CN107963621B - Three-dimensional porous carbon material, preparation thereof and application thereof in sodium-ion battery - Google Patents

Three-dimensional porous carbon material, preparation thereof and application thereof in sodium-ion battery Download PDF

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CN107963621B
CN107963621B CN201711210219.4A CN201711210219A CN107963621B CN 107963621 B CN107963621 B CN 107963621B CN 201711210219 A CN201711210219 A CN 201711210219A CN 107963621 B CN107963621 B CN 107963621B
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dimensional porous
porous carbon
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CN107963621A (en
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张治安
陈玉祥
李劼
赖延清
尹盟
肖志伟
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Hunan Chenyu Fuji New Energy Technology Co ltd
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Central South University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the field of sodium ion battery materials, and particularly discloses a three-dimensional porous carbon material which is a three-dimensional porous material formed by carbon nanosheets and has a specific surface area of 100-2000 m2(ii)/g; the thickness of the carbon nano sheet is 10-100 nm. The invention also discloses a preparation method of the three-dimensional porous carbon material, which comprises the steps of placing dopamine and smectite in a solution, and carrying out polymerization reaction to obtain a precursor; carrying out heat treatment and washing on the precursor to obtain a layered carbon nanosheet material; and carrying out hydrothermal reaction on the layered carbon nanosheet material in a solution in which a positive surfactant is dissolved, and then carbonizing the hydrothermal reaction product to obtain the three-dimensional porous carbon material. The method has the advantages of easily available raw materials, simple preparation process and good repeatability; the prepared three-dimensional porous carbon material has the advantages of rich pores, high crosslinking degree, stable structure, large specific surface area, good conductivity and the like, and shows good battery performance when being used for a sodium ion battery.

Description

Three-dimensional porous carbon material, preparation thereof and application thereof in sodium-ion battery
Technical Field
The invention relates to a negative electrode material of a sodium-ion battery, in particular to a three-dimensional porous carbon material used as the negative electrode material of the sodium-ion battery.
Background
The sodium ion battery is rich in sodium reserves, and becomes a research hotspot of a new generation of secondary battery systems. Compared with a lithium ion battery, the sodium ion battery has the problems of high negative electrode voltage, large sodium ion radius and the like, and provides a plurality of problems for the development of the high-efficiency sodium ion battery. The electrode material determines important parameters of the battery, such as capacity, operating voltage, and cycle life. Although the reaction mechanism in the sodium ion battery is similar to that in the lithium ion battery, the sodium ion is about 55% larger than the lithium ion, the intercalation and diffusion of the sodium ion in the same structural material are often relatively difficult, and the structural change of the material after intercalation is larger, so that the specific capacity, the dynamic performance, the cycle performance and the like of the electrode material are correspondingly deteriorated. For example, graphite is an excellent negative electrode material in a lithium ion battery, and sodium ions are difficult to be embedded into a graphite layer, so that it is necessary to develop a material having excellent sodium storage performance in view of the existing efforts of lithium ion batteries while aiming at the characteristics of sodium ions.
Graphene materials are attracting attention due to their excellent in-layer conductivity and high carrier mobility. However, the graphene material used as the negative electrode material of the sodium-ion battery still has some problems to be solved (Advanced Materials, 2015, 27 (12): 2042-. Therefore, the carbon nano sheet material with simple preparation process and low cost has wide application prospect in the field of commercial sodium ion battery carbon cathode materials. However, the common carbon nano-sheet material still has the problems of poor structural stability and the like, so that the construction of the carbon nano-sheet material with stable structure is urgent.
Disclosure of Invention
In order to solve the technical problems of poor structural stability, easy agglomeration, easy stacking and the like of carbon nano sheets, the invention provides a three-dimensional porous carbon material, and aims to provide a carbon material with a stable structure and multiple pores.
The second purpose of the invention is to provide a preparation method of the three-dimensional porous carbon material.
The third purpose of the invention is to provide an application method of the three-dimensional porous carbon material as a negative electrode material of a sodium ion battery, and the purpose is to obviously improve the rate capability and the cycle performance of the sodium ion battery.
A three-dimensional porous carbon material (also called carbon aerogel in the invention) is composed of carbon nanosheetsThe specific surface area of the three-dimensional porous material is 100-2000 m2(ii)/g; the thickness of the carbon nano sheet is 10-100 nm.
The three-dimensional porous carbon material is composed of carbon nanosheets with the thickness of 10-100 nm; the three-dimensional porous carbon material has high crosslinking degree and porosity, moderate interlayer spacing, large specific surface area and good electrical conductivity; the material is used as the cathode material of the sodium ion battery, and the rate capability and the cycle performance of the sodium ion battery can be obviously improved.
Preferably, the specific surface area of the three-dimensional porous carbon material is 500-2000 m2(ii)/g; more preferably 1000 to 2000m2/g。
The invention also discloses a preparation method of the three-dimensional porous carbon material, which comprises the steps of placing dopamine and smectite in a solution, and carrying out polymerization reaction to obtain a precursor; carrying out heat treatment and washing on the precursor to obtain a layered carbon nanosheet material; and carrying out hydrothermal reaction on the layered carbon nanosheet material in a solution in which a positive surfactant is dissolved, and then carbonizing the hydrothermal reaction product to obtain the three-dimensional porous carbon material.
According to the preparation method, dopamine and smectite are placed in a solution, and the dopamine is subjected to self-polymerization on the surface of the smectite to obtain a precursor; and then carrying out low-temperature carbonization and template removal to obtain a layered carbon nanosheet material, and carrying out hydrothermal reaction and high-temperature carbonization on the obtained layered carbon nanosheet material and a positive surfactant to obtain the aerogel material. According to the method, the carbon nanosheets are prepared in advance under the conditions, and then the hydrothermal method and carbonization are matched, so that the three-dimensional porous carbon material with moderate interlayer spacing, large specific surface area, rich reactive active sites and the like can be prepared.
The key point of the technical scheme is that the three-dimensional porous carbon material is prepared by chemical polymerization and a hydrothermal method, the extensive smectite ore is used as a template, and the obtained three-dimensional porous carbon material has high porosity, high pore channel crosslinking degree, large specific surface area and stable structure, and can overcome the defect that a common carbon nanosheet is easy to collapse. In addition, the raw materials adopted by the invention are green and environment-friendly, are cheap and easily available, and have simple process, strong operability and good process repeatability, thereby being suitable for industrial production. The carbon cathode material of the sodium ion battery has good wettability with electrolyte, moderate interlayer spacing and good sodium ion embedding and removing capacity.
The smectite is a natural mineral of silicate.
Preferably, dopamine and smectite are placed in a solution, and a precursor is obtained through polymerization; the carbon nanosheet obtained in the way is more beneficial to preparing the three-dimensional porous carbon with excellent performance by matching with subsequent heat treatment.
According to the technical scheme, the specific surface area of the three-dimensional porous carbon material can be well regulated and controlled and the porosity of the material can be controlled by controlling the proportion of the smectite and the dopamine and the concentration of the cationic surfactant; thereby improving the electrical property of the obtained three-dimensional porous carbon.
According to the invention, the appropriate mass ratio of dopamine to smectite is favorable for improving the specific surface area of the aerogel. Preferably, the mass ratio of the dopamine to the smectite is 0.01-0.5. In this preferable range, the properties of the obtained carbon nanosheet are more suitable for producing three-dimensional porous carbon having excellent properties.
Still more preferably, the mass ratio of dopamine to smectite is 0.01-0.2.
The polymerization reaction is preferably carried out in an alkaline solution, for example, in an alkaline solution or a buffer solution having a pH of 8 to 9.5.
Preferably, the polymerization temperature is 10 to 90 ℃.
Preferably, the polymerization reaction time is from 1 to 50 hours.
The obtained precursor is preferably subjected to heat treatment in a nitrogen atmosphere.
Preferably, the heat treatment temperature is 400-.
The preferable heat treatment time is 0.5-10 h at the heat treatment temperature.
After heat treatment, the smectite in the heat treatment product is removed by washing to obtain the carbon nano sheet.
In the invention, the cationic surfactant is cetyl trimethyl ammonium bromide.
Researches show that hydrothermal reaction is carried out on the obtained thin-walled carbon nanosheet in a proper cationic surfactant concentration, so that the porosity of the material is improved, and further, the electrical property of the obtained three-dimensional porous carbon is improved; preferably, the concentration of the cationic surfactant in the starting solution of the hydrothermal reaction is 0.01 to 10 g/L.
Further preferably, the concentration of the cationic surfactant in the starting solution of the hydrothermal reaction is 0.5 to 1 g/L.
Preferably, the hydrothermal reaction temperature is 100-. The preferred hydrothermal reaction temperature is favorable for improving the stability of the subsequent three-dimensional porous carbon.
Further preferably, the hydrothermal reaction temperature is 160-. At this further preferable hydrothermal temperature, the stability of the obtained three-dimensional porous carbon is more excellent.
Under the hydrothermal reaction condition, the preferred hydrothermal reaction time is 1-50 h.
The carbonization process is carried out under protective atmosphere, wherein the protective atmosphere is nitrogen and inert gas.
Suitable carbonization temperatures are advantageous for further increasing the electrical conductivity of the material. Preferably, the carbonization temperature is 500-.
More preferably, the carbonization temperature is 1000-.
And (3) preserving heat and carbonizing at the carbonizing temperature, wherein the preferable carbonizing time is 0.5-10 h.
The invention discloses a preparation method of a preferable three-dimensional porous carbon material, which comprises the following steps:
step (1): placing dopamine and smectite in a buffer solution, and washing a template after a polymerization reaction to obtain a precursor; the mass ratio of the dopamine to the smectite is 0.01-0.5; the polymerization reaction time is 1-50 h; the polymerization temperature is 10-90 ℃.
Step (2): carbonizing the obtained precursor at the temperature of 400 ℃ and 600 ℃ for 0.5-10 h; carbonizing in an inert atmosphere;
and (3): the layered carbon nano sheet material and the surfactant dispersion liquid are subjected to hydrothermal reaction and high-temperature carbonization. The concentration of the surfactant is 0.01-10g/L, the hydrothermal reaction temperature is 100-220 ℃, the hydrothermal reaction time is 1-50h, the hydrothermal product is subjected to freeze drying and high-temperature carbonization to obtain the three-dimensional porous carbon material, the carbonization temperature is 500-1200 ℃, and the time is 0.5-10 h.
The invention also provides application of the three-dimensional porous carbon material as a negative electrode material of a sodium ion battery to preparation of a negative electrode of the sodium ion battery.
According to the invention, the three-dimensional porous carbon material is used as a negative electrode material, and the sodium ion battery prepared by the existing method has excellent rate performance and good cycle performance.
The carbon cathode material prepared by the technical scheme is applied to the sodium ion battery, the three-dimensional porous carbon material of the sodium ion battery is high in crosslinking degree, high in porosity and large in specific surface area, the sodium ion transmission distance can be shortened, the carbon cathode material has good sodium ion embedding and extracting capacity, a buffering effect is provided for the problem of volume expansion and shrinkage caused by sodium ion embedding and extracting, and good dynamic conditions are provided for the transmission of sodium ions and electrolyte.
The three-dimensional porous carbon material prepared by the technical scheme of the invention has the advantages of moderate space between the material layers, rich reactive active sites, high conductivity, short distance for embedding and removing sodium ions and large specific surface area, realizes the preparation of the three-dimensional porous carbon material and can obviously improve the sodium storage performance.
According to the invention, the three-dimensional porous carbon material can be prepared into the negative electrode of the sodium-ion battery by adopting the existing method, and then the sodium-ion battery is assembled. For example, the three-dimensional porous carbon material obtained by the invention is mixed with a conductive agent and a binder, and is coated on a copper foil current collector by a coating method to prepare the negative electrode of the sodium-ion battery.
Has the advantages that:
1. the technical scheme of the invention adopts smectite widely existing in the nature as a template, a precursor is obtained through supermolecule polymerization, and on the basis, the ultra-thin carbon nanosheet material is obtained through heat treatment (low-temperature carbonization) and template washing. The three-dimensional porous carbon material with rich pores and stable structure is obtained through simple and efficient hydrothermal treatment. The method adopts cheap and easily-obtained templates, has simple process and good reproducibility, and is suitable for industrial production.
2. The aerogel material obtained by the technical scheme of the invention has the advantages of high porosity, large specific surface area, high crosslinking degree, good conductivity and stable structure.
3. The aerogel material prepared by the technical scheme of the invention overcomes the problems of poor stability and lack of pore channels commonly existing in the conventional carbon nano sheet material, and the three-dimensional porous carbon material has rich pore channel structures, high conductivity and large specific surface area, can shorten the transmission distance of sodium ions, increases the reaction active sites of the sodium ions, and provides good relief for the problem of volume expansion and shrinkage caused by the intercalation and deintercalation of the sodium ions; meanwhile, the three-dimensional porous carbon material has super-strong structural stability, and the sodium storage performance of the obtained three-dimensional porous carbon material is excellent.
4. The three-dimensional porous carbon material is used for the sodium ion battery, and the sodium ion battery with high specific capacity, long cycle life and stable long cycle performance can be obtained.
Drawings
Fig. 1 is a Scanning Electron Micrograph (SEM) of the three-dimensional porous carbon material prepared in example 1.
FIG. 2 shows the cycle curve of the three-dimensional porous carbon material obtained in example 1 when used as the negative electrode carbon material of the sodium ion battery, at a current density of 50 mA/g.
Detailed Description
The present invention will be described in further detail with reference to examples, but these examples should not be construed as limiting the scope of the present invention.
Example 1
Putting 10g of smectite in a solution (aqueous solution of alkali) with the pH value of 8.5 for ultrasonic dispersion, putting 1g of dopamine in the solution, controlling the polymerization temperature at 30 ℃ and the polymerization time at 40h, carbonizing the obtained precursor, introducing inert gas for protection, carbonizing (thermally treating) the obtained precursor at 400 ℃ for 1h, and washing the template by using hot sodium hydroxide to obtain the carbon nanosheet material. Adding the obtained carbon nano sheet material into a CTAB (cetyltrimethylammonium bromide) solution with the concentration of 1g/L, ultrasonically dispersing, and placing inIn the hydrothermal reaction kettle, the hydrothermal reaction temperature is controlled to be 200 ℃, and the hydrothermal reaction time is 12 h. And carrying out heat treatment on the obtained hydrothermal product, introducing inert gas for protection, and obtaining the three-dimensional porous carbon material with the carbonization temperature of 1000 ℃ and the time of 2 h. The thickness of the carbon nano-sheet is concentrated at about 40nm, and the specific surface area of the obtained aerogel material is 1940m2/g。
The three-dimensional porous carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the flow density of 50mA/g, after 100 cycles (the cycle curve is shown in figure 2), the specific capacity of 234mA/g can be still maintained (the capacity retention rate is 99.5%).
Example 2
The difference from example 1 is only that the carbonization (heat treatment) temperature after hydrothermal reaction was 500 ℃. The thickness of the obtained carbon nano-sheet is concentrated at about 60nm, and the specific surface area of the obtained aerogel material is 1540m2/g。
The three-dimensional porous carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the flow density of 50mA/g, the specific capacity of 202mA/g can be still maintained after 100 cycles (the capacity retention rate is 98%).
Example 3
Putting 20g of smectite in a solution with the pH value of 8.5 for ultrasonic dispersion, putting 1g of dopamine in the solution, controlling the polymerization temperature to be 50 ℃ and the polymerization time to be 20 hours, carbonizing the obtained precursor, introducing inert gas for protection, washing the template by using hot sodium hydroxide to obtain the carbon nanosheet material, wherein the carbonization temperature is 500 ℃ and the carbonization time is 2 hours. Adding the obtained carbon nano sheet material into a solution with CTAB concentration of 0.5g/L, carrying out ultrasonic dispersion, placing in a hydrothermal reaction kettle, controlling the hydrothermal reaction temperature at 160 ℃ and the hydrothermal reaction time at 24 h. The obtained hydrothermal product is subjected to heat treatment,and introducing inert gas for protection, wherein the carbonization temperature is 1100 ℃, and the time is 4h to obtain the three-dimensional porous carbon material. The thickness of the carbon nano-sheet is concentrated at about 30nm, and the specific surface area of the obtained aerogel material is 570m2/g。
The three-dimensional porous carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the flow density of 50mA/g, after 100 cycles, the specific capacity of 217mA/g can be still maintained (the capacity retention rate is 99%).
Example 4
Placing 5g of smectite in a solution with the pH value of 8.5 for ultrasonic dispersion, placing 1g of dopamine in the solution, controlling the polymerization temperature to be 80 ℃ and the polymerization time to be 10 hours, carbonizing the obtained precursor, introducing inert gas for protection, washing a template by using hot sodium hydroxide to obtain the carbon nanosheet material, wherein the carbonization temperature is 600 ℃ and the carbonization time is 10 hours. Adding the obtained carbon nano sheet material into a solution with CTAB concentration of 0.8g/L, carrying out ultrasonic dispersion, placing in a hydrothermal reaction kettle, controlling the hydrothermal reaction temperature at 200 ℃ and the hydrothermal reaction time at 30 h. And carrying out heat treatment on the obtained hydrothermal product, introducing inert gas for protection, and obtaining the aerogel material with the carbonization temperature of 800 ℃ and the time of 3 h. The thickness of the carbon nano-sheet is concentrated at about 70nm, and the specific surface area of the obtained three-dimensional porous carbon material is 1580m2/g。
The three-dimensional porous carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the flow density of 50mA/g, after 100 cycles, the specific capacity of 225mA/g can be still maintained (the capacity retention rate is 98%).
Example 5
Compared with the embodiment 4, the difference is only that the CTAB concentration is 5g/L, the thickness of the obtained carbon nano sheet is concentrated on about 70nm, and the specific surface area of the obtained three-dimensional porous carbon material is1690m2/g。
The three-dimensional porous carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the condition of the flow density of 50mA/g, after 100 cycles, the specific capacity of 241mA/g can be still maintained (the capacity retention rate is 98%).
Example 6
Compared with example 4, the difference is only that 50g of smectite is placed in a solution with pH of 8.5 for ultrasonic dispersion, 1g of dopamine is placed in the solution, the thickness of the obtained carbon nanosheet is concentrated to about 70nm, and the specific surface area of the obtained three-dimensional porous carbon material is 1874m2/g。
The three-dimensional porous carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the flow density of 50mA/g, after 100 cycles, the specific capacity of 248mA/g can be still maintained (the capacity retention rate is 98%).
Comparative example 1
Putting 10g of smectite in a solution with the pH value of 8.5 for ultrasonic dispersion, putting 1g of dopamine in the solution, controlling the polymerization temperature to be 30 ℃ and the polymerization time to be 40h, carbonizing the obtained precursor, introducing inert gas for protection, washing a template by using hot sodium hydroxide to obtain the carbon nanosheet material, wherein the carbonization temperature is 400 ℃ and the carbonization time is 1 h. The thickness of the carbon nano-sheet is concentrated at about 40nm, and the specific surface area of the obtained carbon nano-sheet is 910m2/g。
The carbon nanosheet material prepared in the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested at the current density of 50 mA/g. The test result shows that the negative electrode of the sodium ion battery prepared by the embodiment has good electrochemical performance: under the flow density of 50mA/g, after 100 cycles, the specific capacity is 162mA/g (the capacity retention rate is 93%).
Comparative example 2
Compared with example 4, the difference is only that the montmorillonite ore is not added, and the specific surface area of the obtained carbon material is 480m2/g。
The carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the condition of the flow density of 50mA/g, after 100 cycles, the specific capacity is 183mA/g (the capacity retention rate is 94%).
Comparative example 3
Compared with example 1, the difference is only that no cationic surfactant is added, and the specific surface area of the obtained three-dimensional porous carbon material is 950m2/g。
The carbon material prepared by the embodiment is used as a working electrode, sodium is used as a counter electrode, a button cell is assembled, and the capacity performance is tested under the current density of 50 mA/g. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the condition of the flow density of 50mA/g, after 100 cycles, the specific capacity is 201mA/g (the capacity retention rate is 95%).

Claims (17)

1. The three-dimensional porous carbon material is characterized by being a three-dimensional porous material consisting of carbon nanosheets, and having a specific surface area of 100-2000 m2(ii)/g; the thickness of the carbon nano sheet is 10-100 nm;
the preparation process comprises the following steps:
taking smectite as a template, placing dopamine and smectite in a solution, and carrying out polymerization reaction to obtain a precursor; the precursor is subjected to heat treatment and washing to remove a smectite template, so that a layered carbon nanosheet material is obtained; and carrying out hydrothermal reaction on the layered carbon nanosheet material in a solution in which a cationic surfactant is dissolved, and then carbonizing the hydrothermal reaction product to obtain the three-dimensional porous carbon material.
2. The three-dimensional porous carbon material according to claim 1, characterized in that: the mass ratio of the dopamine to the smectite is 0.01-0.5.
3. The three-dimensional porous carbon material according to claim 1, characterized in that: the polymerization reaction time is 1-50 h; the polymerization temperature is 10-90 ℃.
4. The three-dimensional porous carbon material according to claim 1, characterized in that: the heat treatment temperature is 400-.
5. The three-dimensional porous carbon material according to claim 1, characterized in that: the cationic surfactant is cetyltrimethylammonium bromide.
6. The three-dimensional porous carbon material according to claim 2, characterized in that: the concentration of the cationic surfactant in the initial solution of the hydrothermal reaction is 0.01-10 g/L.
7. The three-dimensional porous carbon material according to claim 1, characterized in that: the hydrothermal reaction temperature is 100-220 ℃, and the hydrothermal reaction time is 1-50 h.
8. The three-dimensional porous carbon material according to claim 1, characterized in that: the carbonization temperature is 500-1200 ℃, and the time is 0.5-10 h.
9. A preparation method of a three-dimensional porous carbon material is characterized in that dopamine and smectite are placed in a solution and subjected to polymerization reaction to obtain a precursor; carrying out heat treatment and washing on the precursor to obtain a layered carbon nanosheet material; and carrying out hydrothermal reaction on the layered carbon nanosheet material in a solution in which a cationic surfactant is dissolved, and then carbonizing the hydrothermal reaction product to obtain the three-dimensional porous carbon material.
10. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the mass ratio of the dopamine to the smectite is 0.01-0.5.
11. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the polymerization reaction time is 1-50 h; the polymerization temperature is 10-90 ℃.
12. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the heat treatment temperature is 400-.
13. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the cationic surfactant is cetyltrimethylammonium bromide.
14. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the concentration of the cationic surfactant in the initial solution of the hydrothermal reaction is 0.01-10 g/L.
15. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the hydrothermal reaction temperature is 100-220 ℃, and the hydrothermal reaction time is 1-50 h.
16. The method for producing a three-dimensional porous carbon material according to claim 9, characterized in that: the carbonization temperature is 500-1200 ℃, and the time is 0.5-10 h.
17. Use of the three-dimensional porous carbon material according to any one of claims 1 to 8, or the three-dimensional porous carbon material produced by the production method according to any one of claims 9 to 16, characterized in that: the material is used as a negative electrode material of a sodium ion battery and is applied to preparing a negative electrode of the sodium ion battery.
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CN115261890B (en) * 2022-09-26 2023-01-17 苏州仕净科技股份有限公司 Method for preparing porous carbon material by electrochemically reducing carbon dioxide

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