CN107895797B - Preparation method of carbon nanosheet material and application of carbon nanosheet material in sodium ion battery - Google Patents

Preparation method of carbon nanosheet material and application of carbon nanosheet material in sodium ion battery Download PDF

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CN107895797B
CN107895797B CN201711261632.3A CN201711261632A CN107895797B CN 107895797 B CN107895797 B CN 107895797B CN 201711261632 A CN201711261632 A CN 201711261632A CN 107895797 B CN107895797 B CN 107895797B
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carbon
carbon nanosheet
nanosheet material
precursor
transition metal
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CN107895797A (en
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张治安
尹盟
陈玉祥
赖延清
张凯
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SHENZHEN RESEARCH INSTITUTE 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
    • 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
    • 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 discloses a preparation method of a carbon nanosheet material and application of the carbon nanosheet material in a sodium ion battery; mixing phenolic resin and KCl in absolute ethyl alcohol or dimethyl formamide to form suspension; after taking the suspension for hydrothermal reaction, taking the product and placing the product into a water solution of transition metal salt to be stirred so as to absorb transition metal ions to obtain a precursor; and carbonizing the precursor at 800-1200 ℃. The method has the advantages of easily available raw materials, simple preparation process and good repeatability; the prepared material is disordered in long range and ordered in short range, has larger interlayer spacing, rich pore channel structure, large specific surface area and good conductivity, shows high cycle efficiency, high specific capacity and rate capability when used for a sodium ion battery, and has wide industrial application prospect.

Description

Preparation method of carbon nanosheet material and application of carbon nanosheet material in sodium ion battery
Technical Field
The invention relates to a preparation method of a carbon nanosheet material and application of the carbon nanosheet material as a carbon cathode material of a sodium ion battery, and belongs to the field of sodium ion batteries.
Background
Along with the gradual decrease of traditional energy sources such as coal, oil, natural gas and the like and the increasingly severe environmental problems, the demand of small-sized separated mobile power sources shows an explosive growth trend, and various rechargeable chemical power sources represented by lithium ion batteries are increasingly paid more attention. With the increasing demand for hybrid vehicles and electrical energy storage devices, the consumption of lithium has also increased dramatically. However, since lithium has a relatively small element content in the earth's crust and extraction and recovery of lithium are difficult, sodium ion batteries having a similar deintercalation mechanism as lithium ion batteries are considered to be an ideal choice for large-scale energy storage.
At present, based on the consideration of material development cost and application prospect, most of the studied sodium ion negative electrode materials are mainly various carbon-based materials, such as graphite, graphene, amorphous carbon and the like, and the electrochemical properties of the carbon-based materials are related to respective structures. For example, graphite has a relatively high lithium storage capacity, but its sodium storage capacity is weak, and it is widely believed that the mismatch between the radius of sodium ions and the graphite layer spacing results. The amorphous carbon has low graphitization degree, is mainly formed by staggered accumulation of a large number of disordered carbon microcrystals, has large interlayer spacing, contains a large number of nano micropores, and provides an ideal active site for the storage of sodium ions, so that the amorphous carbon material has high reversible sodium storage capacity, but the material has poor conductivity, poor performance cycle stability and fast capacity attenuation, and the application of the material in sodium ion batteries is greatly limited. Therefore, how to improve the specific capacity and the long-term cycling stability of the carbon material as the negative electrode of the sodium-ion battery becomes a key problem for limiting the large-scale application of the carbon material as the negative electrode material of the sodium-ion battery.
Disclosure of Invention
Aiming at the defects of the existing sodium ion battery electrode material, the invention aims to provide a preparation method of a carbon nanosheet which is short-range ordered, long-range disordered, large in specific surface area, rich in reactive active sites, moderate in interlayer spacing and has a certain graphitization degree.
Another object of the present invention is to provide the above carbon nanosheet material as a negative electrode material for application in a sodium ion battery, and the obtained sodium ion battery exhibits high specific capacity, good rate capability and long cycle stability.
The invention relates to a preparation method of a carbon nano sheet material, which comprises the following steps:
step one
Dissolving phenolic resin serving as a carbon source in absolute ethyl alcohol or dimethyl formamide, adding KCl, stirring to form a suspension, carrying out hydrothermal reaction on the suspension, carrying out first solid-liquid separation after the reaction is finished to obtain solid particles A, and washing and drying to obtain a carbon nanosheet material precursor;
in the suspension, the mass ratio of the phenolic resin to the KCl is 1-10: 1;
the reaction temperature of the hydrothermal reaction is 160-220 ℃, and the reaction time is 16-24 h;
step two
The precursor of the carbon nano sheet material obtained in the step one is subjected to a chemical vapor deposition treatment; putting the carbon nano-sheet material precursor into a transition metal salt solution to obtain a mixed turbid solution, stirring, carrying out solid-liquid separation for the second time to obtain solid particles B, and drying to obtain a carbon nano-sheet material precursor for adsorbing transition metal ions;
the mass fraction of the carbon nano sheet material precursor in the transition metal salt aqueous solution is 1-15 wt%;
step three
The carbon nano sheet material precursor adsorbing transition metal ions obtained in the step two is used; carbonizing the raw material under the protection of inert atmosphere to obtain a crude product, wherein the carbonization temperature is 800-1200 ℃, and washing and drying the crude product to obtain the product carbon nanosheet material.
The invention relates to a preparation method of a carbon nanosheet material, wherein in the first step, the mass fraction of phenolic resin in a suspension is 15 wt% -30 wt%. Preferably, the mass fraction of the phenolic resin in the suspension is 17 wt% to 25 wt%.
The invention relates to a preparation method of a carbon nanosheet material.
The invention relates to a preparation method of a carbon nanosheet material, which comprises the following steps of in step one, the mass ratio of phenolic resin to KCl is 2-6: 1.
the invention relates to a preparation method of a carbon nanosheet material, which comprises the step one, wherein the reaction temperature of the hydrothermal reaction is 160-180 ℃, and the reaction time is 16-18 h.
In the second step, the transition metal salt solution is at least one selected from a ferric chloride solution, a cobalt nitrate solution and a copper sulfate solution, and the concentration of the transition metal salt solution is 1-3 mol/L.
The invention relates to a preparation method of a carbon nanosheet material, and in the second step, the mass fraction of a precursor of the carbon nanosheet material in a transition metal salt aqueous solution is 4 wt% -8 wt%.
The invention relates to a preparation method of a carbon nanosheet material, wherein in the second step, the stirring time is 16-24 h.
The invention relates to a preparation method of a carbon nanosheet material. Preferably, the inert atmosphere is a nitrogen atmosphere.
The invention relates to a preparation method of a carbon nanosheet material, which comprises the third step of carbonizing at 800-900 ℃ for 1-4 h at a temperature rising rate of 1-10 ℃/min. Preferably, the carbonization time is 2 to 3 hours.
The invention relates to a preparation method of a carbon nanosheet material, which comprises the following steps of washing a crude product by adopting an inorganic acid solution with the concentration of 1-3 mol/L and water alternately for more than or equal to 3 times, placing the product at the temperature of 50-80 ℃, and drying the product in vacuum for 8-12 hours; and obtaining the carbon nano sheet material.
The preparation method of the carbon nanosheet material comprises the third step of preparing the carbon nanosheet material from graphitized carbon and amorphous carbon nanosheets, wherein the graphitized carbon is uniformly dispersed on the amorphous carbon nanosheets, and the thickness of the carbon nanosheet material is 50-500 nm.
In the present invention, graphitized carbon means carbon having a graphitization degree R.ltoreq.1.2, and the formula of R is represented by R ═ ID/IGSaid I isDMeans 1360cm in Raman spectrum-1The integrated intensity of said IGMean 1580cm in Raman spectrum-1Integrated intensity of (G peak).
The invention relates to a preparation method of a carbon nano sheet material, which comprises the third step that the specific surface area of the carbon nano sheet material is 100m2/g～1200m2(ii) in terms of/g. In a preferred embodiment, the specific surface area of the carbon nanosheet material is 200 m2/g～1000m2(ii) in terms of/g. In a further preferred embodiment, the specific surface area of the carbon nanosheet material is 400m2/g ～800m2/g
The invention also provides an application of the carbon nanosheet material, and the carbon nanosheet material is applied to a sodium ion battery as a negative electrode material of the sodium ion battery.
The carbon nano sheet material prepared by the invention is used as a negative electrode material for preparationThe method for detecting the performance of the sodium-ion battery comprises the following steps: weighing the carbon nano sheet material, adding 10 wt.% of Super P as a conductive agent, adding 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, fully grinding, adding a small amount of deionized water, mixing to form uniform black pasty slurry, coating the slurry on a copper foil current collector to serve as a test electrode, and assembling a button cell by taking a metal sodium sheet as a contrast electrode, wherein an electrolytic liquid system is 1M NaClO4DEC (1: 1). The charge-discharge current density used for testing the cycle performance is 100 mA/g.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the method adopts easily-obtained phenolic resin as a carbon source, KCl as a crystal structure template, and then the carbon nanosheet precursor with regular morphology is prepared through hydrothermal reaction, and meanwhile, common transition metal ions are adsorbed as a catalyst, and then the carbon nanosheet precursor is obtained through high-temperature carbonization on the basis. The method has the advantages of cheap and easily-obtained raw materials, simple process, good repeatability, environmental friendliness and easy realization of industrial production.
The technical scheme of the invention is based on; the organic layer is coated on the surface of the inorganic salt crystal serving as a template, and under the action of transition metal ions, the organic layer is subjected to phase conversion in a high-temperature carbonization process, and part of carbon is converted into an ordered graphitized carbon material, so that the carbon nanosheet material is obtained, has a composite structure in which graphitized carbon is uniformly dispersed on amorphous carbon nanosheets, and effectively promotes the embedding and separating process of sodium ions among carbon layers, so that the specific capacity of the porous carbon material is greatly improved, the coulomb efficiency of a battery is effectively improved, and the performance of a sodium ion battery is improved. The invention realizes the perfect combination of high sodium storage specific capacity and high cycle coulombic efficiency.
The carbon nanosheet material prepared by the method is used as a sodium ion battery cathode material, has good wettability with electrolyte, good conductivity, moderate interlayer spacing, large specific surface area and rich active sites, can shorten the transmission distance of sodium ions, has good sodium ion embedding and removing capacity, has rich ordered graphite annular structure and high conductivity, is beneficial to electron conduction, reduces impedance, and improves the multiplying power performance and the cycle efficiency of the battery.
The carbon nano sheet material has a special composite carbon structure, the loose porous structure provides rich active sites for the storage of sodium ions, the relatively large carbon layer spacing of the porous carbon material can effectively promote the embedding and separating process of the sodium ions among the carbon layers, the specific capacity of the carbon material is improved, and meanwhile, the high-graphitization carbon obtained by uniform dispersion provides excellent conductive capability and sodium storage capability. The method can be used for preparing the sodium ion battery with high coulombic efficiency, excellent rate capability and long cycle stability.
Drawings
Fig. 1 is an SEM scanning electron micrograph of the carbon nanosheet material prepared in example 1.
Fig. 2 is a graph of cycle number-cycle discharge capacity and coulombic efficiency of the carbon nanosheet material prepared in example 1 applied to a sodium ion battery.
Fig. 3 is a raman spectrum of the carbon nanosheet material prepared in example 1.
Fig. 4 is an XRD diffractogram of the carbon nanosheet material prepared in example 1.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
Dissolving 12.8g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 2.23g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, keeping the temperature at 180 ℃, and keeping the temperature for 18 h. And (3) washing the product for 3 times by using deionized water after filtering, and then drying the product for 10 hours in a vacuum drying oven at 60 ℃ to obtain a two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 2mol/L cobalt nitrate solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing transition metal ions. Carbonizing the precursor at 900 ℃ in nitrogen atmosphereThe chemical reaction time is 2h, and the heating rate is 2 ℃/min. And then repeatedly washing the high-temperature carbonized product with 2mol/L dilute hydrochloric acid solution and water for three times, placing the washed product at the temperature of 50 ℃, and drying the product in vacuum for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the carbon nano sheet material is 792m2The Scanning Electron Micrograph (SEM) of the prepared carbon nanosheet material is shown in FIG. 1.
The carbon nanosheet material prepared in this example was added with 10 wt.% of Super P as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, ground thoroughly, and then mixed with a small amount of deionized water to form a uniform black paste, the paste was coated on a copper foil current collector to form a test electrode, and a metal sodium sheet was used as a contrast electrode to assemble a button cell, which was assembled using an electrolytic liquid system of 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first circle is 75 percent, the discharge capacity of the first circle is 366mA/g, and after 100 circles of circulation, the specific capacity of 296mA/g can still be kept; under the discharge densities of 1000mA/g and 2000mA/g, the specific capacities of 252mAh/g and 209mAh/g can be still respectively maintained.
Example 2
Dissolving 13.1g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 3.34g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, keeping the temperature at 180 ℃, and keeping the temperature for 16 h. And washing for 3 times by using deionized water after filtering, and then drying for 10 hours in a vacuum drying oven at 60 ℃ to obtain the two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 1mol/L ferric chloride solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing the transition metal ions. And carbonizing the precursor under the nitrogen atmosphere, wherein the carbonization temperature is 1200 ℃, the carbonization time is 2h, and the heating rate is 2 ℃/min. Then repeatedly washing the high-temperature carbonized product with 2mol/L dilute acid solution and water for three times, and then placing the product at 50 DEG CAnd (4) drying for 8 hours in vacuum under the mild condition. And obtaining the carbon nano sheet material. The specific surface area of the material is 690m2/g
The carbon nanosheet material prepared in this example was added with 10 wt.% of Super P as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, ground thoroughly, and then mixed with a small amount of deionized water to form a uniform black paste, the paste was coated on a copper foil current collector to form a test electrode, and a metal sodium sheet was used as a contrast electrode to assemble a button cell, which was assembled using an electrolytic liquid system of 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the first-turn coulombic efficiency is 74%, the first-turn discharge capacity is 341mA/g, and the specific capacity of 283mA/g can be still maintained after circulation for 100 turns; under the discharge densities of 1000mA/g and 2000mA/g, the specific capacities of 244mAh/g and 201mAh/g can be still respectively maintained.
Example 3
Dissolving 9.8g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 3.3g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, keeping the temperature at 180 ℃, and keeping the temperature for 16 h. And washing for 3 times by using deionized water after filtering, and then drying for 10 hours in a vacuum drying oven at 60 ℃ to obtain the two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 3mol/L cobalt nitrate solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing transition metal ions. Carbonizing the precursor under the nitrogen atmosphere, wherein the carbonizing temperature is 900 ℃, the carbonizing time is 2h, and the heating rate is 2 ℃/min. And then repeatedly washing the high-temperature carbonization product by using a dilute nitric acid solution with the concentration of 2mol/L and water, and then placing the product at the temperature of 50 ℃ for vacuum drying for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the material is 581m2/g。
The carbon nanosheet material prepared in this example was added with 10 wt.% Super P as a conductive materialThe preparation is characterized in that 10 wt.% of sodium carboxymethylcellulose (CMC) is used as a binder, a small amount of deionized water is added after the sodium carboxymethylcellulose (CMC) is fully ground to form uniform black paste slurry, the slurry is coated on a copper foil current collector to be used as a test electrode, a metal sodium sheet is used as a contrast electrode to be assembled into a button cell, and an electrolytic liquid system is 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first circle is 70 percent, the discharge capacity of the first circle is 310mA/g, and the specific capacity of 230mA/g can still be kept after 100 circles of circulation; under the discharge densities of 1000mA/g and 2000mA/g, the specific capacities of 201mAh/g and 188mAh/g can be still respectively maintained.
Example 4
Dissolving 12.8g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 1.28g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, keeping the temperature at 160 ℃, and keeping the temperature for 16 h. And washing for 3 times by using deionized water after filtering, and then drying for 10 hours in a vacuum drying oven at 60 ℃ to obtain the two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 2mol/L nickel chloride solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing the transition metal ions. Carbonizing the precursor under the nitrogen atmosphere, wherein the carbonization temperature is 800 ℃, the carbonization time is 3h, and the heating rate is 2 ℃/min. And then repeatedly washing the high-temperature carbonized product for three times by using a dilute sulfuric acid solution with the concentration of 2mol/L and water, and then placing the washed product at the temperature of 50 ℃ for vacuum drying for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the material is 433m2The carbon nanosheet material prepared in the example was added with 10 wt.% of Super P as a conductive agent and 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, and after being sufficiently ground, a small amount of deionized water was added to mix the materials to form a uniform black paste slurry, and the slurry was coated on a copper foil current collector as a test electrode and assembled with a sodium metal sheet as a reference electrodeIs a button cell, which adopts an electrolytic liquid system of 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first circle is 65%, the discharge capacity of the first circle is 289mA/g, and after 100 circles of circulation, the specific capacity of 233mA/g can still be kept; specific capacities of 195mAh/g and 177mAh/g can be still respectively maintained under the discharge densities of 1000mA/g and 2000 mA/g.
Comparative example 1
Dissolving 12.8g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 2.23g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, keeping the temperature at 160 ℃, and keeping the temperature for 24 hours. And washing for 3 times by using deionized water after filtering, then drying for 10 hours at 60 ℃ in a vacuum drying oven to obtain a two-dimensional carbon nanosheet precursor, and carbonizing the precursor under the nitrogen atmosphere at the carbonization temperature of 900 ℃ for 2 hours at the heating rate of 2 ℃/min. And then repeatedly washing the high-temperature carbonized product with 2mol/L dilute hydrochloric acid solution and water for three times, and then placing the washed product at the temperature of 50 ℃ for vacuum drying for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the material is 683m2/g。
The comparative example is adopted to prepare a carbon nano sheet material, 10 wt.% of Super P is added to serve as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) serves as a binder, a small amount of deionized water is added to be mixed after the mixture is fully ground to form uniform black paste slurry, the slurry is coated on a copper foil current collector to serve as a test electrode, a metal sodium sheet serves as a contrast electrode to be assembled into a button cell, and an electrolytic liquid system is adopted to be 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first loop is 77 percent, the discharge capacity of the first loop is 202mA/g,after circulating for 100 circles, keeping the specific capacity of 142 mA/g; specific capacities of 126mAh/g and 102mAh/g were maintained at discharge densities of 1000mA/g and 2000mA/g, respectively.
Comparative example 2
Dissolving 13.1g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, transferring the phenolic resin to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, and keeping the temperature at 180 ℃ for 16 h. And washing for 3 times by using deionized water after filtering, and then drying for 10 hours in a vacuum drying oven at 60 ℃ to obtain the two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 1mol/L ferric chloride solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing the transition metal ions. And carbonizing the precursor under the nitrogen atmosphere, wherein the carbonization temperature is 1200 ℃, the carbonization time is 2h, and the heating rate is 2 ℃/min. And then repeatedly washing the high-temperature carbonized product with 2mol/L dilute acid solution and water for three times, and then placing the product at the temperature of 50 ℃ for vacuum drying for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the material is 302m2/g。
The carbon nanosheet material prepared in this example was added with 10 wt.% of Super P as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, ground thoroughly, and then mixed with a small amount of deionized water to form a uniform black paste, the paste was coated on a copper foil current collector to form a test electrode, and a metal sodium sheet was used as a contrast electrode to assemble a button cell, which was assembled using an electrolytic liquid system of 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. Test results show that the first-turn coulombic efficiency of the material is 64% under the current density of 50mA/g, the first-turn discharge capacity is 201mA/g, and the specific capacity of 130mA/g is kept after 100-turn circulation; under the discharge densities of 1000mA/g and 2000mA/g, the specific capacities of 101mAh/g and 91mAh/g can be still respectively maintained.
Comparative example 3
Dissolving 12.8g phenolic resin in 20ml absolute ethyl alcohol, stirring until completely dissolved, uniformly spreading on a culture dish paved with 2.23g KCl, placing the culture dish on a culture dishDrying in an oven at 60 deg.C until the ethanol is completely evaporated. And (3) washing the product for 3 times by using deionized water after filtering, and then drying the product for 10 hours in a vacuum drying oven at 60 ℃ to obtain a two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 2mol/L cobalt nitrate solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing transition metal ions. Carbonizing the precursor under the nitrogen atmosphere, wherein the carbonizing temperature is 900 ℃, the carbonizing time is 2h, and the heating rate is 2 ℃/min. And then repeatedly washing the high-temperature carbonized product with 2mol/L dilute hydrochloric acid solution and water for three times, placing the washed product at the temperature of 50 ℃, and drying the product in vacuum for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the carbon nano sheet material is 633m2/g。
The carbon nanosheet material prepared in this example was added with 10 wt.% of Super P as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, ground thoroughly, and then mixed with a small amount of deionized water to form a uniform black paste, the paste was coated on a copper foil current collector to form a test electrode, and a metal sodium sheet was used as a contrast electrode to assemble a button cell, which was assembled using an electrolytic liquid system of 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first circle is 66%, the discharge capacity of the first circle is 249mA/g, and after 100 circles of circulation, the specific capacity of 180mA/g is kept; specific capacities of 152mAh/g and 109mAh/g were maintained at discharge densities of 1000mA/g and 2000mA/g, respectively.
Comparative example 4:
dissolving 12.8g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 2.23g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction, keeping the temperature at 150 ℃, and keeping the temperature for 18 h. And (3) washing the product for 3 times by using deionized water after filtering, and then drying the product for 10 hours in a vacuum drying oven at 60 ℃ to obtain a two-dimensional carbon nanosheet precursor. 3.1g of two-dimensional carbon nanosheet precursorAnd (3) placing the precursor into 50mL of 2mol/L cobalt nitrate solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing the transition metal ions. Carbonizing the precursor under the nitrogen atmosphere, wherein the carbonizing temperature is 900 ℃, the carbonizing time is 2h, and the heating rate is 2 ℃/min. And then repeatedly washing the high-temperature carbonized product with 2mol/L dilute hydrochloric acid solution and water for three times, placing the washed product at the temperature of 50 ℃, and drying the product in vacuum for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the carbon nano sheet material is 401m2/g。
The carbon nanosheet material prepared in this example was added with 10 wt.% of Super P as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, ground thoroughly, and then mixed with a small amount of deionized water to form a uniform black paste, the paste was coated on a copper foil current collector to form a test electrode, and a metal sodium sheet was used as a contrast electrode to assemble a button cell, which was assembled using an electrolytic liquid system of 1M NaClO4/
EC: DEC (1:1), at a current density of 50mA/g, cycle performance was tested; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first circle is 66%, the discharge capacity of the first circle is 233mA/g, and after 100 circles of circulation, the specific capacity of 168mA/g is kept; specific capacities of 144mAh/g and 101mAh/g were maintained at discharge densities of 1000mA/g and 2000mA/g, respectively.
Comparative example 5
Dissolving 17.1g of phenolic resin in 50ml of absolute ethyl alcohol, stirring until the phenolic resin is completely dissolved, adding 1.13g of KCl, continuously stirring until suspension is formed, transferring the suspension to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, keeping the temperature at 180 ℃, and keeping the temperature for 18 h. And (3) washing the product for 3 times by using deionized water after filtering, and then drying the product for 10 hours in a vacuum drying oven at 60 ℃ to obtain a two-dimensional carbon nanosheet precursor. And (3.1 g) placing the two-dimensional carbon nanosheet precursor into 50mL of 2mol/L cobalt nitrate solution, stirring for 24h, and performing suction filtration and drying to obtain the two-dimensional carbon nanosheet precursor adsorbing transition metal ions. The precursor is fed into the reactor under the nitrogen atmosphereCarbonizing at 900 deg.C for 2h at a heating rate of 2 deg.C/min. And then repeatedly washing the high-temperature carbonized product with 2mol/L dilute hydrochloric acid solution and water for three times, placing the washed product at the temperature of 50 ℃, and drying the product in vacuum for 8 hours. And obtaining the carbon nano sheet material. The specific surface area of the carbon nano sheet material is 299m2/g。
The carbon nanosheet material prepared in this example was added with 10 wt.% of Super P as a conductive agent, 10 wt.% of sodium carboxymethylcellulose (CMC) as a binder, ground thoroughly, and then mixed with a small amount of deionized water to form a uniform black paste, the paste was coated on a copper foil current collector to form a test electrode, and a metal sodium sheet was used as a contrast electrode to assemble a button cell, which was assembled using an electrolytic liquid system of 1M NaClO4DEC (1:1), at a current density of 50mA/g, to test the cycling performance; the rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g and the like. The test result shows that the negative electrode of the sodium-ion battery prepared by the embodiment has good electrochemical performance: under the current density of 50mA/g, the coulombic efficiency of the first circle is 66%, the discharge capacity of the first circle is 245mA/g, and after 100 circles of circulation, the specific capacity of 177mA/g is kept; specific capacities of 156mAh/g and 110mAh/g were maintained at discharge densities of 1000mA/g and 2000mA/g, respectively.

Claims (8)

1. A preparation method of a carbon nano sheet material is characterized by comprising the following steps:
step one
Dissolving phenolic resin serving as a carbon source in absolute ethyl alcohol or dimethyl formamide, adding KCl, stirring to form a suspension, carrying out hydrothermal reaction on the suspension, carrying out first solid-liquid separation after the reaction is finished to obtain solid particles A, and washing and drying to obtain a carbon nanosheet material precursor;
in the suspension, the mass ratio of the phenolic resin to the KCl is 2-6: 1;
the reaction temperature of the hydrothermal reaction is 160-220 ℃, and the reaction time is 16-24 h;
step two
The precursor of the carbon nano sheet material obtained in the step one is subjected to a chemical vapor deposition treatment; putting the carbon nano-sheet material precursor into a transition metal salt solution to obtain a mixed turbid solution, stirring, carrying out solid-liquid separation for the second time to obtain solid particles B, and drying to obtain a carbon nano-sheet material precursor for adsorbing transition metal ions;
the mass fraction of the carbon nano sheet material precursor in the transition metal salt aqueous solution is 1-15 wt%;
step three
The carbon nano sheet material precursor adsorbing transition metal ions obtained in the step two is used; carbonizing at 800-1200 ℃ under the protection of inert atmosphere to obtain a crude product, washing and drying the crude product to obtain a product carbon nanosheet material,
the carbon nanosheet material is composed of graphitized carbon and amorphous carbon nanosheets, the graphitized carbon is uniformly dispersed on the amorphous carbon nanosheets, the thickness of the carbon nanosheet material is 50 nm-500 nm, and the specific surface area of the carbon nanosheet material is 100m2/g～1200m2/g。
2. The method for preparing a carbon nanosheet material according to claim 1, wherein in the first step, the mass fraction of the phenolic resin in the suspension is 15 wt% to 30 wt%.
3. The method for preparing a carbon nanosheet material according to claim 1, wherein in the first step, the hydrothermal reaction is carried out at a reaction temperature of 160 ℃ to 180 ℃ for a reaction time of 16h to 18 h.
4. The method for preparing a carbon nanosheet material as claimed in claim 1, wherein in step two, the transition metal salt solution is at least one selected from a ferric chloride solution, a cobalt nitrate solution and a copper sulfate solution, and the concentration of the transition metal salt solution is 1mol/L to 3 mol/L.
5. The method for preparing a carbon nanosheet material according to claim 1, wherein in step two, the stirring time is 16 to 24 hours;
in the second step, the mass fraction of the carbon nanosheet material precursor in the transition metal salt solution is 4 wt% -8 wt%.
6. The method for preparing a carbon nanosheet material according to claim 1, wherein in step three, the temperature of the carbonization is 800 ℃ to 900 ℃, the time of the carbonization is 1h to 4h, and the temperature rise rate of the carbonization is 1 ℃/min to 10 ℃/min.
7. The method for preparing a carbon nanosheet material as claimed in claim 1, wherein the carbon nanosheet material has a specific surface area of 400m2/g～800m2/g。
8. The application of the carbon nanosheet material in the sodium-ion battery is characterized in that the carbon nanosheet material as defined in any one of claims 1 to 7 is applied to the sodium-ion battery as a negative electrode material of the sodium-ion battery.
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