CN105006559B - A kind of core shell structure of graphene coated silicon or its oxide and preparation method thereof - Google Patents
A kind of core shell structure of graphene coated silicon or its oxide and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000010703 silicon Substances 0.000 title claims abstract description 97
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000011258 core-shell material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 106
- 239000012530 fluid Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003595 mist Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 66
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 34
- 229910052786 argon Inorganic materials 0.000 claims description 33
- 230000001788 irregular Effects 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229920000945 Amylopectin Polymers 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 238000010924 continuous production Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 81
- 239000000047 product Substances 0.000 description 43
- 239000008187 granular material Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- 238000000151 deposition Methods 0.000 description 16
- 230000008021 deposition Effects 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 15
- 239000010439 graphite Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229920002472 Starch Polymers 0.000 description 14
- 239000012159 carrier gas Substances 0.000 description 14
- 238000011049 filling Methods 0.000 description 14
- 239000008246 gaseous mixture Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 229910052814 silicon oxide Inorganic materials 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 235000019698 starch Nutrition 0.000 description 14
- 239000008107 starch Substances 0.000 description 14
- 238000010792 warming Methods 0.000 description 14
- 239000000084 colloidal system Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- 239000000416 hydrocolloid Substances 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- -1 graphene alkene Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Silicon Compounds (AREA)
Abstract
A kind of core shell structure of graphene coated silicon or its oxide and preparation method thereof, the core shell structure is using the Asia/micron particles of silicon or its oxide as core, graphene for shell, grain size is 0.05 15 μm, the graphene number of plies is 5 30 layers, the weight of graphene is accounted between 1 8wt% of core-shell structure particles gross weight, and the specific surface area of the core shell structure is equal to or less than original silicon or the specific surface area of its oxide particle.The present invention utilizes the equipment such as mist projection granulating, fluid bed, vibratory sieve, air-flow crushing, the technical process that the secondary structure assembling, the growth of graphene shell and secondary structure of silicon or its oxide particle independently crush is completed, finally gives the core shell structure product for meeting above-mentioned requirements.Because obtained core-shell structure not only has silicon or the property of its oxide, while also there are some characteristics of graphene, therefore it is with a wide range of applications in electrochemical industry.Meanwhile fluidized-bed reactor can realize continuous production, whole technique can realize industrialization.
Description
Technical field
The present invention relates to core shell structure of a kind of graphene coated silicon or its oxide and preparation method thereof, belong to new energy
Material and its preparing technical field.
Background technology
Early in 1991, first generation commercial li-ion battery was invented by Sony companies so that the electronic device such as mobile phone it is general
And become possibility.It experienced the development of more than 20 years, the species and performance of mobile electronic device have occurred that huge
Change, it is lighter, stand-by time is longer, quickly charging, flexibility, safety and environmental protection etc., people battery system is proposed again one
The new requirement of series.Moreover, the fast development of electric automobile and hybrid vehicle in recent years, also further excites people
For high-energy-density and the electrokinetic cell of high power density demand and exploration.
According to the part of battery system --- positive electrode, negative material, barrier film, electrolyte, collector and packaging
Shell etc., it can be found that the performance of battery depends primarily on the specific capacity performance of positive and negative electrode material.For negative material
Speech, commercial Li-ion battery is generally using graphite carbon material as negative pole at present, and the theoretical capacity of graphite is only 372mAh/
G, which greatly limits the further development of lithium ion battery.As the silicium cathode with highest theoretical specific capacity, its theoretical ratio
Capacity can reach 4200mAh/g, be the ideal chose of high-energy-density negative material of new generation.However, in the application of reality
During, the capacity attenuation of silicium cathode is too fast, causes the poor circulation of battery, turns into silicium cathode commercialization and has to what is solved
One of problem.
In terms of the electrochemical cycle stability of silicon or its oxide is improved, forefathers have done substantial amounts of work.One side
Face, researcher are wished by the way that silicon grain nanosizing and the specific nanostructured of design are improved caused by volumetric expansion
Capacity attenuation, such as aligned nanowires (Cui Y, et al.Nature Nanotechnology, 2008,3:31-35), nanometer
Manage (Jaephil Cho, et al.Nano Letter, 2009,9 (11):3844-3847), nanofiber (Lee YM, Park
JK,et al.ACS Appl.Mater.Interfaces,2013,5(22):12005-12010) the silicon multilevel hierarchy such as.From experiment
As a result from the point of view of, nanosizing can actually improve the cycle performance of battery to a certain extent.However, in the business application of reality
In, these novel structures are but faced with the problems such as preparation process is complicated, growth conditions is harsh and cost is too high, therefore at present
Large batch of preparation can not also be realized.Moreover, these nano-silicons usually require to add carbon black to strengthen intergranular conduction
Property.For such situation, if can uniformly be wrapped in different nanometer or micron silicon or its oxide particle surface
Form the few-layer graphene alkene is covered, can not only so improve the material caused by Volume Changes occur during embedding lithium ionic insertion/deinsertion well
The problem of feed powder and secondary agglomeration, additionally it is possible to by the superpower electron transfer characteristic of graphene itself, strengthen between particle
And the electric conductivity between particle and collector.
According to the difference of particle surface carbon coating method, hydrothermal carbonization, high temperature cabonization and chemical gas can be largely classified into
Mutually three kinds of deposition.Either hydrothermal carbonization or high temperature cabonization (ten thousand vertical fine horses etc., patent publication No.：101931076A), all it is pre-
The raw material for being first readily able to be dehydrated carries out physical mixed with active particle (silicon or its oxide), then in high temperature or hydro-thermal
In the environment of occur carbonization and be wrapped in active particle surface.Liquid or solid carbon source and silicon or its oxidation due to generally use
Density variation between thing be present, the uniformity of physical mixed is difficult to ensure that, especially during production in enormous quantities, in product
Easily contain micropore carbon impurity.And some surfactants can be realized in activity as carbon source by weak chemical interactions
Grain top layer coats and is carbonized, but itself expensive cost and the requirement for active particle pattern and surface characteristic,
Making its industrialization, there is also bigger difficulty.Moreover, the carbon products that dehydration carbonization obtains usually contain abundant micropore, than
Surface area is big, and SEI film (solid electrolyte interface, solid electrolyte interface are formed in electrode material surface
Film) during, it is necessary to consume more lithiums, reduce the coulombic efficiency of first circle discharge and recharge, increase battery cost.Comparatively speaking,
The carbon coating layer that chemical vapor deposition is formed is mainly graphitic carbon, has good electric conductivity, and substantially without micropore
Formed, the specific surface area of the silicon-carbon compound formed is small compared with the specific surface area of original silicon or its oxide particle.Consider
Fluid bed have preferably heat transfer and mass-transfer efficiency, using its as reactor realize the different nanoscale of pattern or micron silicon or its
The chemical vapor carbon deposition cladding process of oxide surface, has important engineering significance.
The content of the invention
It is an object of the invention to provide core shell structure of a kind of graphene coated silicon or its oxide and preparation method thereof,
Make its core shell structure formed on the one hand can reduce it to crush because embedding lithium takes off lithium, improve cycle performance of battery,
On the other hand be advantageous to increase intergranular electric conductivity, conductive additive dosage can be reduced and reduce the internal resistance of cell, so that
Electrochemical industry is with a wide range of applications, while can realize continuous industrialization generation.
Technical scheme is as follows：
A kind of core shell structure of graphene coated silicon or its oxide, it is characterised in that：The core shell structure be with silicon or its
The nanometer or micron particles that oxide is core, graphene is shell, grain size are 0.05~15 μm；The number of plies of graphene shell is 5
~30 layers, the weight of graphene accounts for 1~8wt% of core-shell structure particles gross weight, and the specific surface area of the core shell structure is equal to
Or the specific surface area less than original silicon or its oxide particle.
Core shell structure of the present invention is further characterized in that：The core shell structure is in crystal or amorphous state, its macro morphology
For the mixture of spherical, bar-shaped, sheet, irregular polyhedronses or two or more patterns in them.
The preparation method of the core shell structure of a kind of graphene coated silicon provided by the invention or its oxide, it is characterised in that
This method comprises the following steps：
5) carbon binder at normal temperatures, will be contained to be dissolved in deionized water, persistently stir and be to slowly warm up to 50~100 DEG C,
Keep constant temperature 1~6 hour, obtain viscous liquid；
6) particle diameter is added in the viscous liquid prepared by step 1) for 0.1~10 μm of silicon or its oxide particle,
It is 30~60wt% suspension slurries that stirring, which obtains solid content,；
7) slurry for obtaining step 2) carries out mist projection granulating, obtains porous ball of the particle diameter distribution between 50~300 μm
Shape particle, i.e. secondary structure particle；
8) secondary structure obtained step 3) is particles filled into fluid bed, is heated to reaction temperature in an inert atmosphere
700~1000 DEG C, then pass to carbon source, total air speed of inert gas and carbon source is 500~900h-1, keep carbon source and indifferent gas
The volume ratio of body carries out chemical vapor deposition, the reaction time is 20~60min, and obtaining grain size is between 0.5~2
The silicon of 0.05~15 μm of graphene coated or its oxide core shell structure.
In the method for the invention, it is characterised in that：Species containing carbon binder include straight chain, amylopectin, glucose,
Polysaccharide or polyhydroxy-alcohol；Mass ratio containing carbon binder and silicon or its oxide particle is between 0.0005~0.03.
In the method for the present invention, mist projection granulating described in step 3) selects atomizer comminutor, charging rate 0.5
~2L/h, between inlet temperature is 280~350 DEG C, rotating speed of shower nozzle is 10~20r/min.
In the method for the present invention, height of secondary structure particle packing described in step 4) in fluidized-bed reactor is stream
Change bed diameter 1~3 times；The carbon source is one kind or several in methane, ethane, ethene, acetylene, propane, propylene, benzene and toluene
The combination of kind；The inert gas is nitrogen, argon gas or the mixture of the two.
The method of the present invention, is further characterized in that：The silicon of the graphene coated obtained in step 4) or its oxide core shell
Structure, which is sent into vibrating sieving machine, carries out product separation, the secondary structure particle not disintegrated for small part, using air-flow crushing, again
It is added to progress graphene shell cladding in fluidized-bed reactor.
The present invention compared with prior art, has the following advantages that and the technique effect of high-lighting：1. realize form the few-layer graphene alkene (5-
30 layers) abnormity, nanometer or micron silicon or its oxide particle surface uniformly coat, the core shell structure formed is on the one hand
It can be reduced to crush because embedding lithium takes off lithium, cycle performance of battery is improved, be on the other hand advantageous to increase intergranular
Electric conductivity, conductive additive dosage can be reduced and reduce the internal resistance of cell；2. the specific surface area of core-shell structure particles is equal to or small
In the specific surface area of original silicon or its oxide particle, extra SEI layers will not be formed, reduce the dosage of positive pole lithium-containing materials,
Advantageously reduce battery cost；3) carbon source used in this method is cheap and easy to get, and fluidized-bed process is easy to engineering amplification and batch
Production.
Brief description of the drawings：
Fig. 1 is the stereoscan photograph of sub-micro level or micron silicon original powder.
Fig. 2 is that nanometer or micron silicon are granulated to obtain the stereoscan photograph of micron-size spherical particles.
Fig. 3 is the stereoscan photograph of nanometer or micron silicon cladding form the few-layer graphene alkene material.
Fig. 4 is the transmission electron microscope photo of nanometer or micron silicon cladding form the few-layer graphene alkene material.
Embodiment
The core shell structure of a kind of graphene coated silicon provided by the invention or its oxide, be using silicon or its oxide as
Core, the nanometer or micron particles that graphene is shell, grain size are 0.05~15 μm；The number of plies of graphene shell is 5~30 layers, stone
The weight of black alkene is accounted between 1~8wt% of core-shell structure particles gross weight, and the specific surface area of the core shell structure is equal to or less than
The specific surface area of original silicon or its oxide particle；The core shell structure is in crystal or amorphous state, and its macro morphology is spherical, rod
Shape, sheet, the mixture of irregular polyhedronses or two or more patterns in them.
The preparation method of the core shell structure of graphene coated silicon of the present invention or its oxide comprises the following steps：
1) carbon binder at normal temperatures, will be contained to be dissolved in deionized water, persistently stir and be to slowly warm up to 50-100 DEG C, guarantor
Constant temperature 1-6 hours are held, obtain viscous liquid；
2) particle diameter is added in the viscous liquid prepared by step 1) for 0.1-10 μm of silicon or its oxide particle, stirred
It is 30-60wt% suspension slurries to mix to obtain solid content；
3) slurry for obtaining step 2) carries out mist projection granulating, obtains porous spherical of the particle diameter distribution between 50-300 μm
Particle, i.e. secondary structure particle；
4) secondary structure obtained step 3) is particles filled into fluid bed, is heated to reaction temperature in an inert atmosphere
700-1000 DEG C, then pass to carbon source, total air speed of inert gas and carbon source is 500-900h-1, keep carbon source and inert gas
Volume ratio between 0.5-2, carry out chemical vapor deposition, reaction time 20-60min, it is 0.05-15 to obtain grain size
μm graphene coated silicon or its oxide core shell structure；
Wherein, the macro morphology of silicon or its oxide particle can be spherical, bar-shaped, sheet, irregular polyhedronses and
The mixture of above pattern.Species containing carbon binder includes straight chain, amylopectin, glucose, polysaccharide, polyhydroxy-alcohol etc.；
Mass ratio containing carbon binder and silicon or its oxide particle is between 0.0005-0.03.In a fluidized bed reactor, filling is high
Spend for the silicon or its oxide secondary structure particle of 1-3 times of fluid bed diameter；Carbon source is methane, ethane, ethene, acetylene, third
One or more of combinations in alkane, propylene, benzene and toluene；Inert gas be nitrogen, argon gas or the two mix according to a certain percentage
Close gained.Because in graphene shell growth course, the secondary structure particle in fluidized state can disintegrate due to collision,
The nucleocapsid product that grain size is distributed in 0.05-15 μm is obtained, product separation is carried out using vibrating sieving machine, and for small part not
The secondary structure particle of disintegration, air-flow crushing will be used, and rejoin progress graphene shell cladding in fluid bed.
Below by several specific embodiments, the present invention is further illustrated.
Embodiment 1：Fluid bed nanometer or micron order prepare silicon-graphene Core-shell structure material
It is that 0.75wt% amylopectin is added to the water by mass percent, stirring is warming up to 80 DEG C, constant temperature 2 under normal temperature
Transparent colloid is obtained after hour.By irregular pattern, particle size be 0.1-10 μm of silicon grain (such as Fig. 1) be added to amylan
In body, wherein solid content is 50wt% (starch/silicon grain=0.0075, mass ratio), is stirred 2 hours under 80 DEG C of constant temperatures
Obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate 1L/h, nozzle temperature
For 320 DEG C, rotating speed 15r/min, obtained product is the spheric granules that porous, size is 50-300 μm, as shown in Figure 2.
In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, the use of argon gas is carrier gas, flow 45L/
h.Temperature of reactor is raised to by 850 DEG C of pretreatment temperature, constant temperature by room temperature with 20 DEG C/min heating rate under the atmosphere
After 5min, the gaseous mixture of propylene and argon gas, wherein propylene are passed through：The volume ratio of argon gas is 1:1, control the total air speed of course of reaction to be
600h-1, carry out chemical vapor deposition processes.Carbon source propylene is closed after 30min, is taken out admittedly after being cooled to room temperature under an argon atmosphere
Phase product.Electron microscopic observation is scanned through, the pattern of the silicon grain of graphene coated is similar with original silicon grain pattern, Size Distribution
Between 0.05-15 μm.As shown in figure 4, under high-resolution-ration transmission electric-lens photo, silicon grain surface is it can be seen that clearly graphite
Rotating fields.In Raman collection of illustrative plates, also with the presence of obvious G peaks, the carbon for illustrating silicon grain surface is mainly form the few-layer graphene alkene structure.
Thermogravimetric result shows that the carbon deposition quantity on silicon grain surface reaches 3.9wt% under the conditions of being somebody's turn to do.Under 77K, isothermal N2 adsorption curve shows,
There is no micropore presence, specific surface area 3.8m in the product2/ g, the specific surface area (4.2m original less than silicon grain2/g)。
Embodiment 2：Fluid bed prepares nanometer or micron silicon-graphene Core-shell structure material
It is that 0.5wt% amylopectin is added to the water by mass percent, stirring is warming up to 75 DEG C, constant temperature 1.5 under normal temperature
Transparent colloid is obtained after hour.By irregular pattern, particle size be 0.1-10 μm of silicon grain be added in starch-hydrocolloid, its
Middle solid content is 60wt% (starch/silicon grain=0.0033, mass ratio), stirs 2.5 hours and obtains under 75 DEG C of constant temperatures
Suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate 0.8L/h, nozzle temperature is
300 DEG C, rotating speed 17r/min, obtained product is the spheric granules that porous, size is 50-200 μm.In fluid bed, dress
Raising degree is the above-mentioned spheric granules of 1 times of fluid bed diameter, the use of argon gas is carrier gas, flow 45L/h.Under the atmosphere with
Temperature of reactor is raised to 850 DEG C of pretreatment temperature by 20 DEG C/min heating rate by room temperature, after constant temperature 5min, be passed through propylene and
The gaseous mixture of argon gas, wherein propylene：The volume ratio of argon gas is 1:1, it is 650h to control the total air speed of course of reaction-1, carry out chemical gas
Phase deposition process.Product is blown out after reaction 40min, rejoins the catalyst with first time phase homogenous quantities, is carried out continuous anti-
Should.Products therefrom is by cooling, shake sieve, obtains the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted electron
Under microscope, particle surface has clear graphite linings clad structure, carbon deposition quantity 4.8wt%, and the specific surface area of product
(4.1m2/ g) it is less than the original specific surface area (4.2m of silicon grain2/g)。
Embodiment 3：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.5wt% amylopectin is added to the water by mass percent, stirring is warming up to 90 DEG C, and constant temperature 3 is small under normal temperature
When after obtain transparent colloid.By irregular pattern, particle size be 0.1-10 μm of Si oxide SiO particle be added to amylan
In body, wherein solid content is 60wt% (starch/silicon grain=0.0033, mass ratio), is stirred 4 hours under 90 DEG C of constant temperatures
Obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate 0.6L/h, shower nozzle temperature
Spend for 340 DEG C, rotating speed 12r/min, obtained product is the spheric granules that porous, size is 80-300 μm.In fluid bed
In, filling height is the above-mentioned spheric granules of 2.5 times of fluid bed diameters, the use of nitrogen is carrier gas, flow 60L/h.At this
Temperature of reactor is raised to by room temperature by 880 DEG C of pretreatment temperature with 40 DEG C/min heating rate under atmosphere, after constant temperature 5min, led to
Enter the gaseous mixture of propylene and nitrogen, wherein propylene：The volume ratio of nitrogen is 2:3, it is 800h to control the total air speed of course of reaction-1, enter
Row chemical vapor deposition processes.Carbon source propylene is closed after 45min, solid product is taken out after being cooled to room temperature in a nitrogen atmosphere.
Sieved through cross to shake, obtain the irregular particle that size is mainly distributed between 0.05-15 μm, under transmission electron microscope, particle table
Face has the specific surface area (2.8m of clear graphite linings clad structure, carbon deposition quantity 5.2wt%, and product2/ g) it is less than silicon
Original specific surface area (the 3.2m of grain2/g)。
Embodiment 4：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.3wt% amylopectin is added to the water by mass percent, stirring is warming up to 100 DEG C, constant temperature 6 under normal temperature
Transparent colloid is obtained after hour.By irregular pattern, particle size be 0.1-10 μm of Si oxide Si oxide (SiOx, 0<x
<2) particle is added in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.003, mass ratio), at 100 DEG C
Stirred 3 hours under constant temperature and obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, fed
Speed is 1.2L/h, and nozzle temperature is 340 DEG C, rotating speed 13r/min, and obtained product is porous, size is 50-250 μm
Spheric granules.In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, the use of nitrogen is carrier gas,
Flow is 40L/h.Temperature of reactor is raised to by pretreatment temperature 750 by room temperature with 25 DEG C/min heating rate under the atmosphere
DEG C, after constant temperature 5min, it is passed through the gaseous mixture of ethene and nitrogen, wherein ethene：The volume ratio of nitrogen is 1:1, control course of reaction
Total air speed is 500h-1, carry out chemical vapor deposition processes.Carbon source ethene is closed after 50min, is cooled to room temperature in a nitrogen atmosphere
After take out solid product.Sieved through cross to shake, mainly obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted
Under electron microscope, particle surface has the ratio surface of clear graphite linings clad structure, carbon deposition quantity 2.8wt%, and product
Product (2.4m2/ g) it is less than the original specific surface area (3.2m of silicon grain2/g)。
Embodiment 5：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.1wt% amylopectin is added to the water by mass percent, stirring is warming up to 100 DEG C, constant temperature 2 under normal temperature
Transparent colloid is obtained after hour.By irregular pattern, particle size be 0.1-10 μm of Si oxide Si oxide (SiOx, 0<x
<2) particle is added in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.001, mass ratio), at 100 DEG C
Stirred 3 hours under constant temperature and obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, fed
Speed is 2.0L/h, and nozzle temperature is 350 DEG C, rotating speed 15r/min, and obtained product is porous, size is 50-220 μm
Spheric granules.In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, the use of argon gas is carrier gas,
Flow is 50L/h.Temperature of reactor is raised to by pretreatment temperature 800 by room temperature with 30 DEG C/min heating rate under the atmosphere
DEG C, after constant temperature 5min, it is passed through the gaseous mixture of ethene and argon gas, wherein ethene：The volume ratio of argon gas is 2:3, control course of reaction
Total air speed is 650h-1, carry out chemical vapor deposition processes.Carbon source ethene is closed after 35min, is cooled to room temperature under an argon atmosphere
After take out solid product.Sieved through cross to shake, mainly obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted
Under electron microscope, particle surface has the ratio surface of clear graphite linings clad structure, carbon deposition quantity 1.0wt%, and product
Product (2.2m2/ g) it is less than the original specific surface area (3.2m of silicon grain2/g)。
Embodiment 6：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.05wt% amylopectin is added to the water by mass percent, stirring is warming up to 85 DEG C, constant temperature 1 under normal temperature
Transparent colloid is obtained after hour.By irregular pattern, particle size be 0.1-10 μm of Si oxide Si oxide (SiOx, 0<x
<2) particle is added in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.0005, mass ratio), at 85 DEG C
Stirred 3 hours under constant temperature and obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, fed
Speed is 0.5L/h, and nozzle temperature is 280 DEG C, rotating speed 20r/min, and obtained product is porous, size is 50-180 μm
Spheric granules.In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, the use of argon gas is carrier gas,
Flow is 50L/h.Temperature of reactor is raised to by pretreatment temperature 900 by room temperature with 20 DEG C/min heating rate under the atmosphere
DEG C, after constant temperature 5min, it is passed through the gaseous mixture of ethene and argon gas, wherein ethene：The volume ratio of argon gas is 2:3, control course of reaction
Total air speed is 650h-1, carry out chemical vapor deposition processes.Carbon source ethene is closed after 60min, is cooled to room temperature under an argon atmosphere
After take out solid product.Sieved through cross to shake, mainly obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted
Under electron microscope, particle surface has the ratio surface of clear graphite linings clad structure, carbon deposition quantity 5.0wt%, and product
Product (3.2m2/ g) it is less than the original specific surface area (4.1m of silicon grain2/g)。
Embodiment 7：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 3wt% amyloses are added to the water by mass percent, stirring is warming up to 90 DEG C, constant temperature 3 hours under normal temperature
After obtain transparent colloid.By irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle adds
Into starch-hydrocolloid, wherein solid content is 50wt% (starch/silicon grain=0.03, mass ratio), is stirred under 90 DEG C of constant temperatures
Mix 2 hours and obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate 1.8L/
H, nozzle temperature are 330 DEG C, rotating speed 12r/min, and obtained product is the spheric granules that porous, size is 70-280 μm.
In fluid bed, filling height is the above-mentioned spheric granules of 2.5 times of fluid bed diameters, the use of argon gas is carrier gas, flow is
60L/h.Temperature of reactor is raised to by 850 DEG C of pretreatment temperature by room temperature with 25 DEG C/min heating rate under the atmosphere, it is permanent
After warm 5min, the gaseous mixture of ethene and argon gas, wherein ethene are passed through：The volume ratio of argon gas is 3:2, control the total air speed of course of reaction
For 600h-1, carry out chemical vapor deposition processes.Carbon source ethene is closed after 35min, is taken out after being cooled to room temperature under an argon atmosphere
Solid product.Sieved through cross to shake, mainly obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted electron shows
Under micro mirror, particle surface has clear graphite linings clad structure, carbon deposition quantity 6.2wt%, and the specific surface area of product
(2.9m2/ g) it is less than the original specific surface area (3.2m of silicon grain2/g)。
Embodiment 8：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 1wt% amyloses are added to the water by mass percent, stirring is warming up to 100 DEG C, and constant temperature 2 is small under normal temperature
When after obtain transparent colloid.By irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle adds
Enter into starch-hydrocolloid, wherein solid content is 60wt% (starch/silicon grain=0.0067, mass ratio), in 100 DEG C of constant temperatures
Lower stirring obtains suspension slurry in 2 hours.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate is
1.0L/h, nozzle temperature are 320 DEG C, rotating speed 12r/min, and obtained product is that porous, size is 60-240 μm spherical
Particle.In fluid bed, filling height is the above-mentioned spheric granules of 2.5 times of fluid bed diameters, the use of nitrogen is carrier gas, flow
For 60L/h.Temperature of reactor is raised to by 800 DEG C of pretreatment temperature by room temperature with 25 DEG C/min heating rate under the atmosphere,
After constant temperature 5min, the gaseous mixture of ethene and nitrogen, wherein ethene are passed through：The volume ratio of nitrogen is 1:1, control course of reaction is always empty
Speed is 600h-1, carry out chemical vapor deposition processes.Carbon source ethene is closed after 20min, is taken after being cooled to room temperature in a nitrogen atmosphere
Go out solid product.Sieved through cross to shake, mainly obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted electron
Under microscope, particle surface has clear graphite linings clad structure, carbon deposition quantity 5.4wt%, and the specific surface area of product
(4.2m2/ g) it is less than the original specific surface area (4.8m of silicon grain2/g)。
Embodiment 9：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.3wt% amylopectin is added to the water by mass percent, stirring is warming up to 90 DEG C, and constant temperature 1 is small under normal temperature
When after obtain transparent colloid.By irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle adds
Enter into starch-hydrocolloid, wherein solid content is 60wt% (starch/silicon grain=0.002, mass ratio), under 90 DEG C of constant temperatures
Stirring obtains suspension slurry in 4 hours.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate is
0.8L/h, nozzle temperature are 340 DEG C, rotating speed 12r/min, and obtained product is that porous, size is 80-300 μm spherical
Particle.In fluid bed, filling height is the above-mentioned spheric granules of 2.5 times of fluid bed diameters, the use of argon gas is carrier gas, flow
For 60L/h.Temperature of reactor is raised to by 950 DEG C of pretreatment temperature by room temperature with 30 DEG C/min heating rate under the atmosphere,
After constant temperature 5min, the gaseous mixture of methane and argon gas, wherein methane are passed through：The volume ratio of argon gas is 2:1, control course of reaction is always empty
Speed is 800h-1, carry out chemical vapor deposition processes.Carbon source methane is closed after 60min, is taken after being cooled to room temperature under an argon atmosphere
Go out solid product.Sieved through cross to shake, obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmission electron microscopy
Under mirror, particle surface has the specific surface area (3.8m of clear graphite linings clad structure, carbon deposition quantity 2.3wt%, and product2/
G) it is less than the original specific surface area (4.8m of silicon grain2/g)。
Embodiment 10：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.5wt% amylopectin is added to the water by mass percent, stirring is warming up to 90 DEG C, and constant temperature 1 is small under normal temperature
When after obtain transparent colloid.By irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle adds
Enter into starch-hydrocolloid, wherein solid content is 60wt% (starch/silicon grain=0.0033, mass ratio), in 90 DEG C of constant temperatures
Lower stirring obtains suspension slurry in 6 hours.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate is
0.8L/h, nozzle temperature are 340 DEG C, rotating speed 12r/min, and obtained product is that porous, size is 120-300 μm spherical
Particle.In fluid bed, filling height is the above-mentioned spheric granules of 2.5 times of fluid bed diameters, the use of argon gas is carrier gas, flow
For 60L/h.Temperature of reactor is raised to by 700 DEG C of pretreatment temperature by room temperature with 30 DEG C/min heating rate under the atmosphere,
After constant temperature 5min, the gaseous mixture of toluene (200 DEG C of preheatings) and argon gas, wherein toluene are passed through：The volume ratio of argon gas is 1:1, control
The total air speed of course of reaction is 800h-1, carry out chemical vapor deposition processes.Carbon source toluene is closed after 25min, it is cold under an argon atmosphere
But to taking out solid product after room temperature.Sieved through cross to shake, obtain the irregular particle that size is mainly distributed between 0.05-15 μm,
Under transmission electron microscope, particle surface has the ratio of clear graphite linings clad structure, carbon deposition quantity 8.0wt%, and product
Surface area (4.6m2/ g) it is less than the original specific surface area (4.8m of silicon grain2/g)。
Embodiment 11：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.2wt% amylopectin is added to the water by mass percent, stirring is warming up to 90 DEG C, and constant temperature 1 is small under normal temperature
When after obtain transparent colloid.By irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle adds
Enter into starch-hydrocolloid, wherein solid content is 50wt% (starch/silicon grain=0.002, mass ratio), under 90 DEG C of constant temperatures
Stirring obtains suspension slurry in 4 hours.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate is
0.8L/h, nozzle temperature are 340 DEG C, rotating speed 12r/min, and obtained product is that porous, size is 80-280 μm spherical
Particle.In fluid bed, filling height is the above-mentioned spheric granules of 1.8 times of fluid bed diameters, the use of argon gas is carrier gas, flow
For 45L/h.Temperature of reactor is raised to by 850 DEG C of pretreatment temperature by room temperature with 20 DEG C/min heating rate under the atmosphere,
After constant temperature 5min, the gaseous mixture of propylene and argon gas, wherein propylene are passed through：The volume ratio of argon gas is 1:1, control course of reaction is always empty
Speed is 650h-1, carry out chemical vapor deposition processes.Product is blown out after reaction 40min, rejoined and first time phase homogenous quantities
Catalyst, carry out successive reaction.Products therefrom is by cooling, shake sieve, obtains size and is mainly distributed between 0.05-15 μm
Irregular particle, under transmission electron microscope, particle surface has a clear graphite linings clad structure, carbon deposition quantity 3.8wt%, and
And specific surface area (the 3.9m of product2/ g) it is less than the original specific surface area (4.8m of silicon oxide particles2/g)。
Embodiment 12：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 1wt% glucose is added to the water by mass percent, stirring is warming up to 60 DEG C, and constant temperature is after 1 hour under normal temperature
Obtain transparency liquid.Irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle is added to Portugal
In grape sugar aqueous solution, wherein solid content is 50wt% (starch/silicon grain=0.01, mass ratio), is stirred under 60 DEG C of constant temperatures
Mix 2 hours and obtain suspension slurry.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate 0.8L/
H, nozzle temperature are 300 DEG C, rotating speed 15r/min, and obtained product is the spheric granules that porous, size is 50-180 μm.
In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, the use of argon gas is carrier gas, flow 45L/
h.Temperature of reactor is raised to by 750 DEG C of pretreatment temperature, constant temperature by room temperature with 20 DEG C/min heating rate under the atmosphere
After 5min, the gaseous mixture of acetylene and argon gas, wherein acetylene are passed through：The volume ratio of argon gas is 1:1, control the total air speed of course of reaction to be
500h-1, carry out chemical vapor deposition processes.Carbon source acetylene is closed after after reaction 30min, after being cooled to room temperature under an argon atmosphere
Take out solid product.Sieved through cross to shake, obtain the irregular particle that size is mainly distributed between 0.05-15 μm, transmitted electron shows
Under micro mirror, particle surface has clear graphite linings clad structure, carbon deposition quantity 5.8wt%, and the specific surface area of product
(4.4m2/ g) it is less than the original specific surface area (4.8m of silicon oxide particles2/g)。
Embodiment 13：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
It is that 0.5wt% glucose is added to the water by mass percent, stirring is warming up to 50 DEG C, constant temperature 1 hour under normal temperature
After obtain transparency liquid.Irregular pattern, particle size be 0.1-10 μm of Si oxide (SiOx, 0<x<2) particle is added to
In D/W, wherein solid content is 50wt% (starch/silicon grain=0.005, mass ratio), under 50 DEG C of constant temperatures
Stirring obtains suspension slurry in 2 hours.Above-mentioned slurry is granulated using centrifugal spray dryer, charging rate is
0.6L/h, nozzle temperature are 280 DEG C, rotating speed 12r/min, and obtained product is that porous, size is 50-200 μm spherical
Particle.In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, the use of nitrogen is carrier gas, flow is
45L/h.Temperature of reactor is raised to by 800 DEG C of pretreatment temperature by room temperature with 20 DEG C/min heating rate under the atmosphere, it is permanent
After warm 5min, the gaseous mixture of propylene and nitrogen, wherein propylene are passed through：The volume ratio of nitrogen is 1:1, control the total air speed of course of reaction
For 600h-1, carry out chemical vapor deposition processes.Product is blown out after reaction 40min, rejoined and first time phase homogenous quantities
Catalyst, carry out successive reaction.Products therefrom by cooling, shake sieve, obtain size be mainly distributed on 0.05-15 μm between not
Rule particle, under transmission electron microscope, particle surface has a clear graphite linings clad structure, carbon deposition quantity 4.4wt%, and
Specific surface area (the 4.0m of product2/ g) it is less than the original specific surface area (4.8m of silicon oxide particles2/g)。
Embodiment 14：Fluid bed prepares nanometer or micron silicon oxide-graphene Core-shell structure material
Under normal temperature, the polyethylene glycol (PEG2000) that mass percent is 1wt% is added to the water, stirring is warming up to 50
DEG C, constant temperature obtains transparency liquid after 1 hour.Irregular pattern, particle size be 0.1-10 μm of Si oxide (Si oxide
(SiOx, 0<x<2) particle is added in the PEG aqueous solution, and wherein solid content is 50wt% (starch/silicon grain=0.01, quality
Than), stirred 2 hours under 50 DEG C of constant temperatures and obtain suspension slurry.Above-mentioned slurry is entered using centrifugal spray dryer
Row is granulated, charging rate 0.8L/h, and nozzle temperature is 300 DEG C, rotating speed 12r/min, and obtained product is porous, size
For 50-160 μm of spheric granules.In fluid bed, filling height is the above-mentioned spheric granules of 2 times of fluid bed diameters, is used
Argon gas is carrier gas, flow 45L/h.With 30 DEG C/min heating rate temperature of reactor is raised to by room temperature under the atmosphere pre-
850 DEG C for the treatment of temperature, after constant temperature 5min, it is passed through the gaseous mixture of propylene and argon gas, wherein propylene：The volume ratio of argon gas is 1:1, control
The total air speed of course of reaction processed is 500h-1, carry out chemical vapor deposition processes.Carbon source propylene is closed after 45min, under an argon atmosphere
Solid product is taken out after being cooled to room temperature.Sieved through cross to shake, obtain irregular that size is mainly distributed between 0.05-15 μm
, under transmission electron microscope, particle surface has clear graphite linings clad structure, carbon deposition quantity 5.3wt%, and product
Specific surface area (4.5m2/ g) it is less than the original specific surface area (4.8m of silicon grain2/g)。
Claims (7)
1. the preparation method of the core shell structure of a kind of graphene coated silicon or its oxide, it is characterised in that this method includes as follows
Step：
1) carbon binder at normal temperatures, will be contained to be dissolved in deionized water, persistently stir and be to slowly warm up to 50~100 DEG C, holding
Constant temperature 1~6 hour, obtains viscous liquid；
2) particle diameter is added in the viscous liquid prepared by step 1) for 0.1~10 μm of silicon or its oxide particle, stirred
It is 30~60wt% suspension slurries to obtain solid content；
3) slurry for obtaining step 2) carries out mist projection granulating, obtains porous spherical of the particle diameter distribution between 50~300 μm
Grain, i.e. secondary structure particle；
4) secondary structure obtained step 3) is particles filled into fluid bed, is heated to reaction temperature 700 in an inert atmosphere
~1000 DEG C, then pass to carbon source, total air speed of inert gas and carbon source is 500~900h-1, keep carbon source and inert gas
Volume ratio carries out chemical vapor deposition, the reaction time is 20~60min, that is, obtains the silicon of graphene coated between 0.5~2
Or its oxide core shell structure.
2. the preparation method of the core shell structure of a kind of graphene coated silicon as claimed in claim 1 or its oxide, its feature
It is：The core shell structure is using the Asia/micron particles of silicon or its oxide as core, graphene for shell, grain size 0.05
~15 μm；The number of plies of graphene shell is 5~30 layers, and the weight of graphene accounts for 1~8wt% of core-shell structure particles gross weight, and
The specific surface area of the core shell structure is equal to or less than original silicon or the specific surface area of its oxide particle.
3. the preparation method of the core shell structure of a kind of graphene coated silicon as claimed in claim 1 or its oxide, its feature
It is：The core shell structure is in crystal or amorphous state, its macro morphology be spherical, bar-shaped, sheet, irregular polyhedronses or they
In two or more patterns mixture.
4. a kind of preparation method of the core shell structure of graphene coated silicon or its oxide according to claim 1,2 or 3,
It is characterized in that：Species containing carbon binder includes direct-connected, amylopectin, glucose, polysaccharide or polyhydroxy-alcohol；Carbon containing bonding
The mass ratio of agent and silicon or its oxide particle is between 0.0005~0.03.
5. a kind of preparation method of the core shell structure of graphene coated silicon or its oxide according to claim 1,2 or 3,
It is characterized in that：Mist projection granulating described in step 3) selects atomizer comminutor, and charging rate is 0.5~2L/h, entrance
Between temperature is 280~350 DEG C, rotating speed of shower nozzle is 10~20r/min.
6. a kind of preparation method of the core shell structure of graphene coated silicon or its oxide according to claim 1,2 or 3,
It is characterized in that：Height of secondary structure particle packing described in step 4) in fluidized-bed reactor is the 1 of fluid bed diameter
~3 times；The carbon source is one or more of combinations in methane, ethane, ethene, acetylene, propane, propylene, benzene and toluene；Institute
It is nitrogen, argon gas or the mixture of the two to state inert gas.
7. a kind of preparation method of the core shell structure of graphene coated silicon or its oxide according to claim 1,2 or 3,
It is characterized in that：The silicon of the graphene coated obtained in step 4) or its oxide core shell structure are sent into vibrating sieving machine and produced
Product separate, and the secondary structure particle not disintegrated for small part, using air-flow crushing, rejoin in fluidized-bed reactor
Row graphene shell coats.
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