CN112174110B - Preparation method of porous carbon fluoride material - Google Patents
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Abstract
The invention relates to a preparation method of a porous carbon fluoride material, which comprises the following steps: (1) introducing inert gas to passivate a reaction system by taking carbide or carbonitride as a raw material, and heating to 700-900 ℃; (2) continuously introducing fluorine gas for high-temperature fluorination etching treatment for 1-5 hours, and closing the fluorine gas; (3) keeping the temperature, continuously introducing inert gas to take away gas phase fluoride formed by the reaction, and cooling to obtain the porous carbon material; (4) introducing inert gas to passivate the reaction system again, and heating to 300-600 ℃; (5) and continuously introducing fluorine gas for fluorination treatment for 1-10 hours, closing the fluorine gas, introducing inert gas, and cooling to obtain the porous carbon fluoride material. By adopting carbide or carbonitride as a raw material, the carbon fluoride material with more uniform pore diameter distribution can be prepared by a method of directly using porous carbon as the raw material.
Description
Technical Field
The invention relates to a preparation method of a carbon fluoride material, in particular to a preparation method of porous carbon fluoride, belonging to the field of preparation of carbon fluoride materials.
Background
The carbon fluoride material is a covalent interlaminar compound consisting of carbon and fluorine, and has a chemical formula of CFx. Carbon fluoride can be used as a positive electrode material of a lithium primary battery, and the lithium carbon fluoride battery has many advantages: large specific capacity, wide range of use temperature, good safety, long service life, good stability and the like. However, the carbon fluoride material has problems of poor conductivity, slow diffusion rate of lithium ions between layers, severe polarization, and the like, and thus the application range thereof is greatly limited. In recent years, many researchers have studied the energy storage of carbon fluoride, mainly by modifying carbon fluoride materials.
The common modification methods at present mainly include methods of controlling the fluorine-carbon ratio (e.g. CN108928809A), surface coating (e.g. CN105336928A), and thermal cracking. However, these methods do not change the structure of the fluorocarbon material itself, and cannot increase the diffusion rate of lithium ions between the inner layers of the fluorocarbon. Therefore, the electrochemical performance of the fluorocarbon battery is not obviously improved when the fluorocarbon battery is discharged at medium and low rates.
The carbon fluoride material is commonly prepared by a high-temperature fluorination method, a low-temperature fluorination method and the like. The carbon fluoride prepared by the high-temperature fluorination method has higher specific energy but has poorer conductivity. However, the carbon fluoride material in the current market is mostly a high-temperature fluorination method product due to the simple preparation process. CN103332669A discloses a method for preparing fluorinated carbon by high temperature fluorination, wherein a mixed gas of nitrogen and fluorine is used as a fluorinating agent. CN109461923A discloses a porous carbon fluoride material prepared by a gas phase fluorination method directly using a porous carbon material (such as activated carbon, mesoporous carbon, etc.) as a raw material. But the pore size distribution of the raw material is not uniform, which is not beneficial to ion transportation.
Disclosure of Invention
In view of the above problems, the present invention provides a method for producing a porous fluorocarbon material from a carbide or carbonitride as a raw material.
The invention provides a preparation method of a porous carbon fluoride material, which comprises the following steps:
(1) introducing inert gas to passivate a reaction system by taking carbide or carbonitride as a raw material, and heating to 700-900 ℃;
(2) continuously introducing fluorine gas to perform high-temperature fluorination etching treatment for 1-5 hours, and closing the fluorine gas;
(3) continuously introducing inert gas to take away the formed gas-phase fluoride, taking away the gas-phase fluoride formed by the reaction by inert gas flow at high temperature, and cooling to obtain the porous carbon material;
(4) introducing inert gas to passivate the reaction system again, and heating to 300-600 ℃;
(5) and continuously introducing fluorine gas for fluorination treatment for 0.5-10 hours, closing the fluorine gas, introducing inert gas, and cooling to obtain the porous carbon fluoride material.
The method provided by the invention comprises the steps of etching non-carbon elements (such as B, metal elements or silicon elements) in carbide or carbonitride by using fluorine gas, leaving porous carbon containing a large number of pores, and then carrying out in-situ fluorination to obtain the fluorocarbon which has a hierarchical pore structure, a pore diameter of 2-10 nm and a specific surface area of 50-400 m and can reach a high fluorine-carbon ratio (0.9-1.2)2The porosity per gram is 10-40%, and the electrochemical performance is excellent: the discharge specific capacity at 1C is 850-950 mAh/g. Carbide or carbonitride is adopted as a raw material,compared with the method of directly taking porous carbon as a raw material, the carbon fluoride material with more uniform pore diameter distribution can be prepared. In addition, the raw materials of the invention are diversified, and the porous carbon fluoride with different pore size distributions can be prepared. In addition to porous fluorinated carbons, the intermediates of the process of the present invention, porous carbons, fluorides are also important industrial feedstocks. The method has simple process and can be industrialized in large scale.
The chemical composition of the carbide or carbonitride in the present invention may be MzCyN1-yWherein M is at least one of B, Ti, Zr, Si and Al, z is more than or equal to 1 and less than or equal to 4, and y is more than 0 and less than or equal to 1. Preferably, the carbide or carbonitride is B4C、TiC、ZrC、Ti3SiC2、Ti2AlC, SiC and/or TiC0.5N0.5。
Preferably, in the step (1), the step (3) and/or the step (4), the flow rate of the inert gas is 10 to 100 mL/min. More preferably 80mL/min, in the step (1) and/or the step (4), firstly introducing inert gas at a flow rate of 70-100 mL/min for 20-40 minutes, and then introducing inert gas at a flow rate of 10-30 mL/min after heating.
Preferably, in the step (2), the flow rate of the fluorine gas is 10 to 30 mL/min. In the step (5), the flow rate of the fluorine gas is 500 to 600 mL/min. Preferably, the inert gas is argon.
Drawings
FIG. 1 shows a schematic flow diagram of the method of the invention;
FIG. 2 shows an SEM image of a material prepared according to example 1 of the present invention;
fig. 3 shows the discharge curves at 0.1C and 5C for cells made from the materials prepared in examples 1, 2, 3, 4;
fig. 4 shows the discharge curves at 0.1C and 5C for cells made from the materials prepared in comparative examples 1 and 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
Referring to FIG. 1, the present invention is shownSchematic flow diagram for preparing porous carbon fluoride: firstly, carbide or carbonitride is selected as raw material. The chemical composition of the carbide or carbonitride may be MzCyN1-yWherein M is at least one of B, Ti, Zr, Si, Al, 1. ltoreq. z.ltoreq.4, 0. ltoreq. y.ltoreq.1, e.g. B4C、TiC、ZrC、Ti3SiC2、Ti2AlC, SiC and/or TiC0.5N0.5. The particle size of the carbide or carbonitride as a raw material powder may be 5 to 20 μm. Preferably, the starting materials are dried before the reaction.
Placing carbide or carbonitride in a reaction furnace, and introducing inert gas to passivate the reaction system. The inert gas may be argon. The flow rate of the inert gas can be 10-100 mL/min. Preferably, the inert gas is introduced in stages, for example, the inert gas is introduced at a flow rate of 70-100 mL/min for 20-40 min to rapidly passivate the reaction system, then the temperature is raised, and the flow rate of the inert gas is adjusted to 10-30 mL/min in the temperature raising process, so that the stability of the material can be ensured.
Raising the temperature to 700-900 ℃, introducing fluorine gas for high-temperature etching after the temperature is stable, wherein the flow rate of fluorine gas introduction can be 10-30 mL/min. At this time, non-carbon elements in the raw material are etched by fluorine gas to form a porous structure in situ, and the non-carbon elements react with fluorine to form gas phase fluoride. The gas phase fluoride can be discharged with the fluorine gas and can be removed with the inert gas which is introduced later. And (3) the high-temperature etching reaction can be continued for 1-5 hours, the fluorine gas is closed, the inert gas is continuously passed through, the flow rate of the inert gas is the same as that of the inert gas, and the temperature is reduced until the temperature is cooled to the room temperature.
And continuously introducing inert gas with the same flow rate, heating to 300-600 ℃, introducing fluorine gas for high-temperature fluorination treatment after the temperature is stable, wherein the flow rate of the fluorine gas can be 500-600 mL/min, and the fluorination treatment time can be 0.5-10 hours. Turning off the fluorine gas, introducing inert gas and cooling to obtain the carbon fluoride CF with a porous structureXX is more than 1, and the yield is more than 60%.
The reaction equation involved in the invention is as follows:
1.B4C+2F2＝4BF+C；2.2C+XF2＝2CFX；
1.TiC+2F2＝TiF4+C；2.2C+XF2＝2CFX；
1.ZrC+2F2＝ZrF4+C；2.2C+XF2＝2CFX；
1.Ti3SiC2+8F2＝3TiF4+SiF4+2C；2.2C+XF2＝2CFX；
1.2Ti2AlC+11F2＝4TiF4+2AlF3+2C；2.2C+XF2＝2CFX；
1.SiC+2F2＝SiF4+C；2.2C+XF2＝2CFX。
the carbon fluoride obtained by the method can reach a high fluorocarbon ratio (the fluorocarbon ratio is 0.9-1.2). Referring to FIG. 2, the particle size of the material prepared by the invention is 5-20 μm, the material has a hierarchical pore structure, the pore diameter is 2-10 nm, and the specific surface area is 50-400 m2The porosity per gram is 10-40%.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
After drying boron carbide powder (carbide) at 110 ℃ for 24 hours, the boron carbide powder was uniformly spread on a quartz boat, and the quartz boat was placed in a reaction furnace. The reaction mainly comprises two steps.
Firstly, introducing argon gas (99.999%) for 30min at a flow rate of 80ml/min before heating; then, the temperature was raised to 800 ℃ by adjusting the flow rate of argon gas to 15ml/min to 20 ml/min. After the temperature has stabilized, toFluorine gas is introduced at the flow rate of 10ml/min to 15ml/min for high-temperature fluorination etching, and the etching time is 3 hours. After the reaction is finished, the fluorine gas is closed, the heating is stopped, meanwhile, the argon gas is introduced for 30min at the flow rate of 80ml/min, and then the flow rate of the argon gas is adjusted to be 15 ml/min-20 ml/min until the tubular furnace is cooled to the room temperature. The first step is to etch off boron atoms layer by layer from the surface to the inside by fluorine gas at high temperature by using boron carbide crystal lattice as a template, and to etch off boron fluoride (gas phase fluoride MF) in gaseous stateX) The form is drained and collected to produce a porous carbon material skeleton.
And step two, uniformly spreading the porous carbon material obtained in the step one on a quartz boat, and putting the quartz boat into a reaction furnace. Argon (99.999%) is introduced for 30min at a flow rate of 80ml/min before heating; adjusting the argon flow to be 15 ml/min-20 ml/min, and starting heating to 400 ℃. After the temperature is stable, fluorine gas is introduced at the flow rate of 500 ml/min-600 ml/min to ensure that the porous carbon material continues to react with the fluorine gas, and the porous carbon material is cooled according to the same method of the first step to obtain the fluoride CF with a porous structure1.1The yield was 64%.
Referring to FIG. 2, the obtained material is granular, the particle size of the material prepared by the method is 5-20 μm, the material has a hierarchical pore structure, the pore diameter is 2-10 nm, the specific surface area is 50-400 m2/g, and the porosity is 10-40%. The obtained carbon fluoride material was assembled into a Li/CFx battery, and the assembled battery was subjected to a discharge test at current densities of 0.1C and 5C, respectively, and had a discharge specific capacity of 750mAh/g at 0.1C and 600mAh/g at 5C (see table 1).
Example 2
After drying the titanium carbide powder at 110 ℃ for 24 hours, the titanium carbide powder was evenly spread on a quartz boat, and the quartz boat was placed in a reaction furnace. Firstly, introducing argon gas (99.999%) for 30min at a flow rate of 80ml/min before heating; then, the temperature was raised to 800 ℃ by adjusting the flow rate of argon gas to 15ml/min to 20 ml/min. And after the temperature is stable, introducing fluorine gas at the flow rate of 10-15 ml/min for high-temperature fluorination etching for 3 hours. And after the reaction is finished, closing the fluorine gas, stopping heating, introducing argon gas at the flow rate of 80ml/min for 30min, and then adjusting the flow rate of the argon gas to be 15 ml/min-20 ml/min until the tubular furnace is cooled to the room temperature to prepare the porous carbon material framework.
And step two, uniformly spreading the porous carbon material obtained in the step one on a quartz boat, and putting the quartz boat into a reaction furnace. Argon (99.999%) is introduced for 30min at a flow rate of 80ml/min before heating; adjusting the argon flow to be 15 ml/min-20 ml/min, and starting heating to 400 ℃. After the temperature is stable, fluorine gas is introduced at the flow rate of 500 ml/min-600 ml/min so that the porous carbon material continues to react with the fluorine gas, and the fluorine gas is cooled according to the same method of the first step to obtain the fluoride CF with a porous structure1.04The yield was 68%.
The obtained material has a particle size of 10-15 μm, a hierarchical pore structure, a pore diameter of 2-8 nm, and a specific surface area of 150-300 m2(ii) a porosity of 20-40%. The obtained carbon fluoride material was assembled into a Li/CFx battery, and the assembled battery was subjected to a discharge test at current densities of 0.1C and 5C, respectively, and had a discharge specific capacity of 690mAh/g at 0.1C and 570mAh/g at 5C (see table 1).
Example 3
Mixing Ti3SiC2After the powder was dried at 110 ℃ for 24 hours, the powder was uniformly spread on a quartz boat, which was put into a reaction furnace. Firstly, introducing argon gas (99.999%) for 30min at a flow rate of 80ml/min before heating; then, the temperature was raised to 800 ℃ by adjusting the flow rate of argon gas to 15ml/min to 20 ml/min. And after the temperature is stable, introducing fluorine gas at the flow rate of 10-15 ml/min for high-temperature fluorination etching for 3 hours. And after the reaction is finished, closing the fluorine gas, stopping heating, introducing argon gas at the flow rate of 80ml/min for 30min, and then adjusting the flow rate of the argon gas to be 15 ml/min-20 ml/min until the tubular furnace is cooled to the room temperature to prepare the porous carbon material framework.
And step two, uniformly spreading the porous carbon material obtained in the step one on a quartz boat, and putting the quartz boat into a reaction furnace. Argon (99.999%) is introduced for 30min at a flow rate of 80ml/min before heating; adjusting the argon flow to be 15 ml/min-20 ml/min, and starting heating to 400 ℃. After the temperature is stable, fluorine gas is introduced at the flow rate of 500 ml/min-600 ml/min so that the porous carbon material continues to react with the fluorine gas, and the reaction product is cooled according to the same method as the first stepTo obtain a fluoride CF with a porous structure1.03The yield was 63%.
The obtained material has a particle size of 12-15 μm, a hierarchical pore structure, a pore diameter of 5-8 nm, and a specific surface area of 240-300 m2(ii) a porosity of 20-40%. The obtained carbon fluoride material was assembled into a Li/CFx battery, and the assembled battery was subjected to a discharge test at current densities of 0.1C and 5C, respectively, and had a discharge specific capacity of 640mAh/g at 0.1C and 550mAh/g at 5C (see table 1).
Example 4
Mixing titanium carbonitride powder (TiC)0.5N0.5) After drying at 110 ℃ for 24 hours, the powder was uniformly spread on a quartz boat, which was placed in a reaction furnace. Firstly, introducing argon gas (99.999%) for 30min at a flow rate of 80ml/min before heating; then, the temperature was raised to 800 ℃ by adjusting the flow rate of argon gas to 15ml/min to 20 ml/min. And after the temperature is stable, introducing fluorine gas at the flow rate of 10-15 ml/min for high-temperature fluorination etching for 3 hours. And after the reaction is finished, closing the fluorine gas, stopping heating, introducing argon gas at the flow rate of 80ml/min for 30min, and then adjusting the flow rate of the argon gas to be 15 ml/min-20 ml/min until the tubular furnace is cooled to the room temperature to prepare the porous carbon material framework.
And step two, uniformly spreading the porous carbon material obtained in the step one on a quartz boat, and putting the quartz boat into a reaction furnace. Argon (99.999%) is introduced for 30min at a flow rate of 80ml/min before heating; adjusting the argon flow to be 15 ml/min-20 ml/min, and starting heating to 400 ℃. After the temperature is stable, fluorine gas is introduced at the flow rate of 500 ml/min-600 ml/min to ensure that the porous carbon material continues to react with the fluorine gas, and the porous carbon material is cooled according to the same method of the first step to obtain the fluoride CF with a porous structure1.01The yield was 67%.
The obtained material has a particle size of 13-15 μm, a hierarchical pore structure, a pore diameter of 6-8 nm, a specific surface area of 170-300 m2/g, and a porosity of 25-40%. The obtained carbon fluoride material was assembled into a Li/CFx battery, and the assembled battery was subjected to a discharge test at current densities of 0.1C and 5C, respectively, and had a discharge specific capacity of 620mAh/g at 0.1C and 450mAh/g at 5C (see table 1).
Comparative example 1 porous activated carbon (available from clony, japan) was uniformly spread on a quartz boat, and the quartz boat was placed in a reaction furnace. Argon (99.999%) is introduced for 30min at a flow rate of 80ml/min before heating; adjusting the argon flow to be 15 ml/min-20 ml/min, and starting heating to 400 ℃. After the temperature is stable, fluorine gas is introduced at the flow rate of 500 ml/min-600 ml/min so that the porous carbon material continues to react with the fluorine gas, and the fluorine gas is cooled according to the same method of the first step to obtain the fluoride CF with a porous structure0.9The yield was 50%.
The obtained material is granular, has the particle size of 10-20 mu m, and has a porous structure, the pore diameter is 3-7 nm, the specific surface area is 1000m2/g, and the porosity is 50%. The resulting carbon fluoride material was assembled into a Li/CFx battery, and the assembled battery was subjected to a discharge test at current densities of 0.1C and 5C, respectively, see fig. 4, which had a discharge specific capacity of 520mAh/g at 0.1C and 410mAh/g at 5C (see table 1).
Table 1: comparison of electrochemical Properties of examples and comparative examples
The above-described embodiments are merely illustrative of several embodiments of the invention and do not represent a limitation on the scope of the invention, which may in fact be embodied in many different forms. Several variations and modifications are within the scope of the invention without departing from the spirit thereof, which is to be determined from the appended claims.
Claims (7)
1. A preparation method of a porous carbon fluoride material is characterized by comprising the following steps:
(1) introducing inert gas to passivate a reaction system by taking carbide or carbonitride as a raw material, and heating to 700-900 ℃; the chemical composition of the carbide or carbonitride is MzCyN1-yWherein M is at least one of B, Ti, Zr, Si and Al, z is more than or equal to 1 and less than or equal to 4, and y is more than 0 and less than or equal to 1;
(2) continuously introducing fluorine gas to perform high-temperature fluorination etching treatment for 1-5 hours, and closing the fluorine gas;
(3) keeping the temperature, continuously introducing inert gas to take away gas phase fluoride formed by the reaction, and cooling to obtain the porous carbon material;
(4) introducing inert gas to passivate the reaction system again, and heating to 300-600 ℃;
(5) continuously introducing fluorine gas for fluorination treatment for 1-10 hours, closing the fluorine gas, introducing inert gas, and cooling to obtain the porous carbon fluoride material; the fluorocarbon ratio of the porous carbon fluoride material is 0.9-1.2; the porous carbon fluoride material has a particle size of 5-20 μm, a hierarchical pore structure, a pore diameter of 2-10 nm, and a specific surface area of 50-400 m2(ii) a porosity of 10-40%.
2. The method according to claim 1, wherein the carbide or carbonitride is B4C、TiC、ZrC、Ti3SiC2、Ti2AlC, SiC and/or TiC0.5N0.5。
3. The method according to claim 1, wherein the flow rate of the inert gas in the step (1), the step (3) and/or the step (4) is 10 to 100 mL/min.
4. The preparation method according to claim 3, wherein in the step (1) and/or the step (4), the inert gas is introduced at a flow rate of 70 to 100 mL/min for 20 to 40 minutes, and after the temperature is raised, the inert gas is introduced at a flow rate of 10 to 30 mL/min.
5. The process according to claim 1, wherein in the step (2), the flow rate of the fluorine gas is 10 to 30 mL/min.
6. The process according to claim 1, wherein in the step (5), the flow rate of the fluorine gas is 500 to 600 mL/min.
7. The method according to any one of claims 1 to 6, wherein the inert gas is argon.
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