CN114649496B - Preparation device and method of silicon composite material - Google Patents
Preparation device and method of silicon composite material Download PDFInfo
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- CN114649496B CN114649496B CN202210309172.1A CN202210309172A CN114649496B CN 114649496 B CN114649496 B CN 114649496B CN 202210309172 A CN202210309172 A CN 202210309172A CN 114649496 B CN114649496 B CN 114649496B
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- H01M4/04—Processes of manufacture in general
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- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
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- 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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation device and a preparation method of a silicon composite material. The first aspect of the invention provides a preparation device of a silicon composite material, which comprises a reaction unit, a gas inlet arranged at the bottom of the reaction unit and a gas outlet arranged at the top of the reaction unit; at least one crushing unit is arranged in the reaction unit, the crushing unit comprises a plurality of crushing members which are arranged in parallel, and each crushing member comprises a first baffle, a second baffle and a flow guide pipe. The preparation device and the preparation method provided by the invention can effectively improve the uniformity of the surface coating layer of the silicon material, improve the cycle performance and the multiplying power performance of the lithium ion battery, and can be used for producing the silicon composite material.
Description
Technical Field
The invention relates to a preparation device and a preparation method of a silicon composite material, and relates to the technical field of battery materials.
Background
In recent years, lithium ion batteries have been considered as the most promising energy storage devices due to their higher operating voltage and energy density, longer cycle life and good safety performance. With the rapid development of human society, portable chargers, electric vehicles, and artificial intelligence have put high demands on energy density, cycle life, and safety performance. However, the capacity of the negative electrode material graphite of the traditional lithium ion battery is low, the capacity improvement of the lithium ion battery is limited, and compared with graphite, silicon shows a theoretical capacity which is more than 10 times, and the theoretical capacity is close to 4000mAh/g, so that the silicon becomes a candidate material for improving the capacity of the lithium ion battery. However, in the cycling process, the silicon conductivity is poor, the volume expansion is serious (-300%), and a Solid Electrolyte Interface (SEI) film is repeatedly formed and destroyed, so that the cycling performance of the lithium ion battery is poor, and the practical application of silicon is limited.
Coating the silicon material is one of effective strategies for improving the electrochemical performance of the silicon anode, for example, coating the carbon layer on the surface of the silicon is helpful for improving the conductivity of the SEI film, the flexibility and the stability of the electrode, the consumption and the crushing of internal silicon particles can be effectively prevented, and the introduction of hetero atoms into the carbon layer can also endow the silicon-carbon composite material with new performances and applications, such as sulfur doping, nitrogen doping and phosphorus doping, and can further improve the conductivity of the carbon layer. However, the existing coating method is complex, has high cost, is not easy to prepare in large scale, and the electrochemical performance of the prepared silicon composite material needs to be further improved.
By adopting the fluidized bed chemical vapor deposition method, the high fluidization of the nano silicon material in the reactor and the high-efficiency heat and mass transfer between the reaction gas and the silicon particles are both beneficial to improving the uniformity degree of the coating layer and improving the production quantity of the silicon composite material, but in the reaction process, the silicon material particles are easy to agglomerate, the reaction gas is easy to form bubbles when contacting with agglomerates, the gas-solid contact efficiency is influenced, the coating effect of the silicon material particles is influenced, and the thickness controllability and the uniformity of the coating layer are poor. By arranging the inner member in the fluidized bed reaction unit, the fluidization quality can be effectively improved, however, the improvement effects of the inner member with different structures on the fluidization quality are different, and how to further improve the fluidization quality and improve the coating uniformity degree of the silicon material is one of the continuous concerns of the technicians in the field.
Disclosure of Invention
The invention provides a preparation device and a preparation method of a silicon composite material, which are used for improving the coating uniformity of the surface of the silicon material and improving the cycle performance and the multiplying power performance of a lithium ion battery.
The first aspect of the invention provides a preparation device of a silicon composite material, which comprises a reaction unit, a gas inlet arranged at the bottom of the reaction unit and a gas outlet arranged at the top of the reaction unit;
at least one crushing unit is arranged in the reaction unit, and the crushing unit comprises a plurality of crushing members which are arranged in parallel;
the crushing member comprises a first baffle, a second baffle and a flow guide pipe, wherein the first baffle and the second baffle are oppositely arranged and form a first opening and a second opening which are communicated with each other, the first opening faces the gas outlet, the second opening faces the gas inlet, and a plurality of through holes are formed in the first baffle and the second baffle; the honeycomb duct is located between the first baffle and the second baffle, the setting direction of honeycomb duct with the direction of gas inlet orientation gas outlet is perpendicular.
In a specific embodiment, the reaction unit is provided with a first crushing unit and a second crushing unit in sequence from one side close to the gas inlet to one side close to the gas outlet, wherein an included angle between a crushing member in the first crushing unit and a crushing member in the second crushing unit is alpha, and 0 degrees is less than alpha and less than 180 degrees.
In a specific embodiment, the first baffle comprises a first upper baffle and a first lower baffle which are connected with each other, the second baffle comprises a second upper baffle and a second lower baffle which are connected with each other, the first upper baffle and the second upper baffle are arranged in parallel, and the included angle between the first lower baffle and the second lower baffle is 15-90 degrees;
the upper baffle plate and the lower baffle plate are respectively provided with an upper through hole, and the upper through holes and the lower through holes are sequentially staggered.
In a specific embodiment, the ratio of the total area of the upper through holes to the total area of the first upper baffle plate and the second upper baffle plate is not more than 10%; the ratio of the total area of the lower through holes to the total area of the first lower baffle plate and the second lower baffle plate is not more than 5%.
In one embodiment, the vertical distance between the first upper baffle plate and the second upper baffle plate is 40-500mm; the heights of the first upper baffle plate and the second upper baffle plate are 20-400mm.
In a specific embodiment, the vertical distance of the crushing unit from the gas inlet is not less than 100mm.
In a specific embodiment, the device further comprises a separation unit arranged on one side of the crushing unit close to the gas outlet, the separation unit comprises a first separation baffle plate close to one side of the gas inlet and a second separation baffle plate close to one side of the gas outlet, the first separation baffle plate encloses and forms a third opening facing the gas inlet and a fourth opening facing the gas outlet, an included angle between a plane where the third opening is located and the first separation baffle plate is not more than 80 degrees, the second separation baffle plate is arranged on the fourth opening and is close to the upper side of the gas outlet, and the first separation baffle plate and the second separation baffle plate are all provided with a plurality of gas through holes.
The second aspect of the present invention provides a method for preparing a silicon composite material, which is carried out in any one of the above-mentioned devices, and comprises the steps of:
placing a silicon-based material at the bottom of a reaction unit, which is close to a gas inlet, inputting gas from the gas inlet, entering the reaction unit, performing cracking reaction on the gas entering the reaction unit, and performing cladding reaction with the fluidized silicon-based material, thereby obtaining the silicon composite material after the reaction is finished.
In one specific embodiment, the temperature of the reaction unit is 380-1000 ℃, the gauge pressure is 0.01-1Mpa, the time is 1-100min, and the apparent gas velocity is 0.001-1m/s.
In a specific embodiment, the ratio of the vertical distance of the crushing unit from the gas inlet to the static bed height of the silicon-based material is not more than 2.5.
The preparation device and the preparation method provided by the invention can effectively improve the uniformity of the surface coating layer of the silicon material, improve the cycle performance and the multiplying power performance of the lithium ion battery, and can be used for producing the silicon composite material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic diagram of a manufacturing apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic view of a crushing member according to an embodiment of the present invention;
FIG. 3 is a schematic view of a crushing member according to a further embodiment of the present invention;
FIG. 4 is a side view of a crushing member provided in an embodiment of the present invention;
FIG. 5 is a schematic view of a crushing unit according to an embodiment of the present invention;
FIG. 6 is a schematic structural view of a separation baffle according to an embodiment of the present invention;
FIG. 7 is an expanded view of a first separator plate according to an embodiment of the present invention;
FIG. 8 is a top view of a second separator plate according to yet another embodiment of the present invention;
FIG. 9 is a scanning electron microscope photograph of the nitrogen-doped silicon-carbon composite material prepared in example 1 of the present invention;
FIG. 10 is a Raman spectrum of the nitrogen-doped silicon-carbon composite material prepared in example 1 of the present invention;
fig. 11 is a charge-discharge curve of the nitrogen-doped silicon-carbon composite material prepared in example 2 of the present invention.
Reference numerals illustrate:
1: gas inlet, 2: reaction unit, 3: crushing unit, 3-1: first crushing unit, 3-2: second crushing unit, 4: separation baffle, 4-1: first separation baffle, 4-2: second separation baffle, 5: cyclone separator, 6: gas outlet, 10: first lower baffle, 11: first upper baffle, 12: second lower baffle, 13: second upper baffle, 14: connecting plate, 15: lower through hole, 16: upper through hole, 17: and a flow guiding pipe.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The process for coating the silicon material by adopting the fluidized bed chemical vapor deposition method mainly comprises the following steps: and (3) adopting a fluidized bed reaction device, introducing gas to fluidize silicon material particles in the fluidized bed, simultaneously, cracking the gas in the fluidized bed to obtain simple substances, reacting the cracked simple substances with the fluidized silicon material particles and coating the surfaces of the silicon material particles to obtain the silicon composite material, for example, placing the silicon material in a fluidized bed reaction unit, introducing methane gas, pushing the silicon material to fluidize on the one hand, cracking the silicon material into carbon simple substances on the other hand, reacting the carbon simple substances with the fluidized silicon material particles and coating the surfaces of the silicon material particles to obtain the silicon composite material coated with the carbon layer.
In the reaction process, silicon material particles are easy to agglomerate, reaction gas is easy to form bubbles when contacting with agglomerates, gas-solid contact efficiency is influenced, coating effect of the silicon material particles is influenced, and the thickness controllability and uniformity of the coating layer are poor. By arranging the inner components in the fluidized bed reaction unit, the fluidization quality can be effectively improved, the improvement effects of the inner components with different structures on the fluidization quality are different, and how to further improve the fluidization quality and the coating uniformity degree of the silicon material are one of the continuous concerns of the technicians in the field.
In order to solve the above-mentioned technical problems, the first aspect of the present invention provides a preparation apparatus for silicon composite material, which may specifically be a fluidized bed, and fig. 1 is a schematic structural diagram of the preparation apparatus provided in an embodiment of the present invention, as shown in fig. 1, the preparation apparatus includes a reaction unit 2, a gas inlet 1 disposed at the bottom of the reaction unit, and a gas outlet 6 disposed at the top of the reaction unit, the bottom of the reaction unit 2, which is close to the gas inlet 1, is used for placing silicon material, the gas inlet 1 is used for introducing gas, and the gas outlet 6 is used for discharging unreacted gas.
At least one crushing unit 3 is arranged in the reaction unit 2 and is used for crushing and updating bubbles, so that the gas exchange quantity between a bubble phase and a milk phase is increased, the gas-solid contact efficiency is increased, the coating of a silicon material is more uniform and controllable, and the cycle performance and the multiplying power performance of the lithium ion battery are improved.
The crushing unit 3 comprises a number of crushing members arranged in parallel, in a specific embodiment, fig. 2 is a schematic structural view of a crushing member according to an embodiment of the present invention, fig. 3 is a schematic structural view of a crushing member according to another embodiment of the present invention, fig. 4 is a side view of a crushing member according to an embodiment of the present invention, as shown in fig. 2-4, the crushing member comprises a first baffle plate and a second baffle plate which are arranged opposite and not in contact, the first baffle plate comprises a first upper baffle plate 11 and a first lower baffle plate 10 which are connected to each other, the second baffle plate comprises a second upper baffle plate 13 and a second lower baffle plate 12 which are connected to each other, the first upper baffle plate 11 and the second upper baffle plate 13 are arranged in parallel, the included angle between the first lower baffle plate 10 and the second lower baffle plate 12 is 15-90 °, i.e. the first upper baffle plate 11 and the second upper baffle plate 13 form a first opening towards the gas inlet 6, the first lower baffle plate 10 and the second lower baffle plate 12 form a second opening towards the gas inlet 1, and the area of the second opening is smaller than the area of the first opening.
The first upper baffle plate 11 and the second upper baffle plate 13 are respectively provided with an upper through hole 16, the first lower baffle plate 10 and the second lower baffle plate 12 are respectively provided with a lower through hole 15, and the upper through holes 16 and the lower through holes 15 are orderly staggered, namely, in the vertical direction of the gas inlet 1 towards the gas outlet 6, the upper through holes 16 and the lower through holes 15 are not overlapped.
The first upper baffle plate 11 and the second upper baffle plate 13 are connected through a plurality of connecting plates 14, the connecting plates 14 are provided with through holes, a flow guide pipe 17 penetrates through the through holes and is arranged between the first upper baffle plate 11 and the second upper baffle plate 13, the flow guide pipe 17 is of a hollow tubular structure and is provided with two side openings, and therefore gas and fluidized silicon material particles can move from one side opening to the other side opening of the flow guide pipe 17.
When the gas and fluidized solid mixture flows through the crushing unit 3, the flow guiding effect of the first lower baffle plate 10 and the second lower baffle plate 12 is achieved, a certain radial separation speed is achieved, radial diffusion of silicon material particles is enhanced, entrained bubbles are facilitated to be crushed, the bubbles entering the inside of the flow guiding pipe 17 are orderly compressed under the synergistic effect of the flow guiding pipe 17, a part of gas and silicon material particles are ejected from the lower through holes 15, a gentle and high-quality gas-solid ejection phase is formed in a certain pressure resistance range, and due to the fact that the ejected particles have a larger radial speed, bubbles in other gas-solid phases outside the crushing unit 3 can be effectively crushed, the fluidization quality outside the crushing unit 3 is improved, and piezoresistance is not very high, and due to the fact that pressure difference exists between the gas-solid phases outside the crushing unit 3, a part of gas and particles outside the crushing unit 3 are pumped into the crushing member through the upper through holes 16, the gas and silicon material particles located between the flow guiding pipe 17 and the first baffle plate and the second baffle plate form a movable flow state, so that the uniformity of dispersing of silicon material particles is facilitated to be improved, and the coating effect is improved.
It will be appreciated that the size of the bubbles in the reaction unit 2 has a great relationship with the structure of the crushing member, and in order to further enhance the crushing effect of the bubbles, the crushing member is further defined by the present invention, specifically, the vertical distance a between the first upper baffle plate 11 and the second upper baffle plate 13 is 40 to 500mm, and the height b between the first upper baffle plate 11 and the second upper baffle plate 13 is 20 to 400mm.
The ratio of the total area of the upper through holes 16 to the total area of the first upper baffle plate 11 and the second upper baffle plate 13 is not more than 10%, further 0.1% -3%; the ratio of the total area of the lower through holes 15 to the total area of the first lower baffle 10 and the second lower baffle 12 is not more than 5%, and further 0.5% -5%, and the shapes of the upper through holes 16 and the lower through holes 15 can be oval and square as shown in fig. 2-3, or can be reasonably set according to the needs.
When the cross section of the flow guide pipe 17 is in the shape of an inverted triangle shown in fig. 2 or a circle shown in fig. 3, the crushing effect on bubbles is good; in addition, the flow guide 17 may be a flow guide having a heat exchange function in order to facilitate transfer of heat in the bed.
The crushing members in different crushing units 3 are arranged in a staggered manner, and are suitable for being used when the gas velocity is high, fig. 5 is a schematic diagram of the crushing unit provided by an embodiment of the invention, as shown in fig. 5, a first crushing unit 3-1 and a second crushing unit 3-2 are sequentially arranged in the reaction unit 2 from one side close to the gas inlet 1 to one side close to the gas outlet 6, and an included angle between the crushing member in the first crushing unit 3-1 and the crushing member in the second crushing unit 3-2 is alpha, 0 degrees is less than alpha and less than 180 degrees, and further alpha is 90 degrees.
The position of the crushing unit 3 in the reaction unit 2 is regulated and controlled, so that the diameter of bubbles in the reaction unit 2 is controlled, the transfer of gas-solid two phases in the reaction unit 2 is improved, specifically, the vertical distance between the crushing unit 3 and the gas inlet 1 is not less than 100mm, and when the crushing unit 3 comprises a first crushing unit 3-1 and a second crushing unit 3-2, the vertical distance between the first crushing unit 3-1 close to the gas inlet 1 and the gas inlet 1 is not less than 100mm.
Since the fluidized bed chemical vapor deposition method for coating silicon material is characterized in that bubbles are large and gas-solid separation is difficult, a gas-solid separator is arranged at one side close to a gas outlet 6, the separation efficiency of a conventional gas-solid separator, such as a cyclone separator, is usually not higher than 99%, and escaping silicon material particles seriously affect the product yield and economic benefits, therefore, the device also comprises a separation unit arranged at one side of a crushing unit 3 close to the gas outlet 6, the separation unit comprises a separation baffle 4 besides the conventional cyclone separator 5, the escape direction of silicon material particles is proved to be four-week and middle-thin distribution, therefore, as shown in figure 6, the separation baffle 4 provided by the invention is sequentially provided with a first separation baffle 4-1 and a second separation baffle 4-2 from one side far away from the gas outlet 6 to one side close to the gas outlet 1, the first separation baffle 4-1 is fan-shaped and surrounds and forms a third opening facing the gas inlet 1 and a fourth opening facing the gas outlet 6, the included angle beta between the plane of the third opening and the first separation baffle 4-1 is not more than 80 degrees, further, the included angle beta between the plane of the third opening and the first separation baffle 4-1 is 15-30 degrees, the second separation baffle 4-2 is arranged above the fourth opening close to the gas outlet 6 and is parallel to the plane of the fourth opening, the first separation baffle 4-1 with an inclined angle is used for blocking most of escaping particles from rising and returning to the reaction unit 2, the second separation baffle 4-2 is used for separating the particles partially flowing in the central area, and the combined design of the separation baffle 4 and the crushing unit 3 is adopted, an integral high-efficiency nanoparticle fluidized bed reaction system is formed.
The first separation baffle 4-1 and the second separation baffle 4-2 are provided with a plurality of gas through holes for passing unreacted gas, fig. 7 is an expanded view of the first separation baffle provided by an embodiment of the present invention, fig. 8 is a plan view of the second separation baffle provided by another embodiment of the present invention, and as shown in fig. 7-8, the first separation baffle 4-1 has square gas through holes as shown in fig. 7, the opening ratio is 1% -10%, that is, the total area of the gas through holes is 1% -10% of the total area of the first separation baffle 4-1; the second separation baffle 4-2 has square gas through holes as shown in fig. 8, and the shape of the gas through holes of the first separation baffle 4-1 and the second separation baffle 4-2 may be circular, corrugated, umbrella-shaped, or the like, in addition to the square holes.
The ratio of the cross-sectional area of the second separation baffle 4-2 to the first separation baffle 4-1 is 0.1-1, and the ratio of the cross-sectional area of the second separation baffle 4-2 to the cross-sectional area of the third opening is not less than 1, further 1.2-1.8.
The vertical distance between the second separation baffle 4-2 and the first separation baffle 4-1 is 10-500mm.
The cyclone 5 may be a conventional device in the art and the invention is not described in detail here.
The second aspect of the present invention provides a method for preparing a silicon composite material, which is carried out in any one of the above devices, comprising the steps of:
placing silicon material at the bottom of a reaction unit 2 close to a gas inlet 1, inputting gas from the gas inlet 1, entering the reaction unit 2, enabling the gas entering the reaction unit 2 to generate cracking reaction, pushing the silicon material to fluidize, gradually breaking bubbles formed by particle aggregates and the gas by a breaking unit 3 to form a high-quality gas-solid state, enabling high-quality fluidized silicon material particles to react with cracked simple substances and cover the surface of the silicon material to form a silicon composite material, separating unreacted gas through a separation baffle 4 and a cyclone separator 5, enabling the unreacted gas to flow out from a gas outlet 6, returning the particle substances to the reaction unit 2 through the separation baffle 4 and the cyclone separator 5, and naturally cooling the reactor to room temperature after the reaction is completed, thus obtaining a reaction product.
In one embodiment, the temperature of the reaction unit is 380-1000 ℃, the gauge pressure is 0.01-1Mpa, the time is 1-100min, the superficial gas velocity is 0.001-1m/s, and further, the superficial gas velocity is 0.05-0.7m/s.
The vertical distance between the crushing unit 3 and the gas inlet 1 is a, the static bed height of the silicon-based material is b, the vertical distance between the first separation baffle 4-1 and the gas inlet 1 is c, and a: c is less than or equal to 2.5, b: c is 2.5-4.
The silicon material is pretreated silicon powder, the grain diameter of the silicon material is 0.01-50 microns, further 0.01-10 microns, the gas can be one or more of a carbon source, a nitrogen source, a sulfur source and inert gases, specifically, the carbon source is one or more of methane, ethane, propane, ethylene, acetylene and propylene, the nitrogen source is one or more of acetonitrile, pyridine, pyrrole, ammonia and nitrogen dioxide, the sulfur source is one or more of hydrogen sulfide, thiophene and sulfur dioxide, and the inert gases are one or more of nitrogen, argon and helium.
The invention is illustrated in detail below with reference to specific examples:
example 1
In the embodiment, a device shown in fig. 1 is adopted, 2 crushing units are arranged, each crushing unit comprises 4 crushing members, an included angle alpha=90° between the crushing members in the first crushing unit and the crushing members in the second crushing unit is shown in fig. 2, each crushing member comprises a first upper baffle plate and a first lower baffle plate which are connected with each other, a second upper baffle plate and a second lower baffle plate which are connected with each other, the first upper baffle plate and the second upper baffle plate are arranged in parallel, and the included angle between the first lower baffle plate and the second lower baffle plate is 60 °; the flow guide pipe has a heat exchange function, and the ratio of the total area of the upper through holes 16 to the total area of the first upper baffle plate and the second upper baffle plate is 6%; the ratio of the total area of the lower through holes 15 to the total area of the first lower baffle plate and the second lower baffle plate is 3%. The vertical distance between the first upper baffle plate and the second upper baffle plate is 150mm; the height of the first upper baffle plate and the second upper baffle plate is 200mm. The vertical distance of the first crushing unit from the gas inlet 1 is 200mm. The gas through holes in the first separation baffle are square, and the shape of the gas through holes in the second separation baffle is umbrella-shaped.
The reaction temperature in the fluidized bed reaction device is 850 ℃, the reaction pressure (gauge pressure) is 0.01Mpa, the carbon source is a mixture of methane, ethylene and propylene, and simultaneously nitrogen source and inert gas are introduced, and the average grain diameter of the silicon-based material is 80nm.
As shown in fig. 9, the particle size of the silicon composite material provided in the embodiment is relatively uniform, which indicates that the uniformity of the surface coating layer of the silicon material is relatively good. FIG. 10 is a Raman spectrum of the nitrogen-doped silicon-carbon composite material prepared in example 1 of the present invention, wherein the silicon composite material has typical D and G peaks as shown in FIG. 10.
After electrode performance measurement is carried out on the silicon composite material prepared in the embodiment by a charge-discharge tester, capacities of 2315, 2021 and 1320mAh/g at current densities of 0.3, 0.5 and 1A/g are respectively obtained, and after 500 circles of circulation is carried out at current densities of 2A/g, the capacity retention rate is 82%.
Example 2
The device used in this embodiment can refer to embodiment 1, and differs in that: the ratio of the total area of the upper through holes to the total area of the first upper baffle plate and the second upper baffle plate is 8%; the ratio of the total area of the lower through holes to the total area of the first lower baffle plate and the second lower baffle plate was 2%. The vertical distance between the first upper baffle plate and the second upper baffle plate is 180mm; the heights of the first upper baffle plate and the second upper baffle plate are 180mm.
The reaction temperature in the fluidized bed reaction device is 850 ℃, the reaction pressure (gauge pressure) is 0.02Mpa, the carbon source is a mixture of methane, ethylene and propylene, and simultaneously nitrogen source and inert gas are introduced, and the average grain diameter of the silicon-based material is 100nm.
The nitrogen content in the silicon composite material is detected, and the nitrogen content is 2.08 weight percent, which indicates that the nitrogen element is successfully doped into the silicon composite material. FIG. 11 is a charge-discharge curve of the nitrogen-doped silicon-carbon composite material prepared in example 2 of the present invention, as shown in FIG. 11, after the electrode performance of the silicon composite material prepared in this example is measured by a charge-discharge tester, the capacities of the silicon composite material at current densities of 0.3, 0.5 and 1A/g are 2367, 2045 and 1386mAh/g, respectively, and after the silicon composite material is cycled for 500 circles at a current density of 2A/g, the capacity retention rate is 85%, and good cycle characteristics are exhibited.
Example 3
The device used in this embodiment can refer to embodiment 1, and differs in that: the ratio of the total area of the upper through holes to the total area of the first upper baffle plate and the second upper baffle plate is 8%; the ratio of the total area of the lower through holes to the total area of the first lower baffle plate and the second lower baffle plate was 2%. The vertical distance between the first upper baffle plate and the second upper baffle plate is 180mm; the heights of the first upper baffle plate and the second upper baffle plate are 180mm.
The reaction temperature in the fluidized bed reaction device is 650 ℃, the reaction pressure (gauge pressure) is 0.02Mpa, the carbon source is a mixture of ethylene and propylene, and simultaneously, the sulfur source and inert gas are introduced, and the average grain diameter of the silicon-based material is 80nm.
The sulfur-doped content in the silicon composite material is detected, and the sulfur-doped content is 2.35 weight percent. By adopting the same method as in example 2, after electrode performance measurement is carried out on the silicon composite material prepared in the example by a charge-discharge tester, the capacities of the silicon composite material are 2336 mAh/g, 2025 mAh/g and 1372mAh/g respectively at current densities of 0.3, 0.5 and 1A/g, and after 800 circles of circulation is carried out at current densities of 2A/g, the capacity retention rate is 81.5%.
Example 4
The device used in this embodiment can refer to embodiment 1, and differs in that: the ratio of the total area of the upper through holes to the total area of the first upper baffle plate and the second upper baffle plate is 8%; the ratio of the total area of the lower through holes to the total area of the first lower baffle plate and the second lower baffle plate was 2%. The vertical distance between the first upper baffle plate and the second upper baffle plate is 180mm; the heights of the first upper baffle plate and the second upper baffle plate are 180mm.
The reaction temperature in the fluidized bed reaction device is 850 ℃, the reaction pressure (gauge pressure) is 0.02Mpa, the carbon source is a mixture of methane, ethylene and propylene, and simultaneously nitrogen source, sulfur source and inert gas are introduced, and the average grain diameter of the silicon-based material is 100nm.
Detecting sulfur-doped and nitrogen-doped contents in the silicon composite material, wherein the sulfur-doped content is 2.42wt% and the nitrogen-doped content is 2.38wt% through detection; by adopting the same method as in example 2, after electrode performance measurement is carried out on the silicon composite material prepared in the example by a charge-discharge tester, capacities of 2356 mAh/g, 2038 mAh/g and 1379mAh/g are respectively set at current densities of 0.3, 0.5 and 1A/g, and after 800 circles of cycles are carried out at current densities of 2A/g, the capacity retention rate is 81%, and excellent cycle characteristics are shown.
Comparative example 1
The comparative example used a conventional fluidized bed reaction apparatus without a crushing unit. The reaction temperature in the fluidized bed reaction device is 850 ℃, the reaction pressure (gauge pressure) is 0.01Mpa, the carbon source is a mixture of methane, ethylene and propylene, and simultaneously nitrogen source and inert gas are introduced, and the average grain diameter of the silicon-based material is 80nm.
The capacity of the silicon composite material obtained after the reaction was 1402, 1085 and 751mAh/g at a current density of 0.3, 0.5 and 1A/g, respectively, and the capacity retention rate was 45% after 500 cycles at a current density of 2A/g.
Comparative example 2
This comparative example uses a conventional fluidized bed reaction apparatus, and a conventional grid is provided as the crushing member. The reaction temperature in the fluidized bed reaction device is 850 ℃, the reaction pressure (gauge pressure) is 0.01Mpa, the carbon source is a mixture of methane, ethylene and propylene, and simultaneously nitrogen source and inert gas are introduced, and the average grain diameter of the silicon-based material is 80nm.
The capacity of the silicon composite material obtained after the reaction is 1442, 1091 and 762mAh/g under the current density of 0.3, 0.5 and 1A/g, and the capacity retention rate is 46% after 500 circles of circulation under the current density of 2A/g.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The preparation device of the silicon composite material is characterized by comprising a reaction unit, a gas inlet arranged at the bottom of the reaction unit and a gas outlet arranged at the top of the reaction unit;
at least one crushing unit is arranged in the reaction unit, and the crushing unit comprises a plurality of crushing members which are arranged in parallel;
the crushing member comprises a first baffle, a second baffle and a flow guide pipe, wherein the first baffle and the second baffle are oppositely arranged and form a first opening and a second opening which are communicated with each other, the first opening faces the gas outlet, the second opening faces the gas inlet, and a plurality of through holes are formed in the first baffle and the second baffle; the flow guide pipe is positioned between the first baffle and the second baffle;
the first baffle comprises a first upper baffle and a first lower baffle which are connected with each other, the second baffle comprises a second upper baffle and a second lower baffle which are connected with each other, the first upper baffle and the second upper baffle are arranged in parallel, and the included angle between the first lower baffle and the second lower baffle is 15-90 degrees;
the first upper baffle plate and the second upper baffle plate are respectively provided with an upper through hole, the first lower baffle plate and the second lower baffle plate are respectively provided with a lower through hole, and the upper through holes and the lower through holes are sequentially staggered;
the ratio of the total area of the upper through holes to the total area of the first upper baffle plate and the second upper baffle plate is not more than 10%; the ratio of the total area of the lower through holes to the total area of the first lower baffle plate and the second lower baffle plate is not more than 5%;
the gas inlet is arranged on the first upper baffle plate, the first upper baffle plate is connected with the second upper baffle plate through a plurality of connecting plates, through holes are formed in the connecting plates, the flow guide pipe penetrates through the through holes and is arranged between the first upper baffle plate and the second upper baffle plate, the flow guide pipe is of a hollow tubular structure, the arrangement direction of the flow guide pipe is perpendicular to the direction of the gas inlet towards the gas outlet, and the flow guide pipe is provided with two side openings.
2. The device according to claim 1, wherein the reaction unit is provided with a first crushing unit and a second crushing unit in sequence from the side close to the gas inlet to the side close to the gas outlet, and an included angle between a crushing member in the first crushing unit and a crushing member in the second crushing unit is alpha, and 0 degrees < alpha < 180 degrees.
3. The apparatus of claim 1, wherein the first and second upper baffles have a vertical separation of 40-500mm; the heights of the first upper baffle plate and the second upper baffle plate are 20-400mm.
4. The apparatus according to claim 1, wherein the vertical distance of the crushing unit from the gas inlet is not less than 100mm.
5. The device according to claim 1, further comprising a separation unit arranged on the side of the crushing unit close to the gas outlet, wherein the separation unit comprises a first separation baffle plate arranged on the side close to the gas inlet and a second separation baffle plate arranged on the side close to the gas outlet, the first separation baffle plate encloses and forms a third opening facing the gas inlet and a fourth opening facing the gas outlet, the included angle between the plane of the third opening and the first separation baffle plate is not more than 80 degrees, the second separation baffle plate is arranged above the fourth opening close to the gas outlet, and the first separation baffle plate and the second separation baffle plate are provided with a plurality of gas through holes.
6. A method of preparing a silicon composite material, carried out in an apparatus according to any one of claims 1 to 5, comprising the steps of:
placing a silicon-based material at the bottom of a reaction unit, which is close to a gas inlet, inputting gas from the gas inlet, entering the reaction unit, performing cracking reaction on the gas entering the reaction unit, and performing cladding reaction with the fluidized silicon-based material, thereby obtaining the silicon composite material after the reaction is finished.
7. The process according to claim 6, wherein the temperature of the reaction unit is 380-1000 ℃, the gauge pressure is 0.01-1Mpa, the time is 1-100min, and the superficial gas velocity is 0.001-1m/s.
8. The method according to claim 6 or 7, wherein the ratio of the vertical distance of the crushing unit from the gas inlet to the static bed height of the silicon-based material is not more than 2.5.
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