CN111072051B - Method and device for producing nano coating material - Google Patents

Method and device for producing nano coating material Download PDF

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Publication number
CN111072051B
CN111072051B CN201811224283.2A CN201811224283A CN111072051B CN 111072051 B CN111072051 B CN 111072051B CN 201811224283 A CN201811224283 A CN 201811224283A CN 111072051 B CN111072051 B CN 111072051B
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reactor
gas
temperature
cyclone
outlet
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CN111072051A (en
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邱新平
张文广
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Beijing Qingchuang Silicon Valley Technology Co ltd
Tsinghua University
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Beijing Qingchuang Silicon Valley Technology Co ltd
Tsinghua University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
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Abstract

The present disclosure relates to a method and apparatus for producing nanocoating material, the method comprising: step (1-3): preheating the core material, the precursor of the shell material and the fluidizing gas to different temperatures; step (4-6): adding the preheated raw materials and the fluidized gas into a reactor for reaction, and sequentially feeding the reaction mixture into a first cyclone separator and a second cyclone separator so that gas substances and solid substances respectively return to the reactor through a circulating pipeline, wherein the step (7): the resulting homogeneous and dense coating material is discharged under the action of the fluidizing gas. The reaction mixture flows and is uniformly dispersed among the reactor, the first cyclone separator and the second cyclone separator under the action of the fluidizing gas, and the problem that nanoparticles are easy to agglomerate is solved. In the reaction of the present disclosure, the thickness and compactness of the coating material can be accurately controlled by controlling the cycle time, so that the physical properties of the material can be accurately controlled.

Description

Method and device for producing nano coating material
Technical Field
The present disclosure relates to a method and apparatus for producing nanocoating material. In particular, the present disclosure relates to a mass production method and apparatus of a nano-coating material for an electrode of an electrochemical device, and more particularly, to a mass production method and apparatus of a nano-silicon material for an electrochemical device.
Background
In the field of lithium ion batteries, in order to improve energy density, electrode materials with high specific capacity need to be developed. The negative electrode material used in the existing commercial lithium ion battery is graphite, the actual specific capacity is close to the theoretical limit, and the problem to be solved urgently is to find a new negative electrode material with high specific capacity.
Among the many alternatives of negative electrode materials, silicon materials have the highest theoretical specific capacity and are widely concerned and valued by research and development workers. Many reports have been made on the research on the nano-silicon particles and the composite material thereof, but the problem of thickening of a solid electrolyte interface film (SEI film) has not been solved; the silicon material adopting the nano hollow structure proposed by the Chinese patent application with the publication number of CN105705460A can solve the thickening of the SEI film, but is still at the laboratory preparation level (gram level: gram/time).
Thus, there remains a need for a commercially viable, large-scale method and apparatus for producing nanocoating materials.
Disclosure of Invention
It is therefore an object of the present disclosure to provide a method of producing nanocoating material.
It is an object of the present disclosure to provide an apparatus for producing nanocoating material.
According to an embodiment of the present disclosure, there is provided a method of producing a nanocoating material, the method including:
the first step is as follows: bringing the temperature of the nuclear material to a first temperature by preheating;
the second step is as follows: bringing the temperature of the precursor of the shell material to a second temperature by preheating;
the third step: bringing the temperature of the fluidization gas to a third temperature by preheating;
wherein the reaction temperature of the precursor of the shell material is T0When the first temperature is T0+100 ℃ to T0+150℃，
The second temperature is T0-100 ℃ to T0-50℃，
The third temperature is T0-50 ℃ to T0+150℃；
The fourth step: adding the preheated core material into a reactor, and continuously introducing fluidizing gas and a precursor of the shell material to enable the precursor of the shell material to react on the surface of the core material to generate the coating material, and simultaneously moving at least part of a reacted first mixture containing the generated coating material to a first cyclone separator under the action of the gas flow;
the fifth step: at least part of the first mixture moved to the first cyclone in the fourth step is separated therein, wherein at least part of the produced solid matter of the coating material, unreacted nuclear material is settled in the first cyclone, heated again and then returned to the reactor, and at least part of the second mixture treated in the first cyclone is sent to the second cyclone;
a sixth step: at least part of the solid matter of the second mixture fed to the second cyclone in the fifth step is settled therein and reheated and then returned to the reactor, at least part of the gaseous matter of the second mixture fed to the second cyclone is filtered and returned to the recycle gas inlet of the reactor through a recycle line,
a seventh step of: the resulting coating material is discharged through the outlet of the reactor.
In some embodiments of the present disclosure, in the seventh step, the generated clad material is discharged under the action of the air flow in a case where the generated clad material satisfies a predetermined condition;
the predetermined condition is, for example, that the thickness of the clad layer is 10 to 30nm or more.
The cycling of the reaction mixture in the fourth, fifth and sixth steps is performed at least twice before the seventh step is performed.
In some embodiments of the present disclosure, in the sixth step, at least a portion of the gaseous species of the filtered second mixture is pressurized on the recirculation line.
In some embodiments of the present disclosure, the fourth to sixth steps are repeatedly performed, and
the fourth step includes: fresh nuclear material heated to a first temperature is added to the reactor without emptying the reactor for continuous production.
In some embodiments of the disclosure, in the method: the core material may or may not participate in the reaction; the shell material can be obtained by the decomposition reaction of a single precursor, or can be obtained by the mutual reaction of more than two precursors.
In some embodiments of the present disclosure, the temperature of the reactor wall is controlled below the reaction temperature of the precursor of the shell material to prevent the precursor of the shell material from reacting on the reactor wall, thereby preventing reactor fouling.
In some embodiments of the present disclosure, the particle size of the core material is between 1nm and 1 μm, 10nm and 200nm, or 30nm and 80 nm.
In some embodiments of the present disclosure, to obtain a shell material with a thickness of 10-30nm, the time of introducing the fluidizing gas is 0.5h-5h, the velocity of the fluidizing gas is 5L/min cm2-25L/min·cm2(ii) a The time for introducing the precursor of the shell material is 0.1h-3h, and the speed of the precursor is 0.2L/min cm2-1.5L/min·cm2。
The fluidizing gas is any suitable gas that does not react with the core material and/or the precursor of the shell material and/or the shell material under temperature/pressure conditions within the reactor, and in some embodiments of the present disclosure, the fluidizing gas initially introduced (i.e., before the gas produced during the reaction has not been recycled as fluidizing gas) may be an inert gas. The fluidizing gas may also be nitrogen.
In some embodiments of the present disclosure, the core material is a nano-or micro-scale metal carbonate, and the precursor of the shell material refers to a compound or mixture including a silicon-containing element, including: at least one of silane, trichlorosilane, dichlorosilane, silicon tetrachloride and a mixture of the silane, the trichlorosilane, the dichlorosilane and the silicon tetrachloride and hydrogen or a combination of the silane, the trichlorosilane, the dichlorosilane and the silicon tetrachloride.
In some embodiments of the present disclosure, the core material refers to a metal carbonate, including at least one of lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, or a combination thereof, as long as a sufficiently uniform particle size distribution of the core material is ensured, with particle sizes between 10nm and 200 nm.
In some embodiments of the present disclosure, the shell material precursor is silane, the initial introduction of the fluidizing gas is nitrogen or argon, the temperature of the preheated initial silane is controlled between 300 ℃ and 350 ℃, and the temperature of the initial fluidizing gas is controlled between 400 ℃ and 500 ℃.
In some embodiments of the present disclosure, the temperature of the metal carbonate is between 410 ℃ and 850 ℃, preferably between 450 ℃ and 550 ℃.
When the silane gas contacts with the carbonate, heat exchange is carried out immediately, so that the temperature of the silane gas reaches the decomposition temperature in a short time, and a coating layer is formed. When the temperature of the preheated silane gas is higher than 400 ℃, it may cause premature decomposition of silane to produce solid silicon particles.
According to another aspect of the present disclosure, there is provided an apparatus for preparing a nano coating material, the coating material coating a surface of a core material with a shell material, the apparatus comprising:
the reactor comprises a first feeding hole, a first air inlet, a second air inlet, a third air inlet, a first discharging hole, a first outlet and a second feeding hole, wherein the first feeding hole is positioned above the first air inlet, the second air inlet and the third air inlet;
a first cyclone separator comprising a fourth gas inlet connected to the first outlet of the reactor, a second outlet, a third outlet, and a filtering device disposed at the third outlet;
a second cyclone separator comprising a fifth inlet connected to the third outlet of the first cyclone separator, a fourth outlet, a fifth outlet and a filtering means disposed at the fifth outlet;
the filtering device of the first cyclone separator and the filtering device of the second cyclone separator are respectively arranged at the third outlet of the first cyclone separator and the fifth outlet of the second cyclone separator,
a first circulation line connecting the fifth outlet of the second cyclone and the third inlet of the reactor,
a second circulation pipeline connected with a second feed inlet of the reactor, a second outlet of the first cyclone separator, and a fourth outlet of the second cyclone separator,
heating means disposed on at least portions of the first cyclone, the second cyclone and the lower circulation line.
In some embodiments of the present disclosure, the apparatus further comprises a gas pressurization device located on the first circulation line such that the first circulation line connects the fifth outlet of the second cyclone and the third inlet of the reactor through the gas pressurization device.
In some embodiments of the present disclosure, the reactor further comprises a gas distribution plate disposed at a bottom of the reactor;
in some embodiments of the present disclosure, the first gas inlet is located above the gas distribution plate, and the second and third gas inlets are located below the gas distribution plate.
The apparatus for preparing a granular material according to the present disclosure may further include components of piping, valves, pumps, flow meters, thermometers, pressure gauges, raw material tanks, etc., which are conventionally used in the art, and the structure and function thereof are the same as those of the prior art, and thus, they will not be described herein again.
In the above-described method according to the present disclosure, the precursor of the shell material, which is in contact with the fluidized core material in the reactor, is decomposed to form the shell material preferentially on the surface of the core material after reaching the reaction temperature, rather than being self-nucleated in the gas (the "nucleation" means the generation of crystal nuclei, which is not the same concept as the nuclei of the aforementioned "core material") and crystallized, whereby a fine-grained uniform coating material can be obtained.
Advantageous effects
The reaction mixture circularly flows and is uniformly dispersed among the reactor, the first cyclone separator and the second cyclone separator under the action of the fluidizing gas, and the problem that nanoparticles are easy to agglomerate in the conveying process is solved. In the reaction of the present disclosure, the thickness and compactness of the coating material can be accurately controlled by controlling the cycle time, so that the physical properties of the material can be accurately controlled.
In addition, the temperature of the nuclear material, the precursor of the shell material and the inner wall of the reactor is accurately controlled, so that the precursor of the shell material is only generated on the surface of the nuclear material, and the problem of reactor fouling is avoided.
In the reaction process of the present disclosure, since the temperatures of the reactants are respectively controlled, the preheated second batch of nuclear material can be directly introduced after the reactants are discharged, so that the adjustment treatment of atmosphere, temperature and the like of the reactor is hardly required, thereby realizing the continuous production of different batches.
The introduction of the gas pressurization device enables the gas in the reaction mixture to smoothly return to the reactor through the circulation line without causing a counter flow.
Drawings
FIG. 1 is a flow diagram of a method according to one embodiment of the invention.
Fig. 2 is a schematic view of a reaction apparatus according to an embodiment of the present invention.
Fig. 3 is a schematic view of a reaction apparatus according to another embodiment of the present invention.
Fig. 4 and 5 are a scanning electron micrograph and a transmission electron micrograph, respectively, of hollow silicon particles prepared according to an embodiment of the present invention.
Fig. 6 is a graph of the cycling performance of a battery prepared according to one embodiment of the present invention containing hollow silicon particles of the present invention.
FIG. 7 is a scanning electron micrograph of hollow silicon particles prepared according to another embodiment of the present invention.
FIG. 8 is a schematic view of a reaction apparatus according to yet another embodiment of the present invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
In this document, unless otherwise stated, "first", "second", etc. are used merely to distinguish different units, steps, etc. without limiting the order thereof, and they may be replaced without departing from the gist of the present invention.
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
As shown in fig. 1, a method of producing a nanocoating material according to an embodiment of the present disclosure may include:
the first step is as follows: bringing the temperature of the nuclear material to a first temperature by preheating;
the second step is as follows: bringing the temperature of the precursor of the shell material to a second temperature by preheating;
the third step: bringing the temperature of the fluidization gas to a third temperature by preheating;
wherein the reaction temperature of the precursor of the shell material is T0When the first temperature is T0+100 ℃ to T0+150℃，
The second temperature is T0-100 ℃ to T0-50℃，
The third temperature is T0-50 ℃ to T0+150℃；
The fourth step: adding the preheated core material into a reactor, and continuously introducing fluidizing gas and a precursor of the shell material to enable the precursor of the shell material to react on the surface of the core material to generate the coating material, and simultaneously moving at least part of a reacted first mixture containing the generated coating material to a first cyclone separator under the action of the gas flow;
the fifth step: at least part of the first mixture moved to the first cyclone in the fourth step is separated therein, wherein at least part of the produced solid matter of the coating material, unreacted nuclear material is settled in the first cyclone, heated again and then returned to the reactor, and at least part of the second mixture treated in the first cyclone is sent to the second cyclone;
a sixth step: at least part of the solid matter of the second mixture fed to the second cyclone in the fifth step is settled therein and reheated and then returned to the reactor, at least part of the gaseous matter of the second mixture fed to the second cyclone is filtered and returned to the recycle gas inlet of the reactor through a recycle line,
a seventh step of: the resulting coating material is discharged through the outlet of the reactor.
In the method, the coating material to be generated can be fully dispersed through the first cyclone separator and the second cyclone separator, so that a product with small particle size and uniform dispersion is obtained.
According to one embodiment of the present disclosure, in the seventh step, in a case where the generated clad material satisfies a predetermined condition, the generated clad material is discharged by an air flow; the cycling of the reaction mixture in the fourth, fifth and sixth steps is performed at least twice before the seventh step is performed. The predetermined condition is, for example, that the thickness of the clad layer reaches 10 to 30nm or more, and may be set in advance according to the requirements for the clad layer in actual processing, whereby a clad material satisfying the processing requirements can be directly obtained. In the above method, by performing the above steps cyclically, for example, at least twice, a densely coated clad material can be obtained.
According to one embodiment of the present disclosure, in the sixth step, at least part of the gaseous species of the filtered second mixture is pressurized on the circulation line. By pressurizing, the pressure in each container can be more effectively controlled, so that the flow direction of solid products and gaseous products is controlled, and the generation of the coating material is facilitated.
According to an embodiment of the present disclosure, the fourth to sixth steps are repeatedly performed, and the fourth step includes: fresh nuclear material heated to a first temperature is added to the reactor without emptying the reactor for continuous production. Thus, the waste of energy and carrier gas due to the repeated change of atmosphere and temperature in the reactor can be greatly reduced.
According to one embodiment of the disclosure, in the method: the core material may or may not participate in the reaction; the shell material can be obtained by a single precursor undergoing a decomposition reaction, and can also be obtained by reacting two or more precursors with each other.
According to an embodiment of the present disclosure, the method further comprises: the temperature of the walls of the reactor is controlled below the reaction temperature of the precursor of the shell material. In this way, precursors of the shell material can be prevented from reacting on the reactor walls leading to reactor fouling.
According to one embodiment of the present disclosure, the particle size of the core material is between 1nm and 1 μm.
When the particle size of the core material is within this range, the resultant coating material is moderately active, that is, it can be used more advantageously for subsequent applications, while reducing the occurrence of particle agglomeration.
According to one embodiment of the disclosure, the time of introducing the fluidizing gas is 0.5h to 5h, and the velocity of the fluidizing gas is 5L/min cm2-25L/min·cm2(ii) a The time for introducing the precursor of the shell material is 0.1h-3h, and the speed of the precursor is 0.2L/min cm2-1.5L/min·cm2。
The process can be used for effectively obtaining a uniform and compact coating material.
According to one embodiment of the present disclosure, the fluidizing gas is an inert gas or nitrogen, the core material is a nano-sized or micro-sized metal carbonate, and the precursor of the shell material is selected from at least one of silane, trichlorosilane, dichlorosilane, silicon tetrachloride and a mixture thereof with hydrogen or a combination thereof.
According to one embodiment of the present disclosure, the core material includes at least one of lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate or a combination thereof, the particle size of which is between 10nm and 200nm, the shell material precursor is silane, the fluidizing gas is nitrogen or argon, the temperature of the preheated original silane is controlled between 300 ℃ and 350 ℃, the temperature of the initial fluidizing gas is controlled between 400 ℃ and 500 ℃, and the temperature of the metal carbonate is controlled between 410 ℃ and 850 ℃.
The coating material for an electrode of a lithium ion battery can be efficiently obtained by using the above-mentioned material.
As shown in fig. 2, a preparation apparatus of a nanocoating material according to an embodiment of the present disclosure may include:
the reactor 1 comprises a first feeding hole 10, a first air inlet 11, a second air inlet 12, a third air inlet 13, a first discharging hole 14, a first outlet 15 and a second feeding hole 16, wherein the first feeding hole 10 is positioned above the first air inlet 11, the second air inlet 12 and the third air inlet 13;
a first cyclone 2 comprising a fourth gas inlet 21, a second outlet 22, a third outlet 23 and a filtering means 24, said fourth gas inlet 21 being connected to the first outlet 15 of the reactor 1, said filtering means 24 being provided at said third outlet 23;
a second cyclone 3 comprising a fifth gas inlet 31, a fourth outlet 32, a fifth outlet 33 and a filtering means 34, the fifth gas inlet 31 being connected to the third outlet 23 of the first cyclone, the filtering means 34 being provided at the fifth outlet 33;
a first circulation line 4, the first circulation line 4 connecting the fifth outlet 33 of the second cyclone and the third inlet 13 of the reactor 1;
a second circulation line 5, wherein the second circulation line 5 is connected with the second feed inlet 16 of the reactor 1, the second outlet 22 of the first cyclone 2 and the fourth outlet 32 of the second cyclone 3;
heating means 7, said heating means 7 being arranged on at least part of the first cyclone 2, the second cyclone 3 and the lower circulation line 5.
According to the preparation device, the coating material to be generated can be fully dispersed through the first cyclone separator and the second cyclone separator, so that a product with small particle size and uniform dispersion can be obtained.
According to one embodiment of the present disclosure, the apparatus further comprises a gas pressurization device 8, said gas pressurization device 8 being located on said first circulation line 4.
The gas supercharging device can more effectively control the pressure in each container, thereby controlling the flow direction of solid products and gaseous products and being beneficial to the generation of coating materials.
According to one embodiment of the present disclosure, the reactor 1 further comprises a gas distribution plate 17, the gas distribution plate 17 being disposed at the bottom of the reactor 1. The gas distribution plate can effectively disperse raw materials, fluidizing gas, circulating gas and other gases entering the preparation device.
According to one embodiment of the present disclosure, the first gas inlet 11 is located above the gas distribution plate 17, and the second and third gas inlets 12 and 13 are located below the gas distribution plate 17. Because the pressure difference exists above and below the gas distribution plate, the pressure distribution in each container can be more accurately controlled through the arrangement, and the gas flow direction is controlled.
In the production apparatus using fig. 3, a specific process to be carried out may have the following flow.
Solid core material preheated to a first temperature (higher than the reaction temperature of the precursor of the shell material) is fed into the reactor through the first feed opening 10 of the reactor 1, fluidizing gas preheated to a third temperature (higher than the reaction temperature of the precursor of the shell material) is fed into the reactor through the second gas inlet 12 of the reactor 1, the fluidizing gas is uniformly distributed under the action of the gas distribution plate 17, and the solid core material is fluidized and kept at a temperature higher than the reaction temperature of the precursor of the shell material. The precursor of the shell material preheated to the second temperature (lower than the reaction temperature of the precursor of the shell material) is added to the reactor through the first gas inlet 11 of the reactor 1, so that the precursor reacts on the surface of the core material to obtain core-shell structured nano-coated particles.
The reaction mixture is fed by the action of the fluidizing gas through the first outlet of the reactor 1 into the first cyclone 2, in which first cyclone 2 most of the solid particles settle and are returned to the reactor 1 via the second recirculation line 5 from the second inlet of the reactor 1, and most of the gas and a small amount of fine solid particles are fed to the second cyclone 3 through the filtering means 24 of the first cyclone 2.
In the second cyclone 3, the mixture is further separated, the solid particles settle and are returned to the reactor 1 from the second feed port of the reactor 1 via the second circulation line 5, and the gaseous components are passed through the filter device 34 of the second cyclone 2, are fed to the third gas inlet of the reactor 1 via the first circulation line, and are fed into the reactor 1 together with the fluidizing gas through the gas distribution plate 17.
Thereby, the reaction mixture circulates and gradually reacts in the reactor, the first cyclone and the second cyclone to form a uniform and dense coating material, and after a predetermined time, the coating material is discharged through the first discharge port 14 of the reactor 1 by a gas flow.
Although one exemplary configuration of the preparation apparatus of the present invention is shown in fig. 2 and 3, it will be understood by those skilled in the art that the location of the components of these apparatus is not limited to this particular configuration.
Specifically, in FIG. 2, the lower gas inlet 11 for feeding the precursor of the preheated shell material is below the gas distribution plate 17 and communicates with the bottom gas inlet 12 and the bypass circulation gas inlet 13. But the lower gas inlet may be provided at other positions in the lower part of the reactor 1.
For example, as shown in fig. 8, lower gas inlets 11 for precursors of the shell material are provided above the gas distribution plate, one each at a bilaterally symmetric position. The air inlet can also be uniformly arranged in a circle along the periphery at the same height below the reactor.
Other parts of fig. 8 are the same as those of fig. 1, and are not described again here.
Examples
The invention will be described below by means of specific examples. Those skilled in the art will appreciate that the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
Example 1
In the apparatus shown in FIG. 1, nano calcium carbonate particles as a core material were preheated to 500 ℃ and then fed into the reactor through the upper feed inlet 10 of the reactor, and the temperature of the reactor wall was maintained at 350 ℃.
Nitrogen is used as fluidizing gas, and after being preheated to 390 ℃, the fluidizing gas passes through a gas inlet 12 at the bottom of the reactor 1 and passes through a gas distribution plate 17 to be uniformly dispersed into the reactor 1, so that the solid calcium carbonate is fluidized.
Silane (SiH) as a precursor of the shell material4) After being preheated to 350 ℃, the mixture passes through the gas distribution plate 17 through the lower gas inlet 11 of the reactor 1 and is introduced into the reactor 1, and the mixture is decomposed on the surface of the reactor 1 to generate a coated silicon layer after contacting high-temperature nano calcium carbonate particles. The fluidized reaction mixture is fed together to the first cyclone 2 under the action of a high-velocity gas stream.
In the first cyclone 2, the majority of the solid particles in the mixture settle and are returned to the reactor 1 via the lower circulation line, and the gas and a small portion of the nanoparticles are fed via the filter device 24 into the second cyclone 3.
In the second cyclone 3, the mixture is further separated, the solid particles settle and are returned to the reactor 1 via the lower circulation line, and the gas is returned to the reactor 1 via the upper circulation line 4 via the filter device 34 through the gas pressure boosting device 8 for the circulating reaction.
Heating means 7 are provided on the first cyclone 2, the second cyclone 3 and the lower circulation line to heat the settled nanoparticles to 500 c again.
After reacting for 60min, a uniform and compact silicon layer is formed on the surface of the nano calcium carbonate particles which are circulated for many times, and at the moment, a bottom discharge port 14 of the reactor 1 is opened to discharge the product.
After the product is discharged, the bottom discharge port 14 of the reactor 1 is closed, and a new batch of nano calcium carbonate particles is put into the reactor, so that continuous production can be performed without changing the state of the reactor.
Experimental example 1
The coating material prepared in example 1 is placed in a reaction kettle to react with 8 wt% of dilute hydrochloric acid for 4 hours, and then washed with ethanol, centrifuged and dried to obtain hollow silicon particles with nanometer sizes, wherein scanning electron micrographs and transmission electron micrographs of the hollow silicon particles are respectively shown in fig. 2 and fig. 3.
Uniformly mixing the prepared hollow silicon material, conductive carbon black, binder carboxymethylcellulose sodium (CMC) and graphite according to the mass ratio of 10:2:4:84, uniformly dispersing by using deionized water as a solvent to prepare negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying for 24 hours under the vacuum condition at 100 ℃ to prepare the pole piece.
An analytically pure metal lithium sheet is taken as a counter electrode, together with the prepared pole piece, a 1M Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio of 1: 1) solution of LiPF6 is taken as a conductive medium, Celgard-2320 (microporous polypropylene film) is taken as a battery diaphragm to assemble a CR2025 type button battery, and the assembly process is carried out in a glove box filled with argon. The button cell is subjected to a capacity cycling test at a current density of 140mA/g, the capacity is stabilized at 696mAh/g, and the capacity is rarely attenuated after 100 cycles, as shown in FIG. 4.
Example 2
A nanocoating material was prepared in the same manner as in example 1, except that the reaction time was changed from 60min to 30 min.
Experimental example 2
The coating material prepared in example 2 was placed in a reaction kettle to react with 8 wt% dilute hydrochloric acid for 4 hours, and then washed with ethanol, centrifuged, and dried to obtain nano-sized hollow silicon particles, and the scanning electron micrograph thereof is shown in fig. 5.
As can be seen from the comparison between FIG. 3 and FIG. 5, the thickness of the nano hollow silicon in FIG. 3 is about 30nm, while the thickness of the nano hollow silicon in FIG. 5 is about 16 nm. Therefore, the thickness of the nano hollow silicon wall can be effectively regulated and controlled by controlling the time of introducing the silane gas.
Example 3
As shown in FIG. 8, SiH in the reactor 1 was changed4Position of gas inlet 11, i.e. SiH4The gas inlet is designed in the gasThe left and right symmetrical positions above the distribution plate are respectively provided with one. The reaction was carried out in accordance with the procedure of example 1 except that the apparatus shown in FIG. 1 was replaced with the apparatus shown in FIG. 8 to obtain a nanocoating material.
SiH in comparison with example 14The temperature regulation range of the circulating fluidizing gas fed from the inlet port of the bottom 12 of the reactor 1 is wider after the inlet port is changed. Can heat the calcium carbonate powder by increasing the temperature of the circulating fluidized gas, and simultaneously avoid SiH4The gas is heated to above T by the circulating gas before contacting the powder0Resulting in decomposition.
The above embodiments are merely exemplary in nature and are not intended to limit the claimed embodiments or the application or uses of such embodiments. In this document, the term "exemplary" represents "as an example, instance, or illustration. Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, while at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing implementations will provide those of ordinary skill in the art with a convenient road map for implementing the described embodiment or embodiments. Further, various changes may be made in the function and arrangement of elements without departing from the scope defined in the claims, which includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims (12)

1. A method of producing a nanocoating material, the method comprising:
the first step is as follows: bringing the temperature of the nuclear material to a first temperature by preheating;
the second step is as follows: bringing the temperature of the precursor of the shell material to a second temperature by preheating;
the third step: bringing the temperature of the fluidization gas to a third temperature by preheating;
wherein the reaction temperature of the precursor of the shell material is T0When the first temperature is T0+100 ℃ to T0+150℃，
The second temperature is T0-100 ℃ to T0-50℃，
The third temperature is T0-50 ℃ to T0+150℃；
The fourth step: adding the preheated core material into a reactor, and continuously introducing fluidizing gas and a precursor of the shell material to enable the precursor of the shell material to react on the surface of the core material to generate the coating material, and simultaneously moving at least part of a reacted first mixture containing the generated coating material to a first cyclone separator under the action of the gas flow;
the fifth step: at least part of the first mixture moved to the first cyclone in the fourth step is separated therein, wherein at least part of the produced solid matter of the coating material, unreacted nuclear material is settled in the first cyclone, heated again and then returned to the reactor, and at least part of the second mixture treated in the first cyclone is sent to the second cyclone;
a sixth step: at least part of the solid matter of the second mixture fed to the second cyclone in the fifth step is settled therein and reheated and then returned to the reactor, at least part of the gaseous matter of the second mixture fed to the second cyclone is filtered and returned to the recycle gas inlet of the reactor through a recycle line,
a seventh step of: the resulting coating material is discharged through the outlet of the reactor,
in the sixth step, at least a portion of the gaseous material of the filtered second mixture is pressurized on the recycle line.
2. The method of claim 1,
in the seventh step, the generated coating material is discharged under the action of air flow when the generated coating material satisfies a predetermined condition;
the cycling of the reaction mixture in the fourth, fifth and sixth steps is performed at least twice before the seventh step is performed.
3. The method of claim 1,
the fourth to sixth steps are repeatedly performed, and
the fourth step includes: fresh nuclear material heated to a first temperature is added to the reactor without emptying the reactor for continuous production.
4. Method according to claim 1, characterized in that in the method:
the core material may or may not participate in the reaction; the shell material can be obtained by a single precursor undergoing a decomposition reaction, and can also be obtained by reacting two or more precursors with each other.
5. The method of claim 1, further comprising: the temperature of the walls of the reactor is controlled below the reaction temperature of the precursor of the shell material.
6. The method of claim 1, wherein the particle size of the core material is between 1nm and 1 μ ι η.
7. The method according to claim 1, characterized in that the time for introducing the fluidizing gas is 0.5h-5h and the velocity of the fluidizing gas is 5L/min-cm2-25L/min·cm2(ii) a The time for introducing the precursor of the shell material is 0.1h-3h, and the speed of the precursor is 0.2L/min cm2-1.5L/min·cm2。
8. The method according to claim 1, wherein the fluidizing gas is an inert gas or nitrogen,
the core material is a nano-or micro-sized metal carbonate,
the precursor of the shell material is selected from at least one or the combination of silane, trichlorosilane, dichlorosilane, silicon tetrachloride and the mixture of the silane, the trichlorosilane, the dichlorosilane and the silicon tetrachloride and hydrogen.
9. The method of claim 1, wherein the core material comprises at least one of lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, or a combination thereof, having a particle size between 10nm and 200nm,
the shell material precursor is silane, the fluidizing gas is argon, the temperature of the preheated original silane is controlled to be 300-350 ℃, the temperature of the initial fluidizing gas is controlled to be 400-500 ℃, and the temperature of the metal carbonate is controlled to be 410-850 ℃.
10. An apparatus for producing a nano-sized clad material in which a shell material is clad on a surface of a core material, comprising:
the reactor (1) comprises a first feeding hole (10), a first air inlet (11), a second air inlet (12), a third air inlet (13), a first discharging hole (14), a first outlet (15) and a second feeding hole (16), wherein the first feeding hole (10) is positioned above the first air inlet (11), the second air inlet (12) and the third air inlet (13);
a first cyclone (2) comprising a fourth gas inlet (21), a second outlet (22), a third outlet (23) and a filtering means (24), the fourth gas inlet (21) being connected to the first outlet (15) of the reactor (1), the filtering means (24) being provided at the third outlet (23);
-a second cyclone (3) comprising a fifth gas inlet (31), a fourth outlet (32), a fifth outlet (33) and filtering means (34), the fifth gas inlet (31) being connected to the third outlet (23) of the first cyclone, the filtering means (34) being provided at the fifth outlet (33);
a first recycle line (4), the first recycle line (4) connecting the fifth outlet (33) of the second cyclone and the third inlet (13) of the reactor (1);
a second circulation line (5), wherein the second circulation line (5) is connected with a second feed inlet (16) of the reactor (1), a second outlet (22) of the first cyclone separator (2) and a fourth outlet (32) of the second cyclone separator (3);
heating means (7), said heating means (7) being arranged on at least part of the first cyclone (2), the second cyclone (3) and the lower circulation line (5),
the device further comprises a gas pressurization device (8), wherein the gas pressurization device (8) is positioned on the first circulation pipeline (4).
11. The apparatus of claim 10,
the reactor (1) further comprises a gas distribution plate (17), and the gas distribution plate (17) is arranged at the bottom of the reactor (1).
12. The apparatus of claim 11,
the first gas inlet (11) is located above the gas distribution plate (17), and the second gas inlet (12) and the third gas inlet (13) are located below the gas distribution plate (17).
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