CN114759174A - Spherical silicon-carbon negative electrode material, preparation method and device thereof, lithium battery negative electrode and lithium battery - Google Patents
Spherical silicon-carbon negative electrode material, preparation method and device thereof, lithium battery negative electrode and lithium battery Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
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- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Manufacturing & Machinery (AREA)
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- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium battery cathode materials, and discloses a spherical silicon-carbon cathode material, a preparation method and a device thereof, a lithium battery cathode and a lithium battery. The preparation method of the spherical silicon-carbon negative electrode material comprises the following steps: (1) uniformly mixing asphalt, spherical graphite and nano silicon powder to obtain silicon-carbon mixed slurry; (2) carrying out spray carbonization on the silicon-carbon mixed slurry to form balls, and obtaining a mixture containing silicon-carbon microspheres and high-temperature oil gas; (3) and carrying out gas-solid separation on the mixture to obtain the spherical silicon-carbon negative electrode material, wherein the particle size of the silicon-carbon-containing microspheres is 3-20 microns. The negative electrode material prepared by the technical scheme of the invention has the characteristics of good sphericity, large compacted density, high specific capacity and excellent charge-discharge cycle performance. Meanwhile, the invention takes the chemical by-products asphalt and silicon powder as raw materials, has obvious economic and ecological benefits, low energy consumption, simple process flow, timely operation and control and small pollution, and is suitable for industrial continuous production.
Description
Technical Field
The invention relates to the field of negative electrode materials, in particular to a spherical silicon-carbon negative electrode material, a preparation method and a device thereof, a lithium battery negative electrode and a lithium battery.
Background
The lithium ion battery has a series of advantages of high specific capacity, high working voltage, good safety, no memory effect and the like, and is widely applied to new energy automobiles, notebook computers, mobile phones and energy storage equipment. The cathode material is one of the core components of the battery and plays a key role in the comprehensive performance of the battery. In the lithium battery negative electrode material, the theoretical specific capacity of graphite in the carbon-based negative electrode material is 372mAh/g, and the theoretical specific capacity of the silicon-based negative electrode material is 4200mAh/g, but the problems of active substance pulverization and shedding, capacity rapid attenuation and the like can occur due to volume expansion in charge-discharge circulation. Researches show that in the charge-discharge cycle of the silicon-carbon composite negative electrode material, the carbon phase is used as a supporting matrix of the buffering framework, the structural stability can be effectively maintained, the volume change of the silicon phase during the process of releasing and inserting lithium is relieved, the electrochemical stability of the composite negative electrode is improved, the lithium storage capacity of the carbon phase can be greatly improved by the silicon phase, and the specific capacity of the composite negative electrode is improved.
However, the existing methods for preparing silicon-carbon negative electrode materials, such as chemical vapor deposition, sol-gel mechanical ball milling, and high temperature pyrolysis, have the problems of high cost, difficulty in controlling process conditions, poor silicon dispersibility, easy particle agglomeration, poor cycle stability, difficulty in industrial production, and the like, and further research is still needed. For example, CN107565115B discloses a method for preparing a silicon-carbon negative electrode material by a chemical vapor deposition method, but the method has the problems of high cost, difficult control of process conditions, and difficult industrial production. CN108598430B discloses a preparation method of a silicon-carbon negative electrode material, which comprises the steps of firstly coating silicon powder and carbon micropowder with a carbon source, then carrying out spray drying and carbonization treatment to prepare a porous silicon-carbon microsphere negative electrode material, wherein the spray drying temperature is 85 ℃, in the subsequent carbonization and temperature rise process, the added carbon source is easy to cause silicon-carbon microspheres to be bonded and agglomerated together, and the continuous temperature rise is carried out to deform and crush spheres, thus affecting the specific capacity and the cycle stability of the negative electrode material.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the preparation cost of a silicon-carbon negative electrode material is high, the process conditions are not easy to control, the energy consumption is high after repeated heating, silicon-carbon microspheres are easy to be bonded and agglomerated after being coated with a carbon source, and spheres are deformed and crushed due to heating and carbonization, so that the specific capacity and the cycling stability of the negative electrode material are poor, and provides a spherical silicon-carbon negative electrode material, a preparation method and a device thereof, a lithium battery negative electrode and a lithium battery.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a spherical silicon carbon negative electrode material, comprising the steps of:
(1) uniformly mixing asphalt, spherical graphite and nano silicon powder to obtain silicon-carbon mixed slurry;
(2) carrying out spray carbonization on the silicon-carbon mixed slurry to form balls to obtain a mixture containing silicon-carbon microspheres and high-temperature oil gas;
(3) carrying out gas-solid separation on the mixture to obtain a spherical silicon-carbon cathode material;
wherein the grain diameter of the silicon-containing carbon microsphere is 3-20 μm.
The invention provides a spherical silicon-carbon anode material, which is prepared by the preparation method of the first aspect.
The third aspect of the present invention provides a negative electrode for a lithium battery, comprising a current collector and a negative electrode material supported on the current collector, wherein the negative electrode material comprises the negative electrode material of the second aspect.
In a fourth aspect, the invention provides a lithium battery, wherein the negative electrode is the negative electrode of the lithium battery of the third aspect.
The fifth aspect of the invention provides a preparation device of a spherical silicon-carbon cathode material for a lithium ion battery, which comprises a silicon-carbon mixed slurry prefabricating unit 10, a spray carbonization ball forming unit 20 and a gas-solid separation unit 30 which are communicated in sequence;
the silicon-carbon mixed slurry prefabricating unit 10 comprises a raw material premixing system 11 and a silicon-carbon mixed slurry feeding system 12 communicated with an outlet of the raw material premixing system 11;
the spray carbonization balling unit 20 comprises a spray tower communicated with an outlet of the silicon-carbon mixed slurry feeding system 12, a heater 22, an air distribution disc, a high-temperature nitrogen inlet 23 for a heat carrier and an outlet 24 for a spray product; wherein, the top of the spraying tower is provided with a nozzle 21.
According to the technical scheme, the asphalt raw material, the spherical graphite and the nano silicon powder are pretreated, and meanwhile, the silicon-carbon mixed slurry can be directly sprayed into balls at high temperature by adjusting the operating conditions of the spraying unit, and the obtained spherical silicon-carbon negative electrode material has the characteristics of good sphericity, high compacted density, high specific capacity and excellent charge-discharge cycle performance, and has a good application prospect in the field of new lithium battery energy. The technical scheme of the invention takes the chemical by-products asphalt and silicon powder as raw materials, and has remarkable economic and ecological benefits. Meanwhile, the preparation method and the device have the advantages of simple process flow, low energy consumption, timely operation and control, small pollution and suitability for industrial continuous production.
Drawings
Fig. 1 is a schematic diagram of a device for preparing a spherical silicon carbon negative electrode material for a lithium ion battery according to the present invention.
Description of the reference numerals
10 silicon-carbon mixed slurry prefabricated unit 11 raw material premixing system
12 silicon carbon mixed slurry feeding system 20 spray carbonization balling unit
21 nozzle 22 heater
23 air distribution disc and 24 spray product outlets of high-temperature carrier gas inlet of heat carrier
30 gas-solid separation unit 31 cyclone separator
32 membrane filter equipment 33 sprays condensing equipment
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a spherical silicon-carbon negative electrode material, which comprises the following steps:
(1) uniformly mixing asphalt, spherical graphite and nano silicon powder to obtain silicon-carbon mixed slurry;
(2) Carrying out spray carbonization on the silicon-carbon mixed slurry to form balls to obtain a mixture containing silicon-carbon microspheres and high-temperature oil gas;
(3) carrying out gas-solid separation on the mixture to obtain a spherical silicon-carbon negative electrode material;
wherein the grain diameter of the silicon-containing carbon microsphere is 3-20 μm.
In the invention, because the viscosity of the raw material asphalt is high, the existing high-temperature spray pelletizing technology cannot directly carry out spray pelletizing on the asphalt raw material, the viscosity of the asphalt is reduced by pretreating the asphalt raw material, and simultaneously, the silicon-carbon mixed slurry is carbonized into pellets while being sprayed at high temperature by adjusting the operating conditions of a spraying unit, so that the silicon-carbon-containing microspheres are directly prepared in one step. The high-temperature spray carbonization balling technology is a special process for preparing silicon-carbon-containing microspheres, and is characterized in that prefabricated silicon-carbon mixed slurry is sprayed into a high-temperature atomizing tower through a nozzle to be atomized into liquid drops with required sizes, and the liquid drops are formed into balls under the action of surface tension. The spherical liquid drops are gradually pyrolyzed and carbonized at high temperature in the process of free descending and finally form silicon-carbon-containing microspheres in a gas phase, so that the problem that the microspheres and mother liquor are difficult to separate in the existing liquid phase balling preparation method is solved. Meanwhile, as the generated microspheres are carbonized at high temperature, micromolecules and light components of the spheres are removed, the spherical appearance of the spheres has thermal stability, the temperature rise carbonization step in the process of preparing the silicon-carbon cathode material by spraying, coating and the like in the prior art is not needed, and the problems of sphere adhesion, deformation and crushing in the temperature rise process are avoided. Preferably, the particle size of the silicon-containing carbon microspheres is 5-15 μm.
According to a preferred embodiment of the present invention, the silicon-carbon mixed slurry is prepared under the following conditions: heating the asphalt from room temperature to 260-350 ℃ at the heating rate of 1-10 ℃/min, uniformly stirring, adding the nano silicon powder and the spherical graphite, carrying out ultrasonic treatment, and stirring at constant temperature for 1-4 h. Preferably, the ultrasonic condition is 60 to 100kHz, more preferably 80 to 100 kHz; the ultrasonic treatment time is 2-4h, preferably 3-4 h. By adopting the ultrasonic dispersion mode, the components of the silicon-carbon mixed slurry are uniformly mixed, the sphericity and the compaction density of the spherical silicon-carbon negative electrode material are improved, and the specific capacity and the cycle performance of the lithium battery are further improved.
In the invention, the adding sequence of the nano silicon powder and the spherical graphite has no special requirement, the nano silicon powder and the spherical graphite can be simultaneously added into the asphalt according to the proportion, or the nano silicon powder and the spherical graphite can be added into the asphalt step by step; preferably, the temperature of the asphalt is increased from room temperature to 260-350 ℃ at the temperature increase rate of 1-10 ℃/min, the asphalt is uniformly stirred, the spherical graphite is added, after ultrasonic treatment, the mixture is stirred at constant temperature for 1-4h to obtain a first mixture, the nano silicon powder is added, and after ultrasonic treatment, the mixture is stirred at constant temperature for 1-4h to obtain the silicon-carbon mixed slurry. By adopting the preferred embodiment, the asphalt, the nano silicon powder and the spherical graphite are fully mixed, and the specific capacitance and the cycle performance of the spherical silicon-carbon negative electrode material are improved.
According to a preferred embodiment of the present invention, the asphalt is at least one of coal liquefied asphalt, petroleum asphalt, coal tar pitch, and natural asphalt, and is preferably coal liquefied asphalt and/or coal tar pitch. Specifically, the coal-liquefied asphalt may be asphalt obtained by direct liquefaction of coal or co-refining of kerosene; the coal coking asphalt is asphalt obtained in the coal coking process; petroleum asphalt is asphalt obtained in the course of crude oil processing. The invention can use the chemical by-product asphalt and silicon powder as raw materials to produce the spherical silicon-carbon cathode material, thereby realizing the high value-added utilization of the by-products. The method is favorable for relieving the pressure of resource economy and environment, and has excellent economic and ecological benefits.
According to a preferred embodiment of the present invention, the spherical graphite has a particle size of 5 to 10 μm, preferably 5 to 7 μm, and the nano-silicon powder has a particle size of 10 to 100nm, preferably 10 to 50 nm.
According to a preferred embodiment of the present invention, the mass ratio of the pitch, the spherical graphite, and the nano silicon powder is 10 (3-5) to (4-7), and more preferably 10: (3-4): (5-6). Under the preferable conditions, the specific capacity and the cycle performance of the lithium battery are improved.
According to a preferred embodiment of the present invention, the temperature of the spray carbonization ball is 800-. The pressure for the spray carbonization to form the spheres is 0.3 to 3.0MPa, and may be, for example, 0.3MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 3MPa or any two of the above values, and preferably 0.3 to 1.0 MPa. Within the above preferred operating pressure and temperature ranges, the high-temperature spray carbonization of the pitch into spheres can improve the quality of the silicon-carbon-containing microspheres to a greater extent, and improve the sphericity and the compacted density without affecting the final product.
In some embodiments of the invention, after the high temperature spray carbonization balling step, the product of the high temperature spray carbonization balling is subjected to a gas-solid separation step.
According to a preferred embodiment of the present invention, the gas-solid separation comprises: under the action of high-temperature cyclone, carrying out cyclone separation on the mixture to obtain the silicon-carbon microspheres and first high-temperature oil gas; the gas high-temperature cyclone separation method can simply and efficiently separate the silicon-carbon-containing microsphere solid particles from the gas flow, and meanwhile, under the high-temperature separation condition, high-temperature oil gas in the cyclone separator is in a gas state, so that the oil gas is prevented from being condensed and attached to the silicon-carbon-containing microsphere and the cyclone separator.
According to a preferred embodiment of the invention, the temperature of the high-temperature cyclone is 800-1000 ℃, preferably 900-1000 ℃, and in the above preferred case, the gas-solid separation is more stable and efficient; the gas inlet velocity is 10-25m/s, preferably 15-25 m/s.
According to a preferred embodiment of the present invention, the gas-solid separation process further comprises: performing membrane filtration separation on the first high-temperature oil gas through a filter membrane to obtain the silicon-carbon microspheres and a second high-temperature oil gas; by adopting the preferred embodiment, the silicon-carbon-containing microsphere particles in the high-temperature gas at the outlet of the cyclone separator can be recycled, and the influence of the particles on the subsequent oil gas condensation recycling link is avoided. Meanwhile, in the membrane separation process, the separated high-temperature oil gas is in a gaseous state and cannot be condensed and attached to the membrane, so that the problem that continuous production is difficult due to membrane hole blockage and system pressure increase is solved.
According to a preferred embodiment of the present invention, in the gas-solid separation step, the operation temperature of the membrane filtration separation is 800-1000 ℃, and the pore size of the membrane is 1-10 μm, preferably 1-3 μm. It will be appreciated by those skilled in the art that the above ranges of operating temperature and pore size are only preferred embodiments and that gas-solid separation can be achieved when operating outside these ranges.
The second aspect of the invention provides a spherical silicon-carbon negative electrode material, which is prepared by the preparation method of the first aspect, wherein the sphericity of the spherical silicon-carbon negative electrode material is not lower than 0.9.
Preferably, the sphericity of the spherical silicon carbon negative electrode material is not less than 0.94. In the preferred case described above, it is advantageous to further increase the compacted density of the material.
According to a preferred embodiment of the present invention, the spherical silicon carbon negative electrode material has a compacted density of more than 1.7g/cm3Preferably, the compacted density of the spherical silicon-carbon negative electrode material is not lower than 1.8g/cm3。
In the present invention, sphericity is measured by the british lattice code SHAPE industrial image analysis and processing software. The compaction density is measured by the energy-saving technology PRCD1100, the test pressure is 30MPa, and the pressure maintaining time is 10 s.
The third aspect of the present invention provides a negative electrode for a lithium battery, comprising a current collector and a negative electrode material supported on the current collector, wherein the negative electrode material comprises the negative electrode material of the second aspect.
In a fourth aspect, the invention provides a lithium battery, wherein the negative electrode is the negative electrode of the lithium battery of the third aspect. The lithium battery has the characteristics of high specific capacity and excellent charge-discharge cycle performance, and is suitable for application in the field of lithium ion batteries.
In the present invention, there is no particular limitation on other compositions in the lithium battery, and conventional selections in the art may be adopted. For example, the positive electrode material in the lithium battery may be selected from at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, manganese nickel cobalt complex oxide, lithium vanadium oxide, lithium iron oxide, or ternary material.
The fifth aspect of the invention provides a preparation device of a spherical silicon-carbon cathode material for a lithium ion battery, which comprises a silicon-carbon mixed slurry prefabricating unit 10, a spray carbonization ball forming unit 20 and a gas-solid separation unit 30 which are communicated in sequence; the silicon-carbon mixed slurry prefabricating unit 10 is provided with a raw material asphalt inlet, a spherical graphite inlet, a nano silicon powder inlet and a silicon-carbon mixed slurry outlet, and the silicon-carbon mixed slurry prefabricating unit 10 is used for heating and stirring an asphalt raw material and uniformly mixing the asphalt raw material with spherical graphite and nano silicon powder to obtain silicon-carbon mixed slurry meeting the spray feeding requirement and realize continuous batching and stable feeding; the spray carbonization ball forming unit 20 is provided with a silicon-carbon mixed slurry inlet, a heat carrier inlet and a spray product outlet, and the spray carbonization ball forming unit 20 is used for preparing silicon-containing carbon microspheres by spraying, carbonizing and ball forming the silicon-carbon mixed slurry in one step.
The silicon-carbon mixed slurry prefabricating unit 10 comprises a raw material premixing system 11 and a silicon-carbon mixed slurry feeding system 12 communicated with an outlet of the raw material premixing system 11;
wherein, the spray carbonization balling unit 20 comprises a spray tower communicated with the outlet of the silicon-carbon mixed slurry feeding system 12, a heater 22, an air distribution disc, a high-temperature carrier gas inlet 23 of a heat carrier, and a spray product outlet 24; wherein, the top of the spraying tower is provided with a nozzle 21.
The preparation method and the device of the invention are different from the prior art, the process flow is simple, one-step carbonization molding can be realized, the separation operation is simple, the energy consumption is low, the operation control is timely, the pollution is small, and the method and the device are suitable for industrial continuous production.
In the present invention, the selection range of the specific equipment for the silicon-carbon mixed slurry preparation unit 10 is wide, as long as the heating and stirring of the raw materials can be realized.
In the invention, the silicon-carbon mixed slurry prefabricating unit 10 comprises a raw material premixing system 11 and a silicon-carbon mixed slurry feeding system 12; the raw material premixing system 11 is provided with a raw material asphalt inlet, a spherical graphite inlet, a nano silicon powder inlet, a heating stirring kettle, a pump and a premixed slurry outlet; the silicon-carbon mixed slurry feeding system 12 is provided with the premixed slurry inlet, the heating and stirring kettle, a pump and a silicon-carbon mixed slurry outlet. The raw material pitch, the spherical graphite and the nano silicon powder are uniformly mixed in the raw material premixing system 11, then are sequentially fed into the silicon-carbon mixed slurry feeding system 12 through the premixed slurry outlet and the premixed slurry inlet, and are introduced into the spray carbonization balling unit 20 through the silicon-carbon mixed slurry outlet.
Preferably, the raw material premixing system 11 is further provided with a high-power ultrasonic rod for performing ultrasonic treatment on the premixed raw material.
The spray carbonization balling unit 20 is used for preparing the silicon-containing carbon microspheres by spraying, carbonizing and balling the silicon-carbon mixed slurry in one step. After being heated by the heating furnace 22, the carrier gas is conveyed to the spray tower through the air distribution disc and the high-temperature carrier gas inlet 23 of the heat carrier.
In the present invention, the carrier gas is preferably an inert gas, and more preferably nitrogen.
According to a preferred embodiment of the invention, the spray tower has a height of 3 to 8m, preferably 5 to 7m, and a diameter of 1 to 2 m.
According to a preferred embodiment of the invention, the nozzle has an orifice diameter of 0.3-1.5mm and a spray angle of 60-90 °.
In the invention, the gas-solid separation unit 30 is provided with a spray product inlet, a spherical silicon-carbon negative electrode material outlet, a liquid product outlet and a gas product outlet, wherein the spray product inlet is connected with the spray product outlet 24 and is used for carrying out gas-solid separation treatment on the spray product to obtain the spherical silicon-carbon negative electrode material and condensed oil gas.
According to a preferred embodiment of the present invention, wherein the gas-solid separation unit 30 comprises:
The cyclone separation equipment 31 is communicated with the spray tower through the spray product outlet 24, and the cyclone separation equipment 31 is provided with a spray product inlet, a spherical silicon-carbon cathode material outlet and a cyclone outlet; and
the membrane filtering device 32 is provided with a membrane filtering inlet, a spherical silicon-carbon cathode material outlet and a membrane filtering gas product outlet, and the membrane filtering inlet is connected with the cyclone outlet; and
In the invention, a product formed by spray pyrolysis in a spray tower is introduced into a gas-solid separation unit 30 through a spray product inlet, the mixture is subjected to cyclone separation through cyclone separation equipment 31 under the action of high-temperature cyclone to obtain the silicon-carbon microspheres and first high-temperature oil gas, the silicon-carbon microspheres are concentrated at the bottom of the cyclone separator for product collection, the first high-temperature oil gas is introduced into a membrane filtering device 32 from the top of the cyclone separator, membrane filtration separation is performed through a filter membrane, the separated silicon-carbon microspheres are collected at the bottom of the membrane filtering device, the separated second high-temperature oil gas enters a spray condensing device 33 to obtain condensed oil and cooling carrier gas, the condensed oil flows into an oil storage tank through the bottom of the spray condensing device, and the cooling carrier gas is recovered and is sent into the spray tower through a heating furnace 22.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the particle size (D50) was measured by a malvern laser particle size analyzer Mastersizer 3000.
Sphericity is measured by british lattice code SHAPE industrial image analysis and processing software.
The compaction density is measured by adopting the metaverse technology PRCD1100, the test pressure is 30MPa, and the pressure maintaining time is 10 s.
The specific capacity and the cycle efficiency are measured by a Switzerland Wantong Autolab 302N, and the specific test method comprises the following steps: weighing 96 g of the negative electrode material for the lithium ion battery, 2.5 g of Styrene Butadiene Rubber (SBR) and 1.5 g of carboxymethyl cellulose (CMC), adding a proper amount of ethanol, uniformly mixing, coating on a copper foil, and preparing the electrode by vacuum drying and rolling. Using lithium as a counter electrode, 1mol of LiPF6The three-component mixed solvent (ethylene carbonate EC, dimethyl carbonate DMC and methyl ethyl carbonate EMC according to EC: DMC: EMC ═ 1:1:1, v/v solution) of (1) is used as the electrolyteAnd the polypropylene microporous membrane is a diaphragm and is assembled into the R2032 type button cell. At 0.5mA/cm2And (2) carrying out a constant-current charge-discharge experiment at a current density of (0.2C), limiting the charge voltage to 0.01-2.0V, and testing the first charge specific capacity, the first discharge specific capacity and the capacity retention rate after 200 cycles of the negative electrode material for the lithium ion battery.
In the following examples and comparative examples, coal-liquefied asphalt is a low ash asphalt product of Shenhua coal-to-liquids chemical Co., Ltd.
The following examples were carried out in the apparatus shown in FIG. 1.
Example l
(1) In a silicon-carbon mixed slurry prefabricating unit 10, introducing coal liquefied asphalt into a raw material premixing system 11 for heating and stirring, heating the coal liquefied asphalt to 300 ℃ at a heating rate of 3 ℃/min for melting, uniformly stirring, and adding spherical graphite accounting for 40% of the mass fraction of the asphalt, wherein the particle size of the spherical graphite is 5-10 mu m; ultrasonic treatment is carried out for 4 hours at 100kHz, and then constant-temperature stirring is carried out for 4 hours to obtain a first mixture. Adding nano silicon powder accounting for 60% of the mass fraction of the asphalt into the first mixture, wherein the particle size of the nano silicon powder is 10-100 nm; ultrasonic treatment is carried out for 4h at 100kHz, and then stirring is carried out for 4h at constant temperature to obtain a second mixture.
(2) Conveying the second mixture to a feeding tank 12, conveying the second mixture to a spray carbonization pelletizing unit 20, performing high-temperature spray carbonization pelletizing in a spray tower through a nozzle 21, and performing rapid pyrolysis on liquid drops formed by spraying in the spray tower to form silicon-carbon composite microspheres, wherein the temperature of the high-temperature spray carbonization pelletizing is 1000 ℃, the pressure is 0.5MPa, and the diameter of a spray hole of the nozzle 21 is 1 mm; the height of the spray tower is 8m, and the diameter of the spray tower is 2 m;
(3) And introducing a product formed by spray pyrolysis into a gas-solid separation unit 30, firstly passing through a cyclone separation device 31, wherein the temperature of high-temperature cyclone is 1000 ℃, the separated silicon-carbon microspheres are collected at the bottom of the cyclone separator, the separated first high-temperature oil gas is introduced into a membrane filtering device 32 from the top of the cyclone separator for further separation, the temperature of membrane filtering and separation is 1000 ℃, the aperture of a filter membrane is 3 mu m, the separated silicon-carbon microspheres are collected at the bottom of the membrane filtering device, the separated second high-temperature oil gas enters a spray condensing device to obtain condensed oil and cooling nitrogen, the condensed oil flows into an oil storage tank through the bottom of the spray condensing device, and the cooling carrier gas is recovered and is sent into a spray tower through a heating furnace 22. The silicon carbon microspheres are collected, and the test results of the obtained spherical silicon carbon negative electrode material are shown in table 1.
Examples 2 to 13
The process of example 1 was followed except that: the operating conditions of each step are shown in table 1, and the test results are shown in table 1 and the following table 1.
TABLE 1 preparation conditions and product properties of spherical silicon carbon cathode materials
TABLE 1 preparation conditions and product properties of spherical silicon-carbon cathode material
Comparative example 1
The process of example 1 was followed except that: no sonication is used in the formulation of the first and second mixtures. The test results are shown in table 2.
Comparative examples 2 to 6
According to the method of example 1, except that the operating conditions of each step are as shown in table 2, a spherical silicon carbon negative electrode material was finally obtained. The test results are shown in table 2.
Comparative example 7
The process of example 1 was followed except that: the silicon-carbon cathode material is prepared without passing through the gas-solid separation unit 30 and is adhered into a random large cluster shape. The test results are shown in table 2.
TABLE 2 preparation conditions and product Properties of the comparative examples
By adopting the technical scheme, chemical by-products of asphalt, spherical graphite and nano silicon powder are taken as raw materials, so that the economic and ecological benefits are remarkable. Meanwhile, the spherical silicon-carbon negative electrode material prepared by the preparation method has the characteristics of good sphericity, large compacted density, high specific capacity and excellent charge-discharge cycle performance, and is suitable for application in the field of lithium ion batteries. Meanwhile, the preparation method and the device of the invention are different from the prior art, and have the advantages of simple process flow, low energy consumption, timely operation and control, small pollution and suitability for industrial continuous production.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. The preparation method of the spherical silicon-carbon negative electrode material is characterized by comprising the following steps of:
(1) uniformly mixing asphalt, spherical graphite and nano silicon powder to obtain silicon-carbon mixed slurry;
(2) carrying out spray carbonization on the silicon-carbon mixed slurry to form balls to obtain a mixture containing silicon-carbon microspheres and high-temperature oil gas;
(3) carrying out gas-solid separation on the mixture to obtain a spherical silicon-carbon cathode material;
wherein the particle size of the silicon-containing carbon microspheres is 3-20 μm.
2. The production method according to claim 1, wherein the conditions for producing the silicon-carbon mixed slurry are as follows: heating the asphalt from room temperature to 260-350 ℃ at the heating rate of 1-10 ℃/min, uniformly stirring, adding the nano silicon powder and the spherical graphite, carrying out ultrasonic treatment, and stirring at constant temperature for 1-4 h.
3. The production method according to claim 1 or 2, wherein the raw material pitch is at least one of coal-liquefied pitch, petroleum pitch, coal-coked pitch, and natural pitch;
and/or the particle size of the spherical graphite is 5-10 mu m, and the particle size of the nano silicon powder is 10-100 nm;
and/or the mass ratio of the asphalt to the spherical graphite to the nano silicon powder is 10 (3-5) to (4-7).
4. The method according to any one of claims 1 to 3, wherein the temperature of the spray carbonization balling is 800-1000 ℃, and the pressure is 0.3-3 MPa.
5. The production method according to any one of claims 1 to 4, wherein, in the step (4), the gas-solid separation process comprises: under the action of high-temperature cyclone, carrying out cyclone separation on the mixture containing the silicon-carbon microspheres and the high-temperature oil gas to obtain the silicon-carbon microspheres and the first high-temperature oil gas;
preferably, the temperature of the high-temperature cyclone is 800-1000 ℃, and the gas inlet speed is 10-25 m/s;
preferably, the gas-solid separation process further comprises: performing membrane filtration separation on the first high-temperature oil gas by using a filter membrane to obtain the silicon-carbon microspheres and the high-temperature oil gas;
preferably, the temperature of the membrane filtration separation is 800-1000 ℃, and the pore diameter of the filter membrane is 1-10 μm.
6. A spherical silicon carbon negative electrode material, which is prepared by the preparation method of any one of claims 1 to 5, wherein the sphericity of the spherical silicon carbon negative electrode material is not less than 0.9.
7. A negative electrode for a lithium battery comprising a current collector and a negative electrode material supported on the current collector, wherein the negative electrode material comprises the negative electrode material according to claim 6.
8. A lithium battery, characterized in that the negative electrode is the negative electrode for a lithium battery according to claim 7.
9. A preparation device of spherical silicon-carbon cathode materials for lithium ion batteries is characterized by comprising a silicon-carbon mixed slurry prefabricating unit (10), a spray carbonization ball forming unit (20) and an air-solid separation unit (30) which are sequentially communicated;
the silicon-carbon mixed slurry prefabricating unit (10) comprises a raw material premixing system (11) and a silicon-carbon mixed slurry feeding system (12) communicated with an outlet of the raw material premixing system (11);
the spray carbonization balling unit (20) comprises a spray tower communicated with an outlet of the silicon-carbon mixed slurry feeding system (12), a heater (22), an air distribution disc, a high-temperature carrier gas inlet (23) of a heat carrier and a spray product outlet (24); wherein, the top of the spray tower is provided with a nozzle (21).
10. The apparatus according to claim 9, wherein the spray tower has a height of 3-8m, preferably 5-7m, and a diameter of 1-2 m;
preferably, the diameter of the spray hole of the spray nozzle (21) is 0.3-1.5mm, and the spray angle is 60-90 degrees.
11. Apparatus according to claim 9 or 10, wherein the gas-solid separation unit (30) comprises:
the spray product outlet (24) is communicated with a spray tower through a cyclone separation device (31), and the cyclone separation device (31) is provided with a spray product inlet, a spherical silicon-carbon cathode material outlet and a cyclone outlet; and
The membrane filtering device (32), the membrane filtering device (32) is provided with a membrane filtering inlet, a spherical silicon carbon cathode material outlet and a membrane filtering gas product outlet, and the membrane filtering inlet is connected with the cyclone outlet; and
spray condensing equipment (33), spray condensing equipment (33) be provided with spray condensation import, spray column, oil storage tank, pump and the gaseous products export, spray condensation import with membrane filtration gaseous products export links to each other.
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| CN103435105A (en) * | 2013-08-07 | 2013-12-11 | 浙江凯恩电池有限公司 | Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof |
| CN106987262A (en) * | 2017-03-29 | 2017-07-28 | 神华集团有限责任公司 | The burnt preparation method of isotropic pitch and producing device |
| CN109216686A (en) * | 2018-10-11 | 2019-01-15 | 天能电池集团有限公司 | A kind of lithium ion battery silicon-carbon composite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435105A (en) * | 2013-08-07 | 2013-12-11 | 浙江凯恩电池有限公司 | Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof |
| CN106987262A (en) * | 2017-03-29 | 2017-07-28 | 神华集团有限责任公司 | The burnt preparation method of isotropic pitch and producing device |
| CN109216686A (en) * | 2018-10-11 | 2019-01-15 | 天能电池集团有限公司 | A kind of lithium ion battery silicon-carbon composite material and preparation method |
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