CN114349052A - Continuous microsphere gas-phase carbon coating production process - Google Patents

Continuous microsphere gas-phase carbon coating production process Download PDF

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CN114349052A
CN114349052A CN202111580628.XA CN202111580628A CN114349052A CN 114349052 A CN114349052 A CN 114349052A CN 202111580628 A CN202111580628 A CN 202111580628A CN 114349052 A CN114349052 A CN 114349052A
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stable
phase carbon
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microspheres
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CN114349052B (en
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赵宽明
王家贵
何平
昌广金
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Zhonghao Heiyuan Chemical Research Design Institute Co ltd
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    • C01G39/00Compounds of molybdenum
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    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B33/00Silicon; Compounds thereof
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    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
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    • C01G23/00Compounds of titanium
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    • C01G23/047Titanium dioxide
    • C01G23/08Drying; Calcining ; After treatment of titanium oxide
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to the technical field of lithium/sodium battery cathode material production, in particular to a continuous microsphere gas-phase carbon coating production process, which comprises the following steps: s1, heating the stable gas to 900-960 ℃; s2, sending the stable gas into a Venturi mixer, and adding the microspheres to heat the microspheres by the stable gas; s3, carrying out gas phase carbon coating on the microspheres through a coating generator and a coating tower by using a carbon source gas, wherein the thickness of the coating layer is more than 4 nm; s4, after passing through a heat exchanger and a water cooler, reducing the temperature of the gas-solid mixture discharged from the coating tower to 150-200 ℃, enabling the gas-solid mixture to enter a bag filter for gas-solid separation, conveying the gas to a gas-gas separation system through a fan, enabling the solid to enter a product tank through an airtight valve for further cooling, and packaging in a packaging system. The invention has the advantages that: low energy consumption and large-scale continuous production.

Description

Continuous microsphere gas-phase carbon coating production process
Technical Field
The invention relates to the technical field of lithium/sodium battery cathode material production, in particular to a continuous microsphere gas-phase carbon coating production process.
Background
With the development of the electric automobile industry, people are urgently required to develop a novel high-performance lithium/sodium ion battery, and the battery performance is closely related to electrode materials. At present, the graphite negative electrode material for industrial production cannot meet the requirements of long service life and high capacity of a power battery. And Si, SiOx and SiOx/C can become a new generation of lithium/sodium ion battery cathode material with good prospect.
In order to improve coulombic efficiency and conductivity, the carbon coating is carried out on the Si, SiOx and SiOx/C microspheres, and the carbon coating process comprises three processes: solid phase coating, liquid phase coating and gas phase coating, wherein the gas phase carbon coating is the best.
According to the existing gas phase coating process, the process is intermittent, the labor intensity is high, the energy consumption is high, and the production scale is difficult to expand. In patent publication No. CN109873135A, patent names: in the carbon coating method by the melody type chemical vapor deposition method, the patent does not consider comprehensive utilization of energy, and the annual output is only 3 to 5 tons.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a continuous microsphere gas-phase carbon coating production process, which has low energy consumption and can realize large-scale continuous production.
The purpose of the invention is realized by the following technical scheme:
a continuous microsphere gas phase carbon coating production process comprises the following steps:
s1, heating the stable gas to 900-960 ℃;
s2, sending the stable gas into a Venturi mixer, and adding the microspheres to heat the microspheres by the stable gas;
s3, carrying out gas phase carbon coating on the microspheres through a coating generator and a coating tower by using a carbon source gas, wherein the thickness of the coating layer is more than 4 nm;
s4, after passing through a heat exchanger and a water cooler, reducing the temperature of the gas-solid mixture discharged from the coating tower to 150-200 ℃, enabling the gas-solid mixture to enter a bag filter for gas-solid separation, conveying the gas to a gas-gas separation system through a fan, enabling the solid to enter a product tank through an airtight valve for further cooling, and packaging in a packaging system.
Further, in step S1, the pressure of the stable gas is adjusted to 0.07-0.09 Mpa, the stable gas is subjected to heat exchange by the heat exchanger to raise the temperature of the stable gas from normal temperature to 600-800 ℃, and the stable gas is further heated by the heater to 940-960 ℃.
Further, the stable gas is stored in a stable gas station, which is a gas holder or a pressure gas tank.
Further, the heater is an electric heater or a tube furnace heater.
Further, the carbon source gas is one or a combination of more than two of acetylene, ethylene, methane, ethane and propane.
Furthermore, the microspheres are one or a combination of more than two of Si, SiOx (x is more than or equal to 1 and less than or equal to 2), MoO2 and TiO2, and the diameter of the microspheres is 0.8-1.2 μm.
Further, the flow rate of the stable gas is 30-35 Nm3/h, and the flow rate of the carbon source gas is 2800-3200 Nm 3/h.
Further, in step S2, the outlet temperature of the Venturi mixer is 810-830 ℃.
Further, the stable gas is nitrogen or inert gas.
The invention has the following advantages:
1. low energy consumption, large-scale continuous production and improved production efficiency.
2. The high-temperature mixed gas containing the microspheres enters a carbon coating generator to be mixed with acetylene (or mixed gas of acetylene and other hydrocarbons), the acetylene starts to crack at the temperature, and the generated free carbon molecules are adsorbed on the surfaces of the microspheres to form compact coating layers with good and stable coating quality.
Drawings
FIG. 1 is a schematic view of a gas phase carbon coating process of microspheres according to the present invention;
in the figure: 1-stable gas station, 2-heat exchanger, 3-heater, 4-Venturi mixer, 5-cladding generator, 6-cladding tower, 7-water cooler, 8-bag filter, 9-airtight valve, 10-product tank, 11-packaging system and 12-fan.
Detailed Description
The invention is further described below with reference to the figures and examples, but the scope of protection of the invention is not limited to the following.
As shown in fig. 1, a continuous microsphere gas phase carbon coating production process comprises the following steps:
s1, storing stable gas in a stable gas station 1, wherein the stable gas station 1 is a gas holder or a pressure gas tank, the stable gas is regulated to 0.07-0.09 Mpa (when the stable gas comes from the gas holder, pressurization is needed, when the stable gas comes from the pressure gas tank, decompression is needed), the flow rate of the stable gas is 30-35 Nm3/h, heat exchange is carried out through a heat exchanger 2, the temperature of the stable gas is increased to 600-800 ℃ from normal temperature, the stable gas is further heated by a heater 3 to 940-960 ℃, the stable gas is heated to 900-960 ℃, the heater 3 is an electric heater or a tubular furnace heater, and the stable gas is nitrogen or inert gas;
s2, sending the stable gas into a Venturi mixer 4, and adding microspheres, wherein the microspheres are one or a combination of more than two of Si, SiOx (x is more than or equal to 1 and less than or equal to 2), MoO2 and TiO2, and the diameter of the microspheres is 0.8-1.2 μm, so that the stable gas heats the microspheres, the temperature of an outlet of the Venturi mixer 4 is 810-830 ℃, at the moment, the surface temperature of the microspheres is basically equivalent to the temperature of the mixed gas, the internal temperature of the microspheres is lower than the surface temperature, and a temperature gradient is formed, so that the physical properties of internal materials cannot be changed;
s3, carrying out gas-phase carbon coating on the microspheres by a high-temperature mixed gas containing the microspheres through a coating generator 5 and a coating tower 6 by using a carbon source gas (the carbon source gas is one or a combination of more than two of acetylene, ethylene, methane, ethane and propane, the flow rate of the carbon source gas is 2800-3200 Nm3/h), cracking the acetylene at the temperature, adsorbing the generated free carbon molecules on the surfaces of the microspheres to form a compact coating layer, and finally, the thickness of the coating layer is more than 4 Nm;
s4, after passing through a heat exchanger 2 and a water cooler 7, the temperature of the gas-solid mixture discharged from the coating tower 6 is reduced to 150-200 ℃, the gas-solid mixture enters a bag filter 8 for gas-solid separation, the gas is conveyed to a gas-gas separation system through a fan 12, the solid enters a product tank 10 through an airtight valve 9 for further cooling, and then the solid is packaged in a packaging system 11.
The reason why acetylene gas is used as the main gas-phase carbon-coated main raw material is that acetylene gas has the following characteristics:
(1) the starting cracking temperature is low, and the reaction equation of starting cracking at 800 ℃ is as follows:
C2H2→2C+H2+226.9kJ
(2) the cracking reaction is exothermic reaction, and the cracking process can not be stopped due to too low temperature, so that the coating quality is good and stable.
(3) The carbon cladding is more conductive than claddings produced by other hydrocarbons.
The mixed gas containing the microspheres enters a coating tower 6 after mixed reaction of acetylene and a coating generator 5, the unreacted acetylene in the coating generator 5 continues to carry out cracking reaction in the tower, and the carbon and the microspheres collide and adsorb each other in the tower by utilizing the difference of the sedimentation velocity of the cracked amorphous carbon and the microspheres, so that the coating layer is thickened until the required thickness is reached.
In the coating tower 6, the temperature in the tower is continuously increased along with the continuous cracking of acetylene, and the internal temperature of the microspheres is further increased. If the microsphere is SiOx, disproportionation reaction will occur, and the performance will be better improved as the negative electrode material. In order to avoid carbonization of the microspheres in the tower and generation of SiC, the temperature of the cladding tower 6 is controlled below a proper temperature.
The method for controlling the temperature of the coating tower 6 comprises the following three methods:
(1) the amount of acetylene is strictly controlled as required.
(2) For the microspheres which do not need to be subjected to disproportionation reaction and need to be coated with carbon, the temperature is controlled and the cost is reduced by mixing propane or butane into acetylene gas.
(3) The microspheres which are required to be carbon-coated for the disproportionation reaction are cooled by refluxing the cooling gas into the coating tower 6.
According to the actual situation, the three methods are adopted simultaneously.
Example 1:
the carbon-coated microspheres are required to be lithium battery cathode materials (Si, SiO/C) and are not subjected to disproportionation reaction. The diameter of the microsphere is 0.8-1.2 microns, and the treatment capacity is 10 kg/h.
Step 1, system preheating and oxygen replacement
25-35 Nm of pressure reduction (from a pressure tank) or pressurization (from a gas tank)3The nitrogen gas per hour passes through equipment and pipelines such as a heat exchanger 2, a heater 3, a Venturi mixer 4, a coating generator 5, a coating tower 6, a bag filter 8, a fan 12 and the like to preheat and replace oxygen in the system, the power of the heater 3 is adjusted to 10kw to 20kw, after 30 minutes to 60 minutes, the oxygen content in the system is less than 3 percent, the outlet temperature of the heater 3 reaches about 950 ℃, and the inlet temperature of the bag filter 8 is less than 150 ℃.
Step 2, carrying out microsphere carbon coating operation
After the technological parameters are stable, the propane and acetylene gas valves are slowly opened, so that the two gases enter the coating generator 5 after passing through the gas/gas mixer. At the same time, the microsphere meter was opened and the microspheres were mixed and heated in the venturi mixer 4 at 10 kg/h. After the process is finally stabilized, typical main operating parameters are as follows:
flow rate:
nitrogen gas 30-35 Nm3/h
Ethane 700-800L/h
2200-2300L/h of acetylene
Temperature:
Figure BDA0003425940760000061
example 2:
the carbon-coated microspheres are needed to be used as lithium battery cathode materials (SiO, SiO 2) for disproportionation reaction. The diameter of the microsphere is 0.8-1.2 microns, and the treatment capacity is 10 kg/h.
Step 1, system preheating and oxygen replacement
By depressurization [ from nitrogen storage tank ] or pressurization [ from nitrogen gas holder ] of 25 to 35Nm3The nitrogen gas passes through equipment and pipelines such as a heat exchanger 2, a heater 3, a cladding tower 6, a bag filter 8, a fan 12 and the like, the system is preheated and oxygen in the system is replaced, the power of the heater 3 is adjusted from 10kW to 20kW, after 30 to 60 minutes, the oxygen content in the system is less than 3 percent, the outlet temperature of an electric heater reaches about 950 ℃, and the inlet temperature of the bag filter is less than 150 ℃.
Step 2, carrying out microsphere carbon coating operation
After the technological parameters are stable, the acetylene gas valve is slowly opened, so that the acetylene gas enters the cladding generator 5. At the same time, the microsphere meter was opened and the microspheres were mixed and heated in the venturi mixer 4 at 10 kg/h. After the process is finally stabilized, typical main operating parameters are as follows:
flow rate:
nitrogen gas 30-35 Nm3/h
2800 to 3200L/h of acetylene
Cooling air flow of 8-15 Nm3/h
Temperature:
Figure BDA0003425940760000071
although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. A continuous microsphere gas phase carbon coating production process is characterized in that: the method comprises the following steps:
s1, heating the stable gas to 900-960 ℃;
s2, sending the stable gas into a Venturi mixer, and adding the microspheres to heat the microspheres by the stable gas;
s3, carrying out gas phase carbon coating on the microspheres through a coating generator and a coating tower by using a carbon source gas, wherein the thickness of the coating layer is more than 4 nm;
s4, after passing through a heat exchanger and a water cooler, reducing the temperature of the gas-solid mixture discharged from the coating tower to 150-200 ℃, enabling the gas-solid mixture to enter a bag filter for gas-solid separation, conveying the gas to a gas-gas separation system through a fan, enabling the solid to enter a product tank through an airtight valve for further cooling, and packaging in a packaging system.
2. The continuous microsphere gas-phase carbon coating production process according to claim 1, which is characterized in that: in step S1, the pressure of the stable gas is adjusted to 0.07-0.09 Mpa, the stable gas is subjected to heat exchange through the heat exchanger, the temperature of the stable gas is increased from normal temperature to 600-800 ℃, and the stable gas is further heated through the heater to 940-960 ℃.
3. The continuous microsphere gas-phase carbon coating production process according to claim 2, which is characterized in that: the stable gas is stored in a stable gas station, which is a gas cabinet or a pressure gas tank.
4. The continuous microsphere gas-phase carbon coating production process according to claim 2, which is characterized in that: the heater is an electric heater or a tube furnace heater.
5. The continuous microsphere gas-phase carbon coating production process according to claim 1, which is characterized in that: the carbon source gas is one or the combination of more than two of acetylene, ethylene, methane, ethane and propane.
6. The continuous microsphere gas-phase carbon coating production process according to claim 1, which is characterized in that: the microspheres are Si, SiOx (x is more than or equal to 1 and less than or equal to 2) and MoO2、TiO2One or a combination of two or more, and the diameter thereof is 0.8 to 1.2 μm.
7. The continuous microsphere gas-phase carbon coating production process according to claim 1, which is characterized in that: the flow rate of the stable gas is 30-35 Nm3The flow rate of the carbon source gas is 2800-3200 Nm3/h。
8. The continuous microsphere gas-phase carbon coating production process according to claim 1, which is characterized in that: in step S2, the outlet temperature of the Venturi mixer is 810-830 ℃.
9. The continuous microsphere gas-phase carbon coating production process according to any one of claims 1 to 9, characterized in that: the stable gas is nitrogen or inert gas.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103094534A (en) * 2012-12-21 2013-05-08 顾向红 Preparation method of negative electrode material for lithium ion battery with high specific capacity
JP2016106358A (en) * 2015-12-25 2016-06-16 信越化学工業株式会社 Method for manufacturing negative electrode active material for nonaqueous electrolyte secondary battery
CN106067547A (en) * 2016-08-10 2016-11-02 深圳市贝特瑞新能源材料股份有限公司 Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite
CN108807884A (en) * 2018-05-31 2018-11-13 中国科学院过程工程研究所 A kind of system and method for lithium ion battery negative material carbon coating modification
CN108963203A (en) * 2018-06-11 2018-12-07 浙江衡远新能源科技有限公司 A kind of preparation method of carbon-coated porous silicon composite material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103094534A (en) * 2012-12-21 2013-05-08 顾向红 Preparation method of negative electrode material for lithium ion battery with high specific capacity
JP2016106358A (en) * 2015-12-25 2016-06-16 信越化学工業株式会社 Method for manufacturing negative electrode active material for nonaqueous electrolyte secondary battery
CN106067547A (en) * 2016-08-10 2016-11-02 深圳市贝特瑞新能源材料股份有限公司 Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite
CN108807884A (en) * 2018-05-31 2018-11-13 中国科学院过程工程研究所 A kind of system and method for lithium ion battery negative material carbon coating modification
CN108963203A (en) * 2018-06-11 2018-12-07 浙江衡远新能源科技有限公司 A kind of preparation method of carbon-coated porous silicon composite material

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