrene is added, is stirred and heated to 70 DEG C, then 0.2g is drawn Agent azo diisobutyl amidine hydrochloride salt is sent out in 30g water, is added in glass reactor and reacts 20 hours, obtain polyphenyl second Alkene (PS) microballoon lotion, microspherulite diameter range are 200nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 5g polystyrene microsphere emulsion dispersion in 100g water, stirs 8 minutes, continuously add containing 0.5g template ten Six alkyl trimethyl ammonium bromides (CTAB), 35g ethyl alcohol, the mixed solution of 1g ammonium hydroxide stir 30 minutes, by 2g ethyl orthosilicate (TEOS) it is slowly added dropwise at above-mentioned mixed solution, 28 DEG C and persistently stirs 8 hours, be centrifugated, 110 DEG C in a vacuum drying oven Dry 5h, obtains polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size between 250nm, Wherein SiO2Layer is with a thickness of 20nm；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) in batch-type furnace GF17Q, 800 DEG C of high temperature are forged It burns 3 hours, uses nitrogen as protection gas, natural cooling obtains carbon/silicon dioxide nanocomposite (C/ of hollow structure SiO2), partial size 250nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
Take 0.3g carbon/silicon dioxide nanocomposite 0.3g magnesium powder ground and mixed in the glove box of applying argon gas uniform, institute Obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, and lower 680 DEG C of argon atmosphere are reacted 4 hours, Obtained product removes oxidation magnesium addition with the salt acid elution of 1mol/L, finally small in 70 DEG C of dryings 12 in a vacuum drying oven When, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 250nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
Be slowly added to artificial graphite powder into deionized water, stir and artificial graphite dispersion liquid is made, then porous carbon/ Silicon nano-complex (C/Si) is added to while stirring in artificial graphite dispersion liquid, artificial graphite and silicon in mass ratio: artificial stone Black 95g, porous carbon/silicon nano-complex (C/Si) 150g, adjustment dispersion fluid solid content is 20wt%, obtains porous carbon/silicon and receives Rice compound (C/Si)/graphite composite dispersion liquid；To porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid spray Mist drying machine is spray-dried, and obtained powder is put into atmosphere batch-type furnace, and 750 DEG C of reactions 8 are small under inert gas protection Shi Jinhang heat treatment, is crushed with pulverizer, is sieved with 200 mesh screens, and the porous nano silicon-carbon for obtaining hollow structure is compound Material (C/Si/C).
Performance, tap density 0.7g/cm are evaluated by the production simulated battery of simulated battery production method described in embodiment 13, Battery is 681mAh/g with 0.1C rate charge-discharge reversible capacity, and first charge discharge efficiency 77%, after 25 weeks, capacity retention ratio is circulation 80.5%, 0.5C rate charge-discharge reversible capacity are 373mAh/g.

Claims (10)

1. a kind of preparation method of porous nano Si-C composite material, it is characterised in that include the following steps:
(1) preparation of polystyrene (PS) microballoon lotion:
1-10 weight account polyethylene pyrrolidones is dissolved in 180 parts by weight water, 5-15 parts by weight of styrene, agitating and heating is added Reaction is added in 30 parts by weight water to 70 DEG C, then by 0.1-1 parts by weight initiator azo diisobutyl amidine hydrochloride salt It is reacted 12-30 hours in system, obtains polystyrene (PS) microballoon lotion, microspherulite diameter range is 50-400nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 3.0-10.0 parts by weight polystyrene microsphere emulsion dispersion in 100 parts by weight water, stirs 5-20 minutes, continuously add Containing 0.2-5 parts by weight of template agent, 30-60 parts by weight of ethanol, the mixed solution of 1 parts by weight ammonium hydroxide is stirred 30 minutes, by 1.0- 10.0 parts by weight ethyl orthosilicates (TEOS), which are slowly added dropwise at above-mentioned mixed solution, 25-35 DEG C, persistently to be stirred 3-10 hours, from Heart separation, is dried to obtain polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size is in 200- Between 600nm, wherein SiO2Layer with a thickness of 10-100nm, wherein the preferred cetyl trimethylammonium bromide of template (CTAB), One kind of polyethylene oxide；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) 600-900 DEG C high-temperature calcination 2-6 hours, nitrogen Under atmosphere protection, carbon/silicon dioxide nanocomposite (C/SiO of hollow structure is obtained2), partial size 200-600nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
0.25-0.35 parts by weight carbon/silicon dioxide nanocomposite is taken, 0.25-0.35 parts by weight magnesium powder is ground in glove box It is uniformly mixed, obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, 600- under argon atmosphere 800 DEG C reaction 2-6 hours, the obtained product salt acid elution of 1mol/L removes oxidation magnesium addition, is finally being dried in vacuo It is 10-18 hours dry in 70-90 DEG C in case, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 200- 600nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
It is slowly added to graphite composite powder into deionized water, stirs and graphite dispersing solution is made, then porous carbon/silicon nano-complex (C/Si) be added in graphite dispersing solution while stirring, graphite and silicon in mass ratio: 80~97 parts by weight of graphite, porous carbon/silicon 20~296 parts by weight of nano-complex (C/Si), adjustment dispersion fluid solid content is 15~25wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；Porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid is sprayed Mist is dry, is heat-treated within reaction 2-12 hours for 300-800 DEG C under lazy gas shield, crushes, is sieved, obtain hollow structure Porous nano Si-C composite material (C/Si/C).
2. the preparation method of porous nano Si-C composite material according to claim 1, it is characterised in that the positive silicic acid second Ester (TEOS) preferably 1.0-2.0 parts by weight.
3. the preparation method of porous nano Si-C composite material according to claim 1, it is characterised in that in the tube furnace Preferred 600-680 DEG C of reaction temperature, the reaction time is 3-4 hours preferred, obtains porous carbon/silicon nano-complex of hollow structure (C/Si) partial size is preferably 200-400nm.
4. the preparation method of porous nano Si-C composite material according to claim 1, it is characterised in that the graphite is preferred One or two kinds of mixtures of natural graphite, artificial graphite.
5. the preparation method of porous nano Si-C composite material according to claim 1, it is characterised in that porous carbon/silicon nanometer Compound (C/Si) is 20~40 parts by weight.
6. a kind of porous nano Si-C composite material, it is characterised in that be prepared using following methods:
(1) preparation of polystyrene (PS) microballoon lotion:
1-10 weight account polyethylene pyrrolidones is dissolved in 180 parts by weight water, 5-15 parts by weight of styrene, agitating and heating is added Reaction is added in 30 parts by weight water to 70 DEG C, then by 0.1-1 parts by weight initiator azo diisobutyl amidine hydrochloride salt It is reacted 12-3 hours in system, obtains polystyrene (PS) microballoon lotion, microspherulite diameter range is 50-400nm；
(2) polystyrene/silica dioxide core-shell structure compound (PS/SiO2) preparation:
It takes 3.0-10.0 parts by weight polystyrene microsphere emulsion dispersion in 100 parts by weight water, stirs 5-20 minutes, continuously add Containing 0.2-5 parts by weight of template agent, 30-60 parts by weight of ethanol, the mixed solution of 1 parts by weight ammonium hydroxide is stirred 30 minutes, by 1.0- 10.0 parts by weight ethyl orthosilicates (TEOS), which are slowly added dropwise at above-mentioned mixed solution, 25-35 DEG C, persistently to be stirred 3-10 hours, from Heart separation, is dried to obtain polystyrene/silica dioxide core-shell structure compound (PS/SiO2) product, whole partial size is in 200- Between 600nm, wherein SiO2Layer with a thickness of 10-100nm, wherein the preferred cetyl trimethylammonium bromide of template (CTAB), One kind of polyethylene oxide；
(3) carbon/silicon dioxide nanocomposite (C/SiO2) preparation:
By polystyrene/silica dioxide core-shell structure compound (PS/SiO2) 600-900 DEG C high-temperature calcination 2-6 hours, nitrogen Under atmosphere protection, carbon/silicon dioxide nanocomposite (C/SiO of hollow structure is obtained2), partial size 200-600nm；
(4) porous carbon/silicon nano-complex (C/Si) preparation:
0.25-0.35 parts by weight carbon/silicon dioxide nanocomposite 0.25-0.35 parts by weight magnesium powder is taken to grind in glove box mixed It closes uniformly, obtained mix powder is uniformly layered in aluminium oxide Noah's ark, is placed in tube furnace, 600- under argon atmosphere 800 DEG C reaction 2-6 hours, the obtained product salt acid elution of 1mol/L removes oxidation magnesium addition, is finally being dried in vacuo It is 10-18 hours dry in 70-90 DEG C in case, obtain porous carbon/silicon nano-complex (C/Si) of hollow structure, partial size 200- 600nm；
(5) preparation of the porous nano Si-C composite material (C/Si/C) of hollow structure:
It is slowly added to graphite composite powder into deionized water, stirs and graphite dispersing solution is made, then porous carbon/silicon nano-complex (C/Si) be added in graphite dispersing solution while stirring, graphite and silicon in mass ratio: 80~97 parts by weight of graphite, porous carbon/silicon 20~296 parts by weight of nano-complex (C/Si), adjustment dispersion fluid solid content is 15~25wt%, obtains porous carbon/silicon nanometer Compound (C/Si)/graphite composite dispersion liquid；Porous carbon/silicon nano-complex (C/Si)/graphite composite dispersion liquid is sprayed Mist is dry, is heat-treated within reaction 2-12 hours for 300-800 DEG C under inert gas protection, crushes, is sieved, obtain hollow structure Porous nano Si-C composite material (C/Si/C).
7. porous nano Si-C composite material according to claim 6, it is characterised in that the ethyl orthosilicate (TEOS) is excellent Select 1.0-2.0 parts by weight.
8. porous nano Si-C composite material according to claim 6, it is characterised in that reaction temperature is excellent in the tube furnace 600-680 DEG C is selected, the reaction time is 3-4 hours preferred, and porous carbon/silicon nano-complex (C/Si) partial size for obtaining hollow structure is excellent It is selected as 200-400nm.
9. porous nano Si-C composite material according to claim 6, it is characterised in that the graphite preferred natural graphite, people Make one or two kinds of mixtures of graphite.
10. preparation method according to claim 1, it is characterised in that porous carbon/silicon nano-complex (C/Si) be 20~ 40 parts by weight.
CN201811047837.6A 2018-09-04 2018-09-04 A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation Pending CN109244401A (en)

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