CN105006559A - Core-shell structure of graphene coated silicon or silicon oxide, and preparation method thereof - Google Patents
Core-shell structure of graphene coated silicon or silicon oxide, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a core-shell structure of graphene coated silicon or silicon oxide, and a preparation method thereof. The core-shell structure is a sub/micron particle with silicon or silicon oxide as a core and graphene as a shell, the dimension of the particle is 0.05-15[mu]m, the quantity of graphene layers is 5-30, the weight of graphene is 1-8wt% of the total weight of the core-shell structure, and the specific surface area of the core-shell structure is equal to or less than the specific surface area of original silicon or silicon oxide particles. The method is characterized in that the core-shell structure product meeting above requirements is finally obtained through completing secondary structure assembling of the silicon or silicon oxide particle, graphene shell growth and secondary structure autonomous fragmentation by using spray granulation, fluidized bed, vibrating screen and airflow crushing devices. The core-shell composite structure obtained in the invention has the properties of the silicon or silicon oxide, and also has some characteristics of graphene, so the core-shell structure has wide application prospect in the electrochemical industry. A fluidized bed reactor can realize continuous production, and the above whole process can be industrialized.
Description
Technical field
The present invention relates to nucleocapsid structure of a kind of graphene coated silicon or its oxide and preparation method thereof, belong to new energy materials and preparing technical field thereof.
Background technology
As far back as 1991, first generation commercial li-ion battery was invented by Sony company, makes the universal of the electronic devices such as mobile phone become possibility.Experienced by the development of two more than ten years, the kind of mobile electronic device and performance there occurs huge change, lighter, stand-by time is longer, charging, flexibility, safety and environmental protection etc. quickly, a series of new requirement that people propose again battery system.Moreover, the fast development of electric automobile and hybrid vehicle in recent years, also excites people further for the demand of the electrokinetic cell of high-energy-density and high power density and exploration.
According to the part of battery system---positive electrode, negative material, barrier film, electrolyte, collector and Package casing etc., can find that the performance of battery depends primarily on the specific capacity performance of positive and negative electrode material.For negative material, current commercial Li-ion battery is generally using graphite carbon material as negative pole, and the theoretical capacity of graphite is only 372mAh/g, which greatly limits further developing of lithium ion battery.As the silicium cathode with the highest theoretical specific capacity, its theoretical specific capacity can reach 4200mAh/g, is the ideal chose of high-energy-density negative material of new generation.But in the application process of reality, the capacity attenuation of silicium cathode is too fast, cause the cycle performance of battery poor, become one of difficult problem that silicium cathode commercialization must solve.
In the electrochemical cycle stability improving silicon or its oxide, forefathers have done a large amount of work.On the one hand, researcher wishes by by silicon grain nanometer and the capacity attenuation that designs specific nanostructure to improve because volumetric expansion causes, such as aligned nanowires (Cui Y, et al.Nature Nanotechnology, 2008,3:31-35), nanotube (Jaephil Cho, etal.Nano Letter, 2009,9 (11): 3844 – 3847), nanofiber (Lee YM, Park JK, et al.ACS Appl.Mater.Interfaces, 2013,5 (22): 12005 – 12010) etc. silicon multilevel hierarchy.From experimental result, nanometer can improve the cycle performance of battery really to a certain extent.But in the business application of reality, the structure of these novelties is but faced with the problems such as preparation process complexity, growth conditions harshness and high cost, therefore also cannot realize large batch of preparation at present.Moreover, these nano-silicons need to add carbon black to strengthen intergranular conductivity usually.For such situation, if can at different sub-micron or micron silicon or the even coated few layer graphene of its oxide particle surface, well can not only improve the problem owing to there is material efflorescence caused by change in volume and secondary agglomeration in doff lithium ion process like this, by the superpower electron transfer characteristic of Graphene self, the conductivity between particle and between particle and collector can also be strengthened.
According to the difference of particle surface carbon method for coating, hydrothermal carbonization, high temperature cabonization and chemical vapour deposition (CVD) three kinds mainly can be divided into.No matter be hydrothermal carbonization or high temperature cabonization (Wan Lijun etc., patent publication No.: 101931076A), be all in advance the raw material and active particle (silicon or its oxide) that are easy to occur dehydration are carried out physical mixed, then under the environment of high temperature or hydro-thermal, carbonization occur and be wrapped in active particle surface.Owing to there is density variation between the liquid or solid carbon source that usually adopts and silicon or its oxide, the uniformity of physical mixed is difficult to ensure, especially in the process produced in enormous quantities, easily containing microporous carbon impurity in product.And some surfactants are as carbon source, rely on weak chemical interactions can realize coated on active particle top layer and carbonization occurs, but the cost of itself costliness and the requirement for active particle pattern and surface characteristic, make its industrialization also there is larger difficulty.Moreover, the carbon products that dehydration carbonization obtains is usually containing abundant micropore, specific area is large, SEI film (solid electrolyte interface is formed in electrode material surface, solid electrolyte interface film) process in, need to consume more lithium, reduce the coulombic efficiency of first circle discharge and recharge, increase battery cost.Comparatively speaking, the carbon coating layer that chemical vapour deposition (CVD) is formed is mainly graphitic carbon, has good conductivity, and does not substantially have the formation of micropore, and the specific area of the silicon-carbon compound formed is little compared with the specific area of original silicon or its oxide particle.Consider that fluid bed has better heat transfer and mass-transfer efficiency, with it for reactor realizes the coated process of chemical vapor carbon deposition of the different submicron order of pattern or micron silicon or its oxide surface, there is important engineering significance.
Summary of the invention
The object of the present invention is to provide nucleocapsid structure of a kind of graphene coated silicon or its oxide and preparation method thereof, can reduce it there is fragmentation because embedding lithium takes off lithium to the nucleocapsid structure making it be formed on the one hand, improve cycle performance of battery, be conducive to increasing intergranular conductivity on the other hand, conductive additive consumption can be reduced and reduce the internal resistance of cell, thus be with a wide range of applications at electrochemical industry, continuous print industrialization can be realized simultaneously and generate.
Technical scheme of the present invention is as follows:
A nucleocapsid structure for graphene coated silicon or its oxide, is characterized in that: this nucleocapsid structure be with silicon or its oxide be core, the Graphene Asia/micron particles that is shell, grain size is 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 total weight, and the specific area of this nucleocapsid structure is equal to or less than the specific area of original silicon or its oxide particle.
The feature of nucleocapsid structure of the present invention is also: described nucleocapsid structure is crystal or amorphous state, and its macro morphology is the mixture of spherical, bar-shaped, sheet, irregular polyhedrons or two or more patterns in them.
The preparation method of the nucleocapsid structure of a kind of graphene coated silicon provided by the invention or its oxide, is characterized in that the method comprises the steps:
5) at normal temperatures, will be dissolved in deionized water containing carbon binder, Keep agitation is also slowly warming up to 50 ~ 100 DEG C, keeps constant temperature 1 ~ 6 hour, obtains viscous liquid;
6) silicon being 0.1 ~ 10 μm by particle diameter or its oxide particle join step 1) prepared by viscous liquid in, stir that to obtain solid content be 30 ~ 60wt% suspension-turbid liquid slurry;
7) by step 2) slurry that obtains carries out mist projection granulating, obtains the porous spherical particles of domain size distribution between 50 ~ 300 μm, i.e. secondary structure particle;
8) by step 3) secondary structure that obtains is particles filled in fluid bed, and be heated to reaction temperature 700 ~ 1000 DEG C in an inert atmosphere, then pass into carbon source, total air speed of inert gas and carbon source is 500 ~ 900h
-1, keep the volume ratio of carbon source and inert gas between 0.5 ~ 2, carry out chemical vapour deposition (CVD), the reaction time is 20 ~ 60min, obtains silicon that grain size is the graphene coated of 0.05 ~ 15 μm or its oxide core shell structure.
In the method for the invention, it is characterized in that: the kind containing carbon binder comprises direct-connected, amylopectin, glucose, polysaccharide or polyhydroxy-alcohol; Containing the mass ratio of carbon binder and silicon or its oxide particle between 0.0005 ~ 0.03.
In method of the present invention, step 3) described in mist projection granulating select atomizer comminutor, charging rate is 0.5 ~ 2L/h, and inlet temperature is between 280 ~ 350 DEG C, and shower nozzle rotating speed is 10 ~ 20r/min.
In method of the present invention, step 4) described in the height of secondary structure particle packing in fluidized-bed reactor be 1 ~ 3 times of fluid bed diameter; Described carbon source is the combination of one or more in methane, ethane, ethene, acetylene, propane, propylene, Benzene and Toluene; Described inert gas is nitrogen, argon gas or the mixture of the two.
Method of the present invention, be further characterized in that: step 4) in the silicon of graphene coated that obtains or its oxide core shell structure send in vibrating sieving machine and carry out separation of products, for the secondary structure particle that small part is not disintegrated, adopt air-flow crushing, rejoin in fluidized-bed reactor that to carry out Graphene shell coated.
The present invention compared to existing technology, tool has the following advantages and the technique effect of high-lighting: 1. realize few layer graphene (5-30 layer) abnormity, Asia/micron silicon or its oxide particle surface evenly coated, can reduce it there is fragmentation because embedding lithium takes off lithium to the nucleocapsid structure formed on the one hand, improve cycle performance of battery, be conducive to increasing intergranular conductivity on the other hand, conductive additive consumption can be reduced and reduce the internal resistance of cell; 2. the specific area of core-shell structure particles is equal to or less than the specific area of original silicon or its oxide particle, can not form extra SEI layer, reduces the consumption of positive pole lithium-containing materials, is conducive to reducing battery cost; 3) carbon source adopted in the method is cheap and easy to get, and fluidized-bed process is convenient to engineering and is amplified and batch production.
Accompanying drawing illustrates:
Fig. 1 is the stereoscan photograph of sub-micro level or the former powder of micron silicon.
Fig. 2 is the stereoscan photograph that sub-micron or micron silicon granulation obtain micron-size spherical particles.
Fig. 3 is the stereoscan photograph of the coated few layer graphene material of sub-micron or micron silicon.
Fig. 4 is the transmission electron microscope photo of the coated few layer graphene material of sub-micron or micron silicon.
Embodiment
The nucleocapsid structure of a kind of graphene coated silicon provided by the invention or its oxide, be with silicon or its oxide be core, the Graphene Asia/micron particles that is shell, grain size is 0.05 ~ 15 μm; The number of plies of Graphene shell is 5 ~ 30 layers, and the weight of Graphene accounts between 1 ~ 8wt% of core-shell structure particles total weight, and the specific area of this nucleocapsid structure is equal to or less than the specific area of original silicon or its oxide particle; This nucleocapsid structure is crystal or amorphous state, and its macro morphology is the mixture of spherical, bar-shaped, sheet, irregular polyhedrons or two or more patterns in them.
The preparation method of the nucleocapsid structure of graphene coated silicon of the present invention or its oxide comprises the steps:
1) at normal temperatures, will be dissolved in deionized water containing carbon binder, Keep agitation is also slowly warming up to 50-100 DEG C, keeps constant temperature 1-6 hour, obtains viscous liquid;
2) silicon being 0.1-10 μm by particle diameter or its oxide particle join step 1) prepared by viscous liquid in, stir that to obtain solid content be 30-60wt% suspension-turbid liquid slurry;
3) by step 2) slurry that obtains carries out mist projection granulating, obtains the porous spherical particles of domain size distribution between 50-300 μm, i.e. secondary structure particle;
4) by step 3) secondary structure that obtains is particles filled is heated to reaction temperature 700-1000 DEG C in an inert atmosphere in fluid bed, and then pass into carbon source, total air speed of inert gas and carbon source is 500-900h
-1, the volume ratio keeping carbon source and inert gas is between 0.5-2, and carry out chemical vapour deposition (CVD), the reaction time is 20-60min, obtains silicon that grain size is the graphene coated of 0.05-15 μm or its oxide core shell structure;
Wherein, the macro morphology of silicon or its oxide particle can be the mixture of spherical, bar-shaped, sheet, irregular polyhedrons and above pattern.Kind containing carbon binder comprises direct-connected, amylopectin, glucose, polysaccharide, polyhydroxy-alcohol etc.; Containing the mass ratio of carbon binder and silicon or its oxide particle between 0.0005-0.03.In a fluidized bed reactor, loading height is that 1-3 is doubly to silicon or its oxide secondary structure particle of fluid bed diameter; Carbon source is the combination of one or more in methane, ethane, ethene, acetylene, propane, propylene, Benzene and Toluene; Inert gas is nitrogen, argon gas or the two mix gained according to a certain percentage.Due in Graphene shell growth course; the secondary structure particle being in fluidized state can disintegrate due to collision; obtain the nucleocapsid product that grain size is distributed in 0.05-15 μm; vibrating sieving machine is utilized to carry out separation of products; and for the secondary structure particle that small part is not disintegrated; to air-flow crushing be adopted, rejoin in fluid bed that to carry out Graphene shell coated.
Below by several specific embodiment, the present invention is further illustrated.
Embodiment 1: fluid bed Asia/micron order prepares silicon-Graphene Core-shell structure material
Under normal temperature, be that 0.75wt% amylopectin is added to the water by mass percent, stir and be warming up to 80 DEG C, constant temperature obtained transparent colloid after 2 hours.By irregular pattern, particle size is that 0.1-10 μm of silicon grain (as Fig. 1) joins in starch-hydrocolloid, wherein solid content is 50wt% (starch/silicon grain=0.0075, mass ratio), stir under 80 DEG C of constant temperatures and obtain suspension-turbid liquid slurry in 2 hours.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 1L/h, and nozzle temperature is 320 DEG C, and rotating speed is 15r/min, the product obtained be porous, be of a size of the spheric granules of 50-300 μm, as shown in Figure 2.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 45L/h.Under this atmosphere, with the heating rate of 20 DEG C/min, temperature of reactor is raised to pretreatment temperature 850 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of propylene and argon gas, wherein propylene: the volume ratio of argon gas is 1:1, controlling the total air speed of course of reaction is 600h
-1, carry out chemical vapor deposition processes.Close carbon source propylene after 30min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through scanning electron microscopic observation, pattern and the original silicon grain pattern of the silicon grain of graphene coated are similar, and distribution of sizes is between 0.05-15 μm.As shown in Figure 4, under high-resolution-ration transmission electric-lens photo, graphite linings structure clearly can be seen in silicon grain surface.In Raman collection of illustrative plates, also there is obvious G peak to exist, illustrate that the carbon on silicon grain surface is mainly few layer graphene structure.Thermogravimetric result shows, under this condition, the carbon deposition quantity on silicon grain surface reaches 3.9wt%.Under 77K, isothermal N2 adsorption curve shows do not have micropore in this product, and specific area is 3.8m
2/ g, is less than the specific area (4.2m that silicon grain is original
2/ g).
Embodiment 2: fluid bed prepares Asia/micron silicon-Graphene Core-shell structure material
Under normal temperature, be that 0.5wt% amylopectin is added to the water by mass percent, stir and be warming up to 75 DEG C, constant temperature obtained transparent colloid after 1.5 hours.By irregular pattern, particle size is that 0.1-10 μm of silicon grain joins in starch-hydrocolloid, wherein solid content is 60wt% (starch/silicon grain=0.0033, mass ratio), stirs and obtain suspension-turbid liquid slurry in 2.5 hours under 75 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.8L/h, and nozzle temperature is 300 DEG C, and rotating speed is 17r/min, the product obtained be porous, be of a size of the spheric granules of 50-200 μm.In fluid bed, loading height be 1 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 45L/h.Under this atmosphere, with the heating rate of 20 DEG C/min, temperature of reactor is raised to pretreatment temperature 850 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of propylene and argon gas, wherein propylene: the volume ratio of argon gas is 1:1, controlling the total air speed of course of reaction is 650h
-1, carry out chemical vapor deposition processes.After reaction 40min, product is blown out, rejoin the catalyst with first time equal in quality, carry out successive reaction.Products therefrom passes through cooling, shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, carbon deposition quantity is 4.8wt%, and the specific area (4.1m of product
2/ g) be less than the original specific area (4.2m of silicon grain
2/ g).
Embodiment 3: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.5wt% amylopectin is added to the water by mass percent, stir and be warming up to 90 DEG C, constant temperature obtained transparent colloid after 3 hours.By irregular pattern, particle size is that 0.1-10 μm of Si oxide SiO particle joins in starch-hydrocolloid, wherein solid content is 60wt% (starch/silicon grain=0.0033, mass ratio), stir under 90 DEG C of constant temperatures and obtain suspension-turbid liquid slurry in 4 hours.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.6L/h, and nozzle temperature is 340 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 80-300 μm.In fluid bed, loading height be 2.5 times to the above-mentioned spheric granules of fluid bed diameter, use nitrogen is carrier gas, and flow is 60L/h.Under this atmosphere, with the heating rate of 40 DEG C/min, temperature of reactor is raised to pretreatment temperature 880 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of propylene and nitrogen, wherein propylene: the volume ratio of nitrogen is 2:3, controlling the total air speed of course of reaction is 800h
-1, carry out chemical vapor deposition processes.Close carbon source propylene after 45min, after being cooled to room temperature in a nitrogen atmosphere, take out solid product.Through to shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 5.2wt%, and the specific area (2.8m of product
2/ g) be less than the original specific area (3.2m of silicon grain
2/ g).
Embodiment 4: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.3wt% amylopectin is added to the water by mass percent, stir and be warming up to 100 DEG C, constant temperature obtained transparent colloid after 6 hours.By irregular pattern, particle size is 0.1-10 μm of Si oxide Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.003, mass ratio), stirs and obtain suspension-turbid liquid slurry in 3 hours under 100 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 1.2L/h, and nozzle temperature is 340 DEG C, and rotating speed is 13r/min, the product obtained be porous, be of a size of the spheric granules of 50-250 μm.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use nitrogen is carrier gas, and flow is 40L/h.Under this atmosphere, with the heating rate of 25 DEG C/min, temperature of reactor is raised to pretreatment temperature 750 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of ethene and nitrogen, wherein ethene: the volume ratio of nitrogen is 1:1, controlling the total air speed of course of reaction is 500h
-1, carry out chemical vapor deposition processes.Close carbon source ethene after 50min, after being cooled to room temperature in a nitrogen atmosphere, take out solid product.Through to shake sieve, mainly obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 2.8wt%, and the specific area (2.4m of product
2/ g) be less than the original specific area (3.2m of silicon grain
2/ g).
Embodiment 5: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.1wt% amylopectin is added to the water by mass percent, stir and be warming up to 100 DEG C, constant temperature obtained transparent colloid after 2 hours.By irregular pattern, particle size is 0.1-10 μm of Si oxide Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.001, mass ratio), stirs and obtain suspension-turbid liquid slurry in 3 hours under 100 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 2.0L/h, and nozzle temperature is 350 DEG C, and rotating speed is 15r/min, the product obtained be porous, be of a size of the spheric granules of 50-220 μm.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 50L/h.Under this atmosphere, with the heating rate of 30 DEG C/min, temperature of reactor is raised to pretreatment temperature 800 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of ethene and argon gas, wherein ethene: the volume ratio of argon gas is 2:3, controlling the total air speed of course of reaction is 650h
-1, carry out chemical vapor deposition processes.Close carbon source ethene after 35min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, mainly obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 1.0wt%, and the specific area (2.2m of product
2/ g) be less than the original specific area (3.2m of silicon grain
2/ g).
Embodiment 6: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.05wt% amylopectin is added to the water by mass percent, stir and be warming up to 85 DEG C, constant temperature obtained transparent colloid after 1 hour.By irregular pattern, particle size is 0.1-10 μm of Si oxide Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.0005, mass ratio), stirs and obtain suspension-turbid liquid slurry in 3 hours under 85 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.5L/h, and nozzle temperature is 280 DEG C, and rotating speed is 20r/min, the product obtained be porous, be of a size of the spheric granules of 50-180 μm.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 50L/h.Under this atmosphere, with the heating rate of 20 DEG C/min, temperature of reactor is raised to pretreatment temperature 900 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of ethene and argon gas, wherein ethene: the volume ratio of argon gas is 2:3, controlling the total air speed of course of reaction is 650h
-1, carry out chemical vapor deposition processes.Close carbon source ethene after 60min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, mainly obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 5.0wt%, and the specific area (3.2m of product
2/ g) be less than the original specific area (4.1m of silicon grain
2/ g).
Embodiment 7: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 3wt% amylose is added to the water by mass percent, stir and be warming up to 90 DEG C, constant temperature obtained transparent colloid after 3 hours.By irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.03, mass ratio), stirs and obtain suspension-turbid liquid slurry in 2 hours under 90 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 1.8L/h, and nozzle temperature is 330 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 70-280 μm.In fluid bed, loading height be 2.5 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 60L/h.Under this atmosphere, with the heating rate of 25 DEG C/min, temperature of reactor is raised to pretreatment temperature 850 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of ethene and argon gas, wherein ethene: the volume ratio of argon gas is 3:2, controlling the total air speed of course of reaction is 600h
-1, carry out chemical vapor deposition processes.Close carbon source ethene after 35min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, mainly obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 6.2wt%, and the specific area (2.9m of product
2/ g) be less than the original specific area (3.2m of silicon grain
2/ g).
Embodiment 8: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 1wt% amylose is added to the water by mass percent, stir and be warming up to 100 DEG C, constant temperature obtained transparent colloid after 2 hours.By irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 60wt% (starch/silicon grain=0.0067, mass ratio), stirs and obtain suspension-turbid liquid slurry in 2 hours under 100 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 1.0L/h, and nozzle temperature is 320 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 60-240 μm.In fluid bed, loading height be 2.5 times to the above-mentioned spheric granules of fluid bed diameter, use nitrogen is carrier gas, and flow is 60L/h.Under this atmosphere, with the heating rate of 25 DEG C/min, temperature of reactor is raised to pretreatment temperature 800 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of ethene and nitrogen, wherein ethene: the volume ratio of nitrogen is 1:1, controlling the total air speed of course of reaction is 600h
-1, carry out chemical vapor deposition processes.Close carbon source ethene after 20min, after being cooled to room temperature in a nitrogen atmosphere, take out solid product.Through to shake sieve, mainly obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 5.4wt%, and the specific area (4.2m of product
2/ g) be less than the original specific area (4.8m of silicon grain
2/ g).
Embodiment 9: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.3wt% amylopectin is added to the water by mass percent, stir and be warming up to 90 DEG C, constant temperature obtained transparent colloid after 1 hour.By irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 60wt% (starch/silicon grain=0.002, mass ratio), stirs and obtain suspension-turbid liquid slurry in 4 hours under 90 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.8L/h, and nozzle temperature is 340 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 80-300 μm.In fluid bed, loading height be 2.5 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 60L/h.Under this atmosphere, with the heating rate of 30 DEG C/min, temperature of reactor is raised to pretreatment temperature 950 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of methane and argon gas, wherein methane: the volume ratio of argon gas is 2:1, controlling the total air speed of course of reaction is 800h
-1, carry out chemical vapor deposition processes.Close carbon source methane after 60min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 2.3wt%, and the specific area (3.8m of product
2/ g) be less than the original specific area (4.8m of silicon grain
2/ g).
Embodiment 10: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.5wt% amylopectin is added to the water by mass percent, stir and be warming up to 90 DEG C, constant temperature obtained transparent colloid after 1 hour.By irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 60wt% (starch/silicon grain=0.0033, mass ratio), stirs and obtain suspension-turbid liquid slurry in 6 hours under 90 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.8L/h, and nozzle temperature is 340 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 120-300 μm.In fluid bed, loading height be 2.5 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 60L/h.Under this atmosphere, with the heating rate of 30 DEG C/min, temperature of reactor is raised to pretreatment temperature 700 DEG C by room temperature, after constant temperature 5min, pass into the gaseous mixture of toluene (200 DEG C of preheatings) and argon gas, wherein toluene: the volume ratio of argon gas is 1:1, controlling the total air speed of course of reaction is 800h
-1, carry out chemical vapor deposition processes.Close carbon source toluene after 25min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 8.0wt%, and the specific area (4.6m of product
2/ g) be less than the original specific area (4.8m of silicon grain
2/ g).
Embodiment 11: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.2wt% amylopectin is added to the water by mass percent, stir and be warming up to 90 DEG C, constant temperature obtained transparent colloid after 1 hour.By irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in starch-hydrocolloid, and wherein solid content is 50wt% (starch/silicon grain=0.002, mass ratio), stirs and obtain suspension-turbid liquid slurry in 4 hours under 90 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.8L/h, and nozzle temperature is 340 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 80-280 μm.In fluid bed, loading height be 1.8 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 45L/h.Under this atmosphere, with the heating rate of 20 DEG C/min, temperature of reactor is raised to pretreatment temperature 850 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of propylene and argon gas, wherein propylene: the volume ratio of argon gas is 1:1, controlling the total air speed of course of reaction is 650h
-1, carry out chemical vapor deposition processes.After reaction 40min, product is blown out, rejoin the catalyst with first time equal in quality, carry out successive reaction.Products therefrom passes through cooling, shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, carbon deposition quantity is 3.8wt%, and the specific area (3.9m of product
2/ g) be less than the original specific area (4.8m of silicon oxide particles
2/ g).
Embodiment 12: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 1wt% glucose is added to the water by mass percent, stir and be warming up to 60 DEG C, constant temperature obtained transparency liquid after 1 hour.Irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in D/W, and wherein solid content is 50wt% (starch/silicon grain=0.01, mass ratio), stirs and obtain suspension-turbid liquid slurry in 2 hours under 60 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.8L/h, and nozzle temperature is 300 DEG C, and rotating speed is 15r/min, the product obtained be porous, be of a size of the spheric granules of 50-180 μm.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 45L/h.Under this atmosphere, with the heating rate of 20 DEG C/min, temperature of reactor is raised to pretreatment temperature 750 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of acetylene and argon gas, wherein acetylene: the volume ratio of argon gas is 1:1, controlling the total air speed of course of reaction is 500h
-1, carry out chemical vapor deposition processes.Close carbon source acetylene after after reaction 30min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 5.8wt%, and the specific area (4.4m of product
2/ g) be less than the original specific area (4.8m of silicon oxide particles
2/ g).
Embodiment 13: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that 0.5wt% glucose is added to the water by mass percent, stir and be warming up to 50 DEG C, constant temperature obtained transparency liquid after 1 hour.Irregular pattern, particle size is 0.1-10 μm of Si oxide (SiO
x, 0<x<2) and particle joins in D/W, and wherein solid content is 50wt% (starch/silicon grain=0.005, mass ratio), stirs and obtain suspension-turbid liquid slurry in 2 hours under 50 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.6L/h, and nozzle temperature is 280 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 50-200 μm.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use nitrogen is carrier gas, and flow is 45L/h.Under this atmosphere, with the heating rate of 20 DEG C/min, temperature of reactor is raised to pretreatment temperature 800 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of propylene and nitrogen, wherein propylene: the volume ratio of nitrogen is 1:1, controlling the total air speed of course of reaction is 600h
-1, carry out chemical vapor deposition processes.After reaction 40min, product is blown out, rejoin the catalyst with first time equal in quality, carry out successive reaction.Products therefrom passes through cooling, shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, carbon deposition quantity is 4.4wt%, and the specific area (4.0m of product
2/ g) be less than the original specific area (4.8m of silicon oxide particles
2/ g).
Embodiment 14: fluid bed prepares Asia/micron silicon oxide-Graphene Core-shell structure material
Under normal temperature, be that the polyethylene glycol (PEG2000) of 1wt% is added to the water by mass percent, stir and be warming up to 50 DEG C, constant temperature obtained transparency liquid after 1 hour.Irregular pattern, particle size is 0.1-10 μm of Si oxide (Si oxide (SiO
x, 0<x<2) and particle joins in the PEG aqueous solution, and wherein solid content is 50wt% (starch/silicon grain=0.01, mass ratio), stirs and obtain suspension-turbid liquid slurry in 2 hours under 50 DEG C of constant temperatures.Utilize atomizer drier to carry out granulation to above-mentioned slurry, charging rate is 0.8L/h, and nozzle temperature is 300 DEG C, and rotating speed is 12r/min, the product obtained be porous, be of a size of the spheric granules of 50-160 μm.In fluid bed, loading height be 2 times to the above-mentioned spheric granules of fluid bed diameter, use argon gas is carrier gas, and flow is 45L/h.Under this atmosphere, with the heating rate of 30 DEG C/min, temperature of reactor is raised to pretreatment temperature 850 DEG C by room temperature, after constant temperature 5min, passes into the gaseous mixture of propylene and argon gas, wherein propylene: the volume ratio of argon gas is 1:1, controlling the total air speed of course of reaction is 500h
-1, carry out chemical vapor deposition processes.Close carbon source propylene after 45min, after being cooled to room temperature under an argon atmosphere, take out solid product.Through to shake sieve, obtain size and be mainly distributed in irregular particle between 0.05-15 μm, under transmission electron microscope, particle surface has clear graphite linings clad structure, and carbon deposition quantity is 5.3wt%, and the specific area (4.5m of product
2/ g) be less than the original specific area (4.8m of silicon grain
2/ g).
Claims (7)
1. a nucleocapsid structure for graphene coated silicon or its oxide, is characterized in that: this nucleocapsid structure be with silicon or its oxide be core, the Graphene Asia/micron particles that is shell, grain size is 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 total weight, and the specific area of this nucleocapsid structure is equal to or less than the specific area of original silicon or its oxide particle.
2. according to the nucleocapsid structure of a kind of graphene coated silicon according to claim 1 or its oxide, it is characterized in that: described nucleocapsid structure is crystal or amorphous state, its macro morphology is the mixture of spherical, bar-shaped, sheet, irregular polyhedrons or two or more patterns in them.
3. the preparation method of the nucleocapsid structure of a kind of graphene coated silicon as claimed in claim 1 or 2 or its oxide, is characterized in that the method comprises the steps:
1) at normal temperatures, will be dissolved in deionized water containing carbon binder, Keep agitation is also slowly warming up to 50 ~ 100 DEG C, keeps constant temperature 1 ~ 6 hour, obtains viscous liquid;
2) silicon being 0.1 ~ 10 μm by particle diameter or its oxide particle join step 1) prepared by viscous liquid in, stir that to obtain solid content be 30 ~ 60wt% suspension-turbid liquid slurry;
3) by step 2) slurry that obtains carries out mist projection granulating, obtains the porous spherical particles of domain size distribution between 50 ~ 300 μm, i.e. secondary structure particle;
4) by step 3) secondary structure that obtains is particles filled in fluid bed, and be heated to reaction temperature 700 ~ 1000 DEG C in an inert atmosphere, then pass into carbon source, total air speed of inert gas and carbon source is 500 ~ 900h
-1, keep the volume ratio of carbon source and inert gas between 0.5 ~ 2, carry out chemical vapour deposition (CVD), the reaction time is 20 ~ 60min, obtains silicon that grain size is the graphene coated of 0.05 ~ 15 μm or its oxide core shell structure.
4. the preparation method of the nucleocapsid structure of a kind of graphene coated silicon according to claim 3 or its oxide, is characterized in that: the kind containing carbon binder comprises direct-connected, amylopectin, glucose, polysaccharide or polyhydroxy-alcohol; Containing the mass ratio of carbon binder and silicon or its oxide particle between 0.0005 ~ 0.03.
5. the preparation method of the nucleocapsid structure of a kind of graphene coated silicon according to claim 3 or its oxide; it is characterized in that: step 3) described in mist projection granulating select atomizer comminutor; charging rate is 0.5 ~ 2L/h; inlet temperature is between 280 ~ 350 DEG C, and shower nozzle rotating speed is 10 ~ 20r/min.
6. the preparation method of a kind of graphene coated silicon according to claim 3,4 or 5 or the nucleocapsid structure of its oxide, is characterized in that: step 4) described in the height of secondary structure particle packing in fluidized-bed reactor be 1 ~ 3 times of fluid bed diameter; Described carbon source is the combination of one or more in methane, ethane, ethene, acetylene, propane, propylene, Benzene and Toluene; Described inert gas is nitrogen, argon gas or the mixture of the two.
7. the preparation method of a kind of graphene coated silicon according to claim 3,4 or 5 or the nucleocapsid structure of its oxide, it is characterized in that: by step 4) in the silicon of graphene coated that obtains or its oxide core shell structure send in vibrating sieving machine and carry out separation of products, for the secondary structure particle that small part is not disintegrated, adopt air-flow crushing, rejoin in fluidized-bed reactor that to carry out Graphene shell coated.
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