CN113793924A - By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material - Google Patents
By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—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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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of battery materials, and discloses a method for utilizing supercritical CO2Preparation of Si/Fe by fluid medium3O4A method for preparing the/C composite material. The method comprises the following steps: (1) adding silicon powder, carbon and an iron source into a ball milling tank, adding a wet grinding agent and ball milling beads, sealing the ball milling tank, and vacuumizing; (2) pumping CO into the ball milling tank2Performing ball milling reaction on the gas in a supercritical environment to obtain Si/FeCO3a/C precursor product; (3) after the ball milling reaction is finished, collecting a product in a ball milling tank and drying to obtain a powder product; (4) sintering the powder in inert atmosphere to obtain Si/Fe3O4a/C composite material. The invention provides a novel method for preparing a silicon-carbon composite material by utilizing greenhouse gases, which has the advantages of simple process, economy, environmental protection, easy industrial implementation and the like, and the prepared Si/Fe3O4the/C composite material has excellent rate performance and cycling stability, and can be widely applied to the fields of high-performance lithium ion batteries and the like as a negative electrode material.
Description
Technical Field
The invention belongs to the field of electrode materials of batteries, and relates to a method for preparing a lithium ion battery by using supercritical CO2Preparation of Si/Fe by fluid medium3O4A method for preparing a/C composite material and application of the composite material as a negative electrode material of a lithium ion battery.
Background
The new energy automobile is a strategic industry which is mainly supported and developed by the nation, the power battery system is the heart of the new energy automobile, the energy density of the power battery at present does not completely solve the anxiety of endurance of the electric automobile, and the development of a new generation of battery anode and cathode materials is urgent. The silicon negative electrode material has extremely high theoretical capacity (4200mAh/g) and relatively low oxidation-reduction potential (<0.5V vs.Li/Li+) Is considered to be a very competitive anode material. However, the silicon negative electrode material also faces many challenges, such as poor silicon conductivity, low coulombic efficiency for the first time, large volume expansion in the charge and discharge process, fast capacity attenuation and the like, and the defects seriously limit the further application of the silicon negative electrode. Silicon-carbon compounding is an effective strategy for solving the problems, and is beneficial to improving the electrical conductivity of the silicon cathode, relieving the volume expansion of silicon and improving the electrochemical performance of the material. In addition, ferroferric oxide can effectively prevent the silicon cathode structure from collapsing and improve the silicon cathodeAnd (4) cycling stability. At reported Si @ Fe3O4In the literature of the/C composite, for example, Liu et al prepared Si @ Fe by mechanical ball milling3O4According to the method, potassium ferrate is used as a raw material, the method has strong oxidizability, is not easy to prepare and store, has potential safety risks, generates byproducts, and is not suitable for industrial production. (C.Liu, Q.Xia, C.Liao, S.Wu, Pseudo-capacitive control to Three-dimensional Micro-sized Silicon @ Fe)3O4@ Few-layerd Graphene for High-rate and Long-life Lithium Ion Batteries, Materials Today Communications,2019,18, 66-73.). Therefore, the Si @ Fe which has high efficiency, low cost, environmental protection and easy industrial production is developed3O4The preparation method of the/C composite material has important significance.
Disclosure of Invention
The invention aims to provide a method for utilizing supercritical CO2Preparation of Si/Fe by fluid medium3O4Novel method for producing/C composite material and said Si/Fe3O4The method is simple in process, efficient, environment-friendly and easy for industrial production to prepare Si/Fe3O4A novel method for preparing a/C composite material. The invention uses supercritical CO2Fluid is used as reaction medium and raw material, silicon powder, carbon and iron source are mixed by mechanical ball milling, and supercritical CO is generated in the ball milling and mixing process of silicon-carbon material2React with Fe to generate FeCO3To obtain Si/FeCO3a/C precursor product; then through thermal sintering treatment, FeCO3Further decomposed into Fe and Fe3O4Further obtaining Si/Fe3O4a/C composite material. The preparation method has simple preparation process, is economic and environment-friendly, is easy to implement industrially, and the prepared Si/Fe3O4the/C composite material has excellent electrochemical performance when being used as a lithium ion battery cathode.
The technical scheme adopted by the invention for solving the technical problems is as follows:
one of the objects of the present invention is to provide a method for utilizing supercritical CO2Preparation of Si/Fe by fluid medium3O4The preparation method of the/C composite material comprises the following steps:
(1) adding silicon powder, carbon material and iron source into a ball milling tank, adding a wet grinding agent and ball milling beads, sealing the ball milling tank, and vacuumizing;
(2) pumping CO into a sealed ball milling tank2Gas, ball milling reaction is carried out under supercritical condition to obtain Si/FeCO3a/C precursor product;
(3) after the ball milling reaction is finished, collecting a solid product in a ball milling tank and drying to obtain powder;
(4) sintering the collected powder in inert atmosphere to finally obtain Si/Fe3O4a/C composite material.
Preferably, in the step (1), the ball milling tank is a stainless steel high-pressure ball milling tank.
Preferably, in the step (1), the iron source is one or a combination of several of elementary iron, ferrous oxide, ferrocene and ferrous hydroxide.
Preferably, in the step (1), the carbon material is one or a combination of several of graphite, mesocarbon microbeads, carbon nanotubes and graphene.
Preferably, in the step (1), the silicon powder, the carbon material and the iron source are fed in a mass ratio of silicon, carbon and iron elements of 1: (0.25-5): (0.2-0.5) feeding, wherein the ball grinding bead and the material have a ball-to-material ratio of (30-100): 1.
preferably, in the step (1), the wet grinding agent is one or more of common solvents such as methanol, ethanol, isopropanol, water and the like, and more preferably, the wet grinding agent is a mixed solution of ethanol and deionized water in a volume ratio of 2: 1.
Preferably, in the step (2), the supercritical condition is CO2In supercritical CO2The fluid state condition, more preferably, the gas pressure is more than 7.3MPa, and the ball milling temperature is more than 32 ℃; more preferably, the gas pressure is 8.5MPa and the ball milling temperature is 35 ℃.
Preferably, in the step (2), the ball milling rotation speed is 300-500 rpm, and the ball milling time is 10-24 h.
Preferably, in the step (3), the treatment manner for collecting the solid product comprises filtration and washing, and more preferably, the filtration is suction filtration and the washing is alcohol washing.
Preferably, in the step (3), the drying manner is vacuum drying, and the temperature is 100-120 ℃.
Preferably, in the step (4), the inert atmosphere is one or a combination of several of nitrogen, argon and helium.
Preferably, in the step (4), the sintering temperature is 500-700 ℃ and the sintering time is 3-5 h.
Preferably, the present invention involves the following reaction:
CO2+H2O→H2CO3；
Fe+H2CO3→FeCO3+H2；
4FeCO3→Fe3O4+Fe+4CO2。
it is a second object of the present invention to provide a method for utilizing supercritical CO as described above2Preparation of Si/Fe by fluid medium3O4Si/Fe prepared by method of/C composite material3O4The application of the/C composite material as a negative electrode material of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a method for utilizing supercritical CO2Preparation of Si/Fe by fluid medium3O4The novel method of the/C composite material has the advantages of simple process, economy, environmental protection, easy industrial implementation and the like;
(2) Si/Fe prepared by the method of the invention3O4the/C composite material as the lithium ion battery cathode material has the characteristics of high specific capacity, good cycle performance and good rate performance.
Drawings
FIG. 1 is a diagram of Si/FeCO prepared in example 1 of the present invention3C precursor and Si/Fe3O4An X-ray diffraction pattern of the/C composite material;
FIG. 2 shows Si/Fe prepared in example 1 of the present invention3O4Scanning electron microscope images of the/C composite material;
FIG. 3 Si/Fe prepared according to examples 1 and 2 of the present invention3O4the/C composite material is used as a cycle performance diagram of the lithium ion battery cathode material;
FIG. 4 Si/Fe prepared according to examples 1 and 2 of the present invention3O4And the/C composite material is used as a rate performance diagram of the lithium ion battery cathode material.
Detailed Description
The technical solution of the present invention is further described below with specific embodiments and with reference to the drawings, but the scope of the present invention is not limited thereto.
The invention provides a method for utilizing supercritical CO2Preparation of Si/Fe by fluid medium3O4The preparation method of the/C composite material comprises the following steps:
(1) adding silicon powder, carbon material and iron source into a ball milling tank, adding a wet grinding agent and ball milling beads, sealing the ball milling tank, and vacuumizing;
(2) pumping CO into a sealed ball milling tank2Gas, ball milling reaction is carried out under supercritical condition to obtain Si/FeCO3a/C precursor product;
(3) after the ball milling reaction is finished, collecting a solid product in a ball milling tank and drying to obtain powder;
(4) sintering the collected powder in inert atmosphere to finally obtain Si/Fe3O4a/C composite material.
In the embodiment of the present invention, in the step (1), the ball milling tank is a stainless steel high-pressure ball milling tank.
In an embodiment of the present invention, in step (1), the iron source is one or a combination of several of elemental iron, ferrous oxide, ferrocene and ferrous hydroxide.
In an embodiment of the present invention, in the step (1), the carbon material is one or a combination of several of graphite, mesocarbon microbeads, carbon nanotubes and graphene.
In an embodiment of the invention, in the step (1), the silicon powder, the carbon material and the iron source are fed in a mass ratio of silicon, carbon and iron elements of 1: (0.25-5): (0.2-0.5), feeding, namely silicon: carbon: the iron is reasonably mixed in the ranges of 1:0.25:0.2, 1:1:0.3, 1:2:0.4, 1:3:0.5, 1:4:0.2, 1:5:0.3, 1:0.25:0.5 and the like, and the ball-material ratio of the ball grinding beads to the materials is (30-100): 1, namely the ball material ratio is 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1 and the like.
In the embodiment of the present invention, in the step (1), the wet grinding agent is one or more of a mixture of common solvents such as methanol, ethanol, isopropanol, water, and the like, and more preferably, the wet grinding agent is a mixed solution of ethanol and deionized water in a volume ratio of 2: 1.
In an embodiment of the present invention, in the step (2), the supercritical condition is CO2In supercritical CO2The fluid state condition, more preferably, the gas pressure is more than 7.3MPa, and the ball milling temperature is more than 32 ℃; more preferably, the gas pressure is 8.5MPa and the ball milling temperature is 35 ℃.
In the embodiment of the invention, in the step (2), the ball milling rotation speed is 300-500 rpm, and the ball milling time is 10-24 h.
In an embodiment of the present invention, in the step (3), the treatment manner of collecting the solid product includes filtration and washing, and more preferably, the filtration is suction filtration and the washing is alcohol washing.
In the embodiment of the present invention, in the step (3), the drying manner is vacuum drying, and the temperature is 100 ℃. about.120 ℃.
In an embodiment of the present invention, in the step (4), the inert atmosphere is one or a combination of several of nitrogen, argon and helium.
In the embodiment of the invention, in the step (4), the sintering temperature is 500-700 ℃ and the sintering time is 3-5 h.
The present invention involves the following reactions:
CO2+H2O→H2CO3；
Fe+H2CO3→FeCO3+H2；
4FeCO3→Fe3O4+Fe+4CO2。
the invention also provides a method for utilizing the supercritical CO2Preparation of Si/Fe by fluid medium3O4Si/Fe prepared by method of/C composite material3O4The application of the/C composite material as a negative electrode material of a lithium ion battery.
Example 1:
adding 0.1g of silicon powder, 0.1g of mesocarbon microbeads, 0.05g of iron powder and ball grinding beads into a ball-milling tank at a ball-material ratio of 50:1, adding 20ml of ethanol and 10ml of deionized water, sealing the ball-milling tank, and vacuumizing; introducing CO2The gas is heated to 35 ℃ to reach the supercritical fluid condition when the pressure in the ball-milling tank reaches 8MPa, the ball-milling tank is subjected to continuous ball-milling reaction for 12 hours at the rotating speed of 500rpm, and Si/FeCO is obtained3Filtering the precursor product, washing with alcohol, vacuum drying at 120 deg.c, collecting the powder product in the ball milling tank, and final drying in N2Calcining for 5h at 550 ℃ under the atmosphere protection to finally obtain Si/Fe3O4a/C composite material. FIG. 1 is a diagram of Si/FeCO prepared in example 1 of the present invention3C precursor product and Si/Fe3O4X-ray diffraction pattern of/C composite material, the main components of the composite material are Si, Fe and Fe3O4And graphitic carbon. FIG. 2 shows Si/Fe prepared in example 1 of the present invention3O4Scanning electron microscope images of the/C composite material.
And (3) adding the following components in an amount of 60: 20: weighing Si/Fe at a mass ratio of 203O4C: super-P: grinding 25% polyacrylic acid water solution uniformly, coating on copper foil to obtain electrode, using metal lithium sheet as counter electrode and electrolyte of 1mol/L LiPF6The simulated lithium ion battery (CR2025) is assembled by adopting/EC-DMC (volume ratio of 1:1) and a polypropylene microporous film as a diaphragm (Celgard 2300). FIG. 3 shows the cycle performance test of the corresponding battery in the voltage range of 0.2A/g and 0.01-3.0V, and it can be found that the composite material has excellent cycle stability, and the discharge capacity after 150 cycles is more than 1000 mAh/g. FIG. 4 is a graph of rate performance of a corresponding cell, the material being at 5The capacity of 528mAh/g still exists under the current density of A/g.
Example 2:
adding 0.1g of silicon powder, 0.4g of mesocarbon microbeads, 0.05g of ferrous oxide and ball milling beads into a ball milling tank, wherein the ball-material ratio is 100:1, adding 20ml of ethanol and 10ml of deionized water, sealing the ball milling tank, and vacuumizing; introducing CO2The gas is put into a tank, the pressure is 8MPa, the gas is heated to 35 ℃ to reach the supercritical fluid condition, the ball milling tank is continuously ball milled and reacted for 20 hours at the rotating speed of 300rpm, the powder product in the ball milling tank is collected after the suction filtration, the alcohol washing and the vacuum drying at 100 ℃, and finally the powder product is put in N2Calcining for 3h at 650 ℃ under the protection of atmosphere to finally obtain Si/Fe3O4a/C composite material.
With the resultant Si/Fe3O4the/C composite material was prepared into an electrode by the method of example 1 and assembled into a simulated lithium ion battery. FIG. 3 shows the cycle performance test of the corresponding battery in the voltage range of 0.2A/g and 0.01-3.0V, and it can be found that the composite material has excellent cycle stability, and the discharge capacity after 150 cycles is more than 800 mAh/g. Fig. 4 is a graph of rate performance of a corresponding battery, which has a capacity of 236mAh/g at a current density of 5A/g.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. By using supercritical CO2Preparation of Si/Fe by fluid medium3O4A method for producing a/C composite material, comprising the steps of:
(1) adding silicon powder, carbon material and iron source into a ball milling tank, adding a wet grinding agent and ball milling beads, sealing the ball milling tank, and vacuumizing;
(2) pumping CO into a sealed ball milling tank2Gas, ball milling reaction is carried out under supercritical condition to obtain Si/FeCO3a/C precursor product;
(3) after the ball milling reaction is finished, collecting a solid product in a ball milling tank and drying to obtain powder;
(4) sintering the collected powder in inert atmosphere to obtain Si/Fe3O4a/C composite material.
2. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4A method of producing a/C composite material, characterized by: in the step (1), the iron source is one or a combination of several of simple substance iron, ferrous oxide, ferrocene and ferrous hydroxide.
3. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4A method of producing a/C composite material, characterized by: in the step (1), the carbon material is one or a combination of several of graphite, mesocarbon microbeads, carbon nanotubes and graphene.
4. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4A method of producing a/C composite material, characterized by: in the step (1), the silicon powder, the carbon material and the iron source are mixed according to the mass ratio of silicon, carbon and iron elements of 1: (0.25-5): (0.2-0.5) feeding.
5. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4The method for preparing the/C composite material is characterized in that in the step (1), the wet grinding agent is one or more of methanol, ethanol, isopropanol and water.
6. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4The method for preparing the/C composite material is characterized in that in the step (2), the supercritical condition is CO2In a supercritical state.
7. The method of claim 6, wherein the supercritical CO is used2Fluid, especially for a motor vehiclePreparation of Si/Fe by medium3O4The method for preparing the/C composite material is characterized in that in the step (2), the supercritical conditions are that the gas pressure is greater than 7.3MPa and the ball milling temperature is greater than 32 ℃.
8. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4The method for preparing the/C composite material is characterized in that in the step (2), the ball milling rotating speed is 300-500 rpm, and the ball milling time is 10-24 hours.
9. The method of claim 1, wherein the supercritical CO is utilized2Preparation of Si/Fe by fluid medium3O4The method for preparing the/C composite material is characterized in that in the step (4), the sintering temperature is 500-700 ℃, and the sintering time is 3-5 hours.
10. Use of supercritical CO according to any one of claims 1 to 92Preparation of Si/Fe by fluid medium3O4Si/Fe prepared by method of/C composite material3O4The application of the/C composite material as a negative electrode material of a lithium ion battery.
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