CN109292785A - A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof - Google Patents

A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof Download PDF

Info

Publication number
CN109292785A
CN109292785A CN201811327192.1A CN201811327192A CN109292785A CN 109292785 A CN109292785 A CN 109292785A CN 201811327192 A CN201811327192 A CN 201811327192A CN 109292785 A CN109292785 A CN 109292785A
Authority
CN
China
Prior art keywords
preparation
sio
sandwich type
certain amount
hybrid microspheres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811327192.1A
Other languages
Chinese (zh)
Inventor
陈志民
王瑞娟
冯磊
杨瑞华
孟迪
陈永
方明明
付建伟
陈加福
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Original Assignee
Zhengzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University filed Critical Zhengzhou University
Priority to CN201811327192.1A priority Critical patent/CN109292785A/en
Publication of CN109292785A publication Critical patent/CN109292785A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to field of new materials, in particular to a kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof.Using soft core/hard shell polystyrene microsphere of crosslinking as template, successively by ethyl orthosilicate in the hydrolysis of microsphere surface, dopamine in the polymerization and carbonization treatment process of microsphere surface, be prepared for hollow sandwich type C/SiO2/ C hybrid microspheres.The hollow sandwich type hybrid microspheres of this method preparation have many advantages, such as different of uniform size, good dispersion, each layer chemical constituent and cavity size and each shell thickness dimension adjustable, are the innovations of hollow carbon hybrid microspheres preparation method.

Description

A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof
Technical field
The invention belongs to field of new materials, in particular to a kind of hollow sandwich type C/SiO2/ C hybrid microspheres and its preparation Method.
Background technique
The rechargeable battery of high-energy density stores equipment, electric car and national grid electric power in portable electronic and deposits The fields such as storage have great application prospect.In order to meet, these fields are higher and higher to rechargeable battery energy density to be wanted It asks, exploitation has superelevation theoretical specific capacity (1672Ahkg-1) and energy density (2500Whkg-1) lithium-sulfur cell become for solution Certainly most means of feasibility in this problem.Currently, the critical issue encountered in lithium-sulfur cell research is how to solve it Elemental sulfur electric conductivity existing for positive electrode is poor, polysulfide " shuttle effect " and the problems such as structural stability, and this The solution key of a little problems is the structure and composition design of elemental sulfur carrier material.
Usually improve elemental sulfur electric conductivity mode be by elemental sulfur and conduction carbon material it is mutually compound, for this purpose, document Elemental sulfur has been loaded in the inside of hollow carbosphere by (Nano Lett. 2014,14,5250-5256.), although this is improved The electric conductivity of elemental sulfur, but since carbon is to the limited sorption capacity of polysulfide, it cannot solve in charge and discharge process very well " the shuttle effect " of polysulfide.Domestic applications number provide a kind of porous carbon ball packet for 201610051835.9 patent of invention The silicon/silicon dioxide nanocomposite wrapped up in.And the patent of invention that domestic applications number are 201610323865.0 then provides one The kind order mesoporous carbon ball composite material of the embedding sulphur of graphene coated.Although these materials, which pass through, and oxide is compound improves it to more The adsorption capacity of sulfide, but due to not having cavity structure, not only load sulfur content is low, while the structural stability of positive electrode Also poor.
Nano SiO 2 particle has size uniformity, large specific surface area, surface nature easy-regulating, thermal stability height, nothing Poison and the features such as good biocompatibility, therefore can be applicable to heterogeneous catalysis, host-guest chemistry, Environmental Technology and absorption etc. and lead Domain.Meanwhile the oxide particles such as silica are due to having stronger adsorptivity to polysulfide with polarity.If energy The composite hollow structure of silica and carbon is enough constructed out, it may be while improving the electric conductivity and useful load of elemental sulfur Carrier material is improved to the adsorption effect of polysulfide, to enhance the performance of entire lithium sulfur battery anode material.But single layer Carbon material and silica dioxide granule compound tense due to the bond strength of two kinds of storerooms it is poor, be easy to cause silica dioxide granule Fall off, if it is possible to silica dioxide granule layer to be fixed on to the structure for forming hollow sandwich type between two layers of carbon film, Effect that is fixed and preventing silica dioxide granule from falling off can be played.However up to the present, domestic patent of invention does not have also There is hollow sandwich type C/SiO2The report of/C hybrid microspheres preparation method.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of hollow sandwich type C/SiO2/ C hybrid microspheres and its preparation side Method.For this method using the crosslinked polystyrene microsphere of soft core/hard shell as template, the soft core of the polystyrene microsphere is linear polyphenyl second Alkene, hard shell are the polystyrene of divinyl benzene crosslinked, then pass through ethyl orthosilicate in the hydrolysis of Surfaces of Polystyrene Microparticles Construct raspberry shape polystyrene/silica dioxide complex microsphere.Then multiple in raspberry shape polystyrene/silica dioxide by dopamine The polymerization for closing microsphere surface, has obtained polystyrene/silica dioxide/poly-dopamine complex microsphere of sandwich type.Then pass through High temperature cabonization processing in a nitrogen atmosphere makes the soft core of polystyrene linear in the crosslinked polystyrene microsphere of soft core/hard shell point Solution forms hollow cavity, and the polystyrene hard shell of crosslinking is carbonized to form interior carbon shell, while converting outer carbon shell for poly-dopamine, most Hollow sandwich type C/SiO is obtained eventually2/ C hybrid microspheres.Since the microballoon is with hollow cavity, two layers of carbon shell and by receiving Rice silica composition oxide skin(coating), be expected to be used for lithium-sulfur cell domain variability solve its positive electrode faced at present it is more Kind problem.
A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof, which is characterized in that microballoon center tool There is hollow cavity, ball wall is made of inside and outside two layers of carbon shell, and the ingredient of internal layer carbon shell is common carbon material, and the ingredient of outer layer carbon shell is The carbon material of N doping, has nano SiO 2 particle layer between two layers of carbon shell, the cavity size of hollow hybrid microspheres, inside and outside Shell thickness and silicon dioxide layer particle size are adjustable.
The size of the hollow cavity of the microballoon can be adjusted between 210-550nm.
The internal layer carbon thickness of the shell of the microballoon can be adjusted between 10-30nm.
The middle layer nanometer silicon dioxide particle size of the microballoon can be adjusted between 40-100nm.
The outer layer carbon thickness of the shell of the microballoon can be adjusted between 35-110nm.
A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof, preparation process includes the following steps:
1) soft core/hard shell polystyrene (PS) microballoon preparation: measuring a certain amount of styrene, be added dropwise 120mL go from In sub- water, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, it is water-soluble that a certain amount of deionization containing potassium peroxydisulfate is then added Liquid stirs 4h as initiator at 70 DEG C, and a certain amount of cross-linker divinylbenzene and anti-is then added in the above system Soft core/hard shell polystyrene microsphere that diameter is 250-600nm should be can be obtained for 24 hours.
2) raspberry shape PS/ silica (SiO2) complex microsphere preparation: take the PS microballoon prepared in a certain amount of step 1) A certain amount of ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, so in a certain amount of ethyl alcohol for ultrasonic disperse A certain amount of ammonium hydroxide is added dropwise again afterwards and continues that raspberry shape PS/SiO can be obtained after stirring 10h2Complex microsphere.
3) sandwich type PS/SiO2The preparation of/poly-dopamine (PDA) complex microsphere: it takes and is prepared in a certain amount of step 2 The PS/SiO of raspberry shape2Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in a certain amount of volume ratio, is added one Trihydroxy aminomethane and dopamine are quantified, is mixed for 24 hours under room temperature, dopamine is in PS/SiO2Microsphere surface polymerization Obtain the PS/SiO of sandwich type2/ PDA organic/inorganic complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it with the heating rate of 2 DEG C/min, will be made in step 3) Standby all sandwich type polystyrene/silica dioxide/poly-dopamine complex microspheres are heated to 800 DEG C and are protected in nitrogen atmosphere Hollow sandwich type C/SiO can be obtained in warm 2h2/ C hybrid microspheres.
A kind of hollow sandwich type C/SiO provided by the present invention2/ C hybrid microspheres and preparation method thereof, with current report The hollow carbon hybrid microspheres in road are compared and are had the advantage that
1) hybrid microspheres prepared are of uniform size, good dispersion；
3) hybrid microspheres prepared have the C/SiO of hollow sandwich type2/ C hybrid structure；
3) hybrid microspheres hollow cavity size, inside and outside C thickness degree and the middle layer SiO prepared2The size of particle is controllable；
4) ingredient of two layers of carbon shell is different inside and outside the hybrid microspheres prepared, and internal layer carbon shell is common C film, and outer layer carbon shell is mixed for nitrogen Miscellaneous C film；
5) for silica dioxide granule layer at two layers between C layers, stable structure is not easily to fall off.
Detailed description of the invention
Fig. 1 is the hollow sandwich type C/SiO that the embodiment of the present invention 1 obtains2The transmission electron microscope of/C hybrid microspheres Photo.
Fig. 2 is the hollow sandwich type C/SiO that the embodiment of the present invention 1 obtains2The high-amplification-factor of/C hybrid microspheres transmits Electron micrograph.
Specific embodiment
Principles and features of the present invention are described with reference to embodiments, listed give an actual example is served only for explaining this hair It is bright, not limit the scope of the invention.
Embodiment 1:
1) soft core/hard shell PS microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water, is passed through high-purity Nitrogen gas stirring 30min is heated to 70 DEG C, the deionized water solution of 14mL potassium peroxydisulfate containing 0.16g is then added as initiator, 4h is stirred at 70 DEG C, then in the above system be added 1.8mL divinylbenzene the reaction was continued for 24 hours, can be obtained diameter is The soft core of 250nm/hard shell PS microballoon.
2) raspberry shape PS/SiO2The preparation of complex microsphere: take the PS microballoon ultrasonic disperse that is prepared in 0.5g step 1) in In 160mL ethyl alcohol, 1mL ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, 20mL ammonium hydroxide is then added dropwise again And continue that raspberry shape PS/SiO will be obtained after stirring 10h2Complex microsphere lotion drying for standby after centrifugal treating.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: the raspberry shape PS/SiO prepared in 0.5g step 2 is taken2 Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in 400mL volume ratio, and 1.5g trihydroxy aminomethane is added With 4.5g dopamine, it is mixed for 24 hours under room temperature, dopamine is in PS/SiO2Sandwich can be obtained in complex microsphere surface aggregate Type PS/SiO2/ PDA complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it with the heating rate of 2 DEG C/min, will be made in step 3) Standby all sandwich type polystyrene/silica dioxide/poly-dopamine complex microspheres are heated to 800 DEG C and are protected in nitrogen atmosphere Hollow sandwich type C/SiO can be obtained in warm 2h2/ C hybrid microspheres.
Fig. 1 is the hollow sandwich type C/SiO that the present embodiment obtains2The transmission electron microscope photo of/C hybrid microspheres, It can be seen that complex microsphere has good dispersibility.Fig. 2 is the hollow sandwich type C/SiO that the present embodiment obtains2/C The high-amplification-factor transmission electron microscope photo of hybrid microspheres, it can be seen that microballoon center has hollow cavity, it is micro- There is the nano SiO 2 particle of black inside spherical shell layer, these particles have been wrapped between two layers of carbon shell.
Embodiment 2:
1) soft core/hard shell polystyrene (PS) microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water In, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, the deionized water solution of 14mL potassium peroxydisulfate containing 0.12g is then added As initiator, 4h is stirred at 70 DEG C, then in the above system be added 1.8mL divinylbenzene the reaction was continued for 24 hours Obtain soft core/hard shell PS microballoon that diameter is 280nm.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 3:
1) soft core/hard shell polystyrene (PS) microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water In, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, the deionized water solution of 14mL potassium peroxydisulfate containing 0.08g is then added As initiator, 4h is stirred at 70 DEG C, then in the above system be added 1.8mL divinylbenzene the reaction was continued for 24 hours Obtain soft core/hard shell PS microballoon that diameter is 320nm.
2) it the preparation of PS/PDA complex microsphere: is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 4:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: take the PS microballoon ultrasonic disperse that is prepared in 0.5g step 1) in In 160mL ethyl alcohol, 1mL ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, 15mL ammonium hydroxide is then added dropwise again And continue that raspberry shape PS/SiO will be obtained after stirring 10h2Complex microsphere lotion drying for standby after centrifugal treating.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 5:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: take the PS microballoon ultrasonic disperse that is prepared in 0.5g step 1) in In 160mL ethyl alcohol, 1mL ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, 25mL ammonium hydroxide is then added dropwise again simultaneously Continue that raspberry shape PS/SiO will be obtained after stirring 10h2Complex microsphere lotion drying for standby after centrifugal treating.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 6:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: the raspberry shape PS/SiO prepared in 0.5g step 2 is taken2 Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in 400mL volume ratio, and 1.25g trihydroxy amino first is added Alkane and 3.75g dopamine are mixed for 24 hours under room temperature, and sandwich can be obtained in Surfaces of Polystyrene Microparticles polymerization in dopamine Type PS/SiO2/ PDA complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 7:
1) it soft core/hard shell polystyrene (PS) microballoon preparation: is carried out according to embodiment 1.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: the raspberry shape PS/SiO prepared in 0.5g step 2 is taken2 Complex microsphere ultrasonic disperse is ethyl alcohol: water=7: 1 in the mixed solvent in 400mL volume ratio, and 1.75g trihydroxy amino first is added Alkane and 5.25g dopamine are mixed for 24 hours under room temperature, and sandwich can be obtained in Surfaces of Polystyrene Microparticles polymerization in dopamine Type PS/SiO2/ PDA complex microsphere.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 8:
1) soft core/hard shell PS microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water, is passed through high-purity Nitrogen gas stirring 30min is heated to 70 DEG C, the deionized water solution of 14mL potassium peroxydisulfate containing 0.16g is then added as initiator, 4h is stirred at 70 DEG C, then in the above system be added 3.5mL divinylbenzene the reaction was continued for 24 hours, can be obtained diameter is The soft core of 275nm/hard shell PS microballoon.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Embodiment 9:
1) soft core/hard shell PS microballoon preparation: 8mL styrene is measured, is added dropwise in 120mL deionized water, is passed through high-purity Nitrogen gas stirring 30min is heated to 70 DEG C, the deionized water solution of 14mL potassium peroxydisulfate containing 0.16g is then added as initiator, 4h is stirred at 70 DEG C, then in the above system be added 5.3mL divinylbenzene the reaction was continued for 24 hours, can be obtained diameter is The soft core of 290nm/hard shell PS microballoon.
2) raspberry shape PS/SiO2The preparation of complex microsphere: it is carried out according to embodiment 1.
3) sandwich type PS/SiO2The preparation of/PDA complex microsphere: it is carried out according to embodiment 1.
4) hollow sandwich type C/SiO2The preparation of/C hybrid microspheres: it is carried out according to embodiment 1.
Hollow sandwich type C/SiO obtained by each embodiment2The structural parameters of/C hybrid microspheres are as shown in table 1.
Examples detailed above shows: preparing sandwich type PS/SiO using each embodiment2When/PDA complex microsphere, initiator is reduced Dosage can increase soft core/hard shell PS microballoon size, and then increase the cavity size of compound carbosphere, increase crosslinking agent diethyl The dosage of alkenyl benzene can increase the thickness of internal layer carbon shell, and the dosage for increasing ammonium hydroxide can increase the straight of nanometer silicon dioxide particle Diameter, and the dosage for increasing dopamine can then increase the thickness of outer layer carbon shell, to realize hollow sandwich type C/SiO2/ C hydridization The preparation of microballoon and its structure regulating.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (4)

1. a kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof, which is characterized in that during the microballoon center has Absolutely empty chamber, internal layer are common carbon film layer, and middle layer is nanometer silicon dioxide particle layer, and outer layer is the carbon film layer of N doping.
2. hollow sandwich type C/SiO according to claim 12/ C hybrid microspheres and preparation method thereof, which is characterized in that The size of the microballoon hollow cavity can be adjusted between 210-550nm.
3. hollow sandwich type C/SiO according to claim 12/ C hybrid microspheres and preparation method thereof, it is characterised in that should The thickness that C layers of microballoon internal layer can be adjusted between 10-30nm, and the nanometer silicon dioxide particle size of middle layer can be in 40- It is adjusted between 100nm, the thickness that C layers of outer layer can be adjusted between 35-110nm.
4. hollow sandwich type C/SiO described in one of -3 according to claim 12/ C hybrid microspheres and preparation method thereof, preparation Process includes the following steps: 1. soft core/hard shell polystyrene microsphere preparation: measuring a certain amount of styrene, is added dropwise In 120mL deionized water, it is passed through high pure nitrogen stirring 30min, 70 DEG C is heated to, is then added and a certain amount of is gone containing potassium peroxydisulfate Deionized water solution stirs 4h as initiator at 70 DEG C, and a certain amount of crosslinking agent divinyl is then added in the above system Base benzo reacts the soft core/hard shell polystyrene microsphere that can be obtained that diameter is 250-600nm for 24 hours；2. raspberry shape polyphenyl second The preparation of alkene/SiO 2 composite microsphere: take a certain amount of step 1. in prepare polystyrene microsphere ultrasonic disperse in a certain amount of Ethyl alcohol in, a certain amount of ethyl orthosilicate is then added into above-mentioned solution and stirs 30min, is then added dropwise again a certain amount of Ammonium hydroxide simultaneously continues that raspberry shape polystyrene/silica dioxide complex microsphere can be obtained after stirring 10h；3. sandwich type polyphenyl second The preparation of alkene/silica/poly-dopamine complex microsphere: a certain amount of step 2. middle raspberry shape polystyrene/dioxy prepared is taken SiClx complex microsphere ultrasonic disperse is ethyl alcohol in a certain amount of volume ratio: water=7: a certain amount of trihydroxy is added in 1 in the mixed solvent Aminomethane and dopamine are mixed for 24 hours under room temperature, and dopamine polymerize in polystyrene/silica dioxide microsphere surface Obtain polystyrene/silica dioxide/poly-dopamine organic/inorganic complex microsphere of sandwich type；4. hollow sandwich type C/ SiO2The preparation of/C hybrid microspheres: with the heating rate of 2 DEG C/min, by step 3. in all sandwich type polyphenyl second for preparing Alkene/silica/poly-dopamine complex microsphere is heated to 800 DEG C in nitrogen atmosphere and keeps the temperature 2h, and hollow Sanming City can be obtained Control type C/SiO2/ C hybrid microspheres.
CN201811327192.1A 2018-11-08 2018-11-08 A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof Pending CN109292785A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811327192.1A CN109292785A (en) 2018-11-08 2018-11-08 A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811327192.1A CN109292785A (en) 2018-11-08 2018-11-08 A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109292785A true CN109292785A (en) 2019-02-01

Family

ID=65145993

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811327192.1A Pending CN109292785A (en) 2018-11-08 2018-11-08 A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109292785A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111495416A (en) * 2020-06-12 2020-08-07 郑州大学 Hollow cage-shaped double-shell carbon/Ru composite microsphere for hydrogen production by electrolyzing water and preparation method thereof
CN111825860A (en) * 2020-06-16 2020-10-27 广州特种承压设备检测研究院 Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof
CN112645327A (en) * 2020-12-21 2021-04-13 中国烟草总公司郑州烟草研究院 Preparation method of porous carbon core-shell composite material
CN113845108A (en) * 2021-10-29 2021-12-28 郑州大学 Hollow carbon bowl with adjustable shell layer distance and shell thickness and preparation method thereof
CN117534058A (en) * 2024-01-04 2024-02-09 内蒙古大学 High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104319402A (en) * 2014-10-28 2015-01-28 上海交通大学 Preparation method for multi-layer carbon hollow sphere anode material
CN108242538A (en) * 2017-12-27 2018-07-03 轻工业化学电源研究所 A kind of preparation method of hollow sandwich type iron-based negative material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104319402A (en) * 2014-10-28 2015-01-28 上海交通大学 Preparation method for multi-layer carbon hollow sphere anode material
CN108242538A (en) * 2017-12-27 2018-07-03 轻工业化学电源研究所 A kind of preparation method of hollow sandwich type iron-based negative material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MINGMING FANG，等: "Design and synthesis of novel sandwich-type C@TiO2@C hollow microspheres as efficient sulfur hosts for advanced lithium–sulfur batteries", 《J. MATER. CHEM. A》 *
田秋格: "高温热解法制备笼状中空碳球-聚苯乙烯大孔膜及其结构和组分的调控", 《万方数据知识服务平台》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111495416A (en) * 2020-06-12 2020-08-07 郑州大学 Hollow cage-shaped double-shell carbon/Ru composite microsphere for hydrogen production by electrolyzing water and preparation method thereof
CN111495416B (en) * 2020-06-12 2022-11-11 郑州大学 Hollow cage-shaped double-shell carbon/Ru composite microsphere for hydrogen production by electrolyzing water and preparation method thereof
CN111825860A (en) * 2020-06-16 2020-10-27 广州特种承压设备检测研究院 Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof
CN112645327A (en) * 2020-12-21 2021-04-13 中国烟草总公司郑州烟草研究院 Preparation method of porous carbon core-shell composite material
CN113845108A (en) * 2021-10-29 2021-12-28 郑州大学 Hollow carbon bowl with adjustable shell layer distance and shell thickness and preparation method thereof
CN117534058A (en) * 2024-01-04 2024-02-09 内蒙古大学 High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof
CN117534058B (en) * 2024-01-04 2024-03-29 内蒙古大学 High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof

Similar Documents

Publication Publication Date Title
Lin et al. Fiber network composed of interconnected yolk-shell carbon nanospheres for high-performance lithium-sulfur batteries
CN109292785A (en) A kind of hollow sandwich type C/SiO2/ C hybrid microspheres and preparation method thereof
Zhang et al. Boron heteroatom-doped silicon–carbon peanut-like composites enables long life lithium-ion batteries
Pei et al. From hollow carbon spheres to N‐doped hollow porous carbon bowls: rational design of hollow carbon host for Li‐S batteries
Zhang et al. Double-shelled hollow carbon sphere with microporous outer shell towards high performance lithium-sulfur battery
CN106207108B (en) Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon
CN104466142B (en) A kind of silicon/silica carbon/composite cathode material of silicon/carbon/graphite for lithium ion battery
Gu et al. Confined Volume Change in Sn‐Co‐C Ternary Tube‐in‐Tube Composites for High‐Capacity and Long‐Life Lithium Storage
KR20210084657A (en) Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof
Ma et al. Enhancement of long stability of Li–S battery by thin wall hollow spherical structured polypyrrole based sulfur cathode
KR102250814B1 (en) Carbon-coated composites containing graphenes, silicon nanoparticles, and carbon nanotubes for lithium secondary battery anode, and preparation method of the same
CN105280890B (en) A kind of core shell structure silicon-carbon composite cathode material and preparation method thereof
CN105226241B (en) A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof
CN109354007A (en) A kind of regulatable bivalve layer hollow caged carbosphere of foreign components of structure
CN108448101B (en) Lithium-sulfur battery positive electrode material and preparation method and application thereof
Wang et al. Separator modified by Y 2 O 3 nanoparticles-Ketjen Black hybrid and its application in lithium-sulfur battery
CN107768617A (en) Lithium-sulfur battery composite anode material and preparation method thereof
Peng et al. Insight into the performance of the mesoporous structure SiOx nanoparticles anchored on carbon fibers as anode material of lithium-ion batteries
Tang et al. Polyaniline-coated activated carbon aerogel/sulfur composite for high-performance lithium-sulfur battery
Liu et al. A Polysulfides‐Confined All‐in‐One Porous Microcapsule Lithium–Sulfur Battery Cathode
CN109802128A (en) A kind of lithium-sulphur cell positive electrode sulphur/silica/polyaniline nuclear-shell structured nano-composite material and preparation method
Ma et al. To achieve controlled specific capacities of silicon-based anodes for high-performance lithium-ion batteries
Guo et al. Controlled synthesis of porous carbon nanostructures with tunable closed mesopores via a silica-assisted coassembly strategy
CN101521273B (en) In-situ synthesis method for preparing tin-carbon/core-shell nano-particle fully filled carbon nano-tube composite anode material
JP7252988B2 (en) Prelithiated negative electrode, method of making same, lithium ion battery containing prelithiated negative electrode, and supercapacitor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190201