CN108428894B - Sulfur-doped two-dimensional carbon material, and preparation method and application thereof - Google Patents
Sulfur-doped two-dimensional carbon material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a sulfur-doped two-dimensional carbon material, a preparation method and application thereof, and more particularly relates to a method for preparing an in-situ sulfur-doped two-dimensional carbon material serving as a sodium ion battery cathode by using hydrotalcite as a template, a product and application thereof. The preparation method is simple and easy in preparation process, high in sulfur content doping amount and capable of realizing large-scale production.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a sulfur-doped two-dimensional carbon material, a preparation method and application thereof, and more particularly relates to a method for preparing an in-situ sulfur-doped two-dimensional carbon material serving as a sodium ion battery cathode by using hydrotalcite as a template, a product and application thereof.
Background
In recent years, lithium ion batteries have advantages of large specific capacity, high discharge voltage, good stability, safe use, long service life and the like, and are widely applied to electronic products such as mobile phones, notebook computers and the like. However, the demand for lithium is rapidly increasing due to the rapid increase in the demand for electronic devices and electric vehicles. And the content of lithium element in the earth crust is only 0.0065%, the abundance of the lithium element is positioned at the 27 th position, and the lithium element is intensively distributed in a few areas. In consideration of large-scale energy storage requirements, the ideal secondary battery has the characteristics of abundant resources, low price and the like besides proper electrochemical performance. Obviously, lithium ion batteries cannot meet the large-scale production requirements. Sodium and lithium are in the same main group and possess similar physicochemical properties. In addition, the content of sodium in the earth crust is 2.74 percent, which is much higher than that of lithium in the earth crust, and the sodium-ion battery is distributed around the world, so the sodium-ion battery is a good choice in large-scale production.
Carbon materials are widely used in various fields, including energy fields, due to their advantages of abundant sources, environmental protection, low price, etc. The negative electrode material used by the current commercial lithium ion battery is graphite, but the radius of sodium ions is larger than that of lithium ions, so that the sodium ions cannot be effectively embedded into the graphite negative electrode, and the sodium storage activity of the graphite negative electrode is poor, so that the graphite negative electrode material cannot be directly applied to the sodium ion battery. In order to effectively apply the carbon material to the sodium ion battery, it is necessary to design it in structure or composition. The carbon material can be made into zero-dimensional, one-dimensional, two-dimensional or three-dimensional nano structures in structure, each structure has unique advantages and has the function of reducing the diffusion path of sodium ions. The components are mainly doped through heteroatoms, so that point defects can be caused, the adsorption of sodium ions is promoted, active sites and conductivity are increased, the interlayer spacing can be enlarged to a certain degree, and the intercalation of more sodium ions is facilitated.
At present, some sulfur-doped carbon materials need to additionally provide a sulfur source, such as elemental sulfur, hydrogen sulfide or some sulfur-containing organic matters; secondly, at present, organic matters which are used as a carbon source and a sulfur source are directly carbonized into a sulfur-doped carbon material, but most of the materials are micron-level block materials, and when the materials are used as negative electrode materials of sodium ion batteries, the diffusion of ions in the materials is not facilitated, so that the capacity of the materials during large-current charging and discharging is low, namely the rate capability is poor.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a sulfur-doped two-dimensional carbon material, a preparation method and application thereof, which are fully combined with the characteristics and requirements of the sulfur-doped two-dimensional carbon material, redesign is performed on the aspects of raw materials, preparation process, principle and the like in a targeted manner, and key parameters are optimized and selected, so that the two-dimensional carbon material with high sulfur doping content, large specific surface area and hierarchical pore structure is correspondingly obtained, the preparation process is simple and feasible, large-scale production can be realized, and the prepared in-situ sulfur-doped two-dimensional carbon material shows high capacity, excellent rate capability and good cycle performance when used as a sodium ion battery cathode material.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a sulfur-doped two-dimensional carbon material, comprising the steps of:
(1) carrying out heat treatment on hydrotalcite by taking the hydrotalcite as a template to remove hydroxyl and carbonate among hydrotalcite layers to obtain the heat-treated hydrotalcite; the hydrotalcite is hydrotalcite with a memory effect;
(2) cooling the hydrotalcites subjected to heat treatment, mixing the cooled hydrotalcites with the precursor solution, and fully stirring to enable the precursor to be inserted into the hydrotalcite layers in an anion form; filtering, washing filter residue with water, and drying to obtain hydrotalcite with precursor intercalation;
(3) under the action of an oxidant, the precursor intercalated hydrotalcite is subjected to oxidative polymerization reaction to obtain precursor polymer intercalated hydrotalcite;
(4) pre-carbonizing the hydrotalcite intercalated with the precursor polymer in an inert gas protective atmosphere to pre-carbonize the precursor polymer in an interlayer structure of the hydrotalcite, and then removing the hydrotalcite template by an acid washing method to obtain a pre-carbonized product;
(5) and carrying out secondary carbonization on the pre-carbonized product in the inert gas protective atmosphere to obtain the sulfur-doped two-dimensional carbon material.
Preferably, the hydrotalcite in the step (1) is Mg-Al hydrotalcite or Zn-Al hydrotalcite.
Preferably, the heat treatment in step (1) is specifically: the heat treatment temperature is 400-600 ℃, and the heat preservation is carried out for 1-4 h.
Preferably, the precursor solution in step (2) is an unsaturated organic sulfonate solution.
Preferably, the unsaturated organic sulfonate is sodium styrene sulfonate.
Preferably, the oxidizing agent of step (3) is a persulfate.
Preferably, the oxidizing agent in the step (3) is potassium persulfate solution with the concentration of 0.1-0.5 mol/L, and the oxidative polymerization time is 0.5-4 h.
Preferably, the pre-carbonization temperature in the step (4) is 600-800 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-6 h.
Preferably, the acid cleaning in the step (4) is performed by using a hydrochloric acid aqueous solution and a hydrofluoric acid aqueous solution.
Preferably, the second carbonization temperature in the step (5) is 600-800 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-6 h.
According to another aspect of the invention, a sulfur-doped two-dimensional carbon material is provided, which is prepared according to the preparation method.
Preferably, the sulfur-doped two-dimensional carbon material has the sulfur doping amount of 4.77-6.90% and the specific surface area of 679m2g-1～930.6m2g-1And has a hierarchical pore structure.
According to another aspect of the invention, the application of the sulfur-doped two-dimensional carbon material is provided for preparing a sodium-ion battery negative electrode material.
In general, the above technical solutions contemplated by the present invention can achieve the following advantageous effects compared to the prior art.
(1) The invention provides a preparation method of a sulfur-doped two-dimensional carbon material, which takes hydrotalcite as a template and sulfonate of unsaturated organic matters as a precursor, and sequentially carries out intercalation of the precursor, oxidative polymerization of the precursor, carbonization and fixation of the precursor, removal of the template and secondary carbonization to realize the preparation of the in-situ sulfur-doped two-dimensional carbon material, wherein the preparation process is simple and easy to implement, has high sulfur doping amount, and can be produced in a large scale;
(2) according to the preparation method of the sulfur-doped two-dimensional carbon material, the hydrotalcite is used as a medium template, and the hydrotalcite is wide in source and environment-friendly;
(3) the invention takes hydrotalcite as a template for the first time and takes unsaturated organic sulfonate as a precursor to prepare the two-dimensional carbon material which is used as a negative electrode material of a sodium-ion battery;
(4) according to the preparation method of the sulfur-doped two-dimensional carbon material, the sulfonate of an unsaturated organic substance is used as a precursor, the precursor is provided with a sulfonic acid group, and is matched with a hydrotalcite medium template with a layered structure, and the in-situ high-content sulfur doping can be carried out by skillfully setting a preparation process without subsequent treatment;
(5) according to the preparation method of the sulfur-doped two-dimensional carbon material, the adjustment and control of the sulfur content can be simply realized by changing the annealing temperature;
(6) the in-situ sulfur-doped two-dimensional carbon material prepared by the method has the advantages of high sulfur doping amount, large specific surface area, hierarchical pore structure, high capacity, excellent rate capability and good cycle performance when used as a negative electrode material of a sodium ion battery.
Drawings
FIG. 1 is a flow chart of the preparation of example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
FIG. 3 is a transmission electron microscope image of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
Fig. 4 is an XRD spectrum of steps (1), (3), (4), and (5) of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
FIG. 5 is an XPS spectrum of a sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
Fig. 6 is an adsorption and desorption curve and a pore size distribution curve of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
FIG. 7 is a diagram showing electrochemical cycle performance of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
FIG. 8 shows the rate capability of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention.
FIG. 9 shows the rate capability of the sulfur-doped two-dimensional carbon material prepared in example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for preparing an in-situ sulfur-doped two-dimensional carbon material by using hydrotalcite as a template, which comprises the following steps:
(1) and (2) carrying out heat treatment on the hydrotalcite by taking the hydrotalcite as a template so as to remove hydroxyl and carbonate among hydrotalcite layers, wherein the heat treatment is carried out in a protective atmosphere at the temperature of 400-600 ℃, and the heat is preserved for 1-4 h to obtain the heat-treated hydrotalcite, so that a precursor containing sulfur and carbon is inserted into an interlayer structure of the hydrotalcite in the next step. The hydrotalcite is hydrotalcite with memory effect, which means that some hydrotalcite materials are heated at a certain temperature (generally 450-. Hydrotalcite having a memory effect such as Mg-Al based hydrotalcite or Zn-Al based hydrotalcite. Taking Mg-Al series hydrotalcite as an example, the hydrotalcite can be prepared by the following method: and adding water into the basic magnesium carbonate and the sodium metaaluminate to mix, stirring, washing with deionized water, and drying to obtain the hydrotalcite template. The choice of the molar ratio of Mg to Al is important, and the difference in Mg-Al ratio results in different charge densities of the layers of the carbon, which changes the distribution of anionic organic compounds between the layers, i.e. the yield of carbon produced in the end product. After the hydrotalcite is subjected to heat treatment, the hydrotalcite is cooled along with the furnace in a protective atmosphere so as to ensure that carbon dioxide and water molecules in the air cannot enter the interlayer.
(2) Cooling the hydrotalcites subjected to heat treatment, mixing the cooled hydrotalcites with the precursor solution, and fully stirring to enable the precursor to be inserted into the hydrotalcite layers in an anion form; the precursor solution is an unsaturated organic sulfonate solution, filtering is carried out, filter residue is washed by water and then dried, and the hydrotalcite with the precursor intercalation is obtained; the unsaturated organic sulfonate is preferably sodium styrene sulfonate, and nitrogen is continuously introduced during the preparation of the sodium styrene sulfonate, preferably under stirring, to prevent carbon dioxide molecules from entering the solution.
(3) Under the action of an oxidant, the precursor intercalated hydrotalcite is subjected to oxidative polymerization reaction to obtain precursor polymer intercalated hydrotalcite; the oxidant is persulfate, preferably potassium persulfate solution with the concentration of 0.1-0.5 mol/L, and the oxidation polymerization time is 0.5-4 h. After the oxidative polymerization of the precursor organic matter, the color of the mixed system can be obviously changed from white powder to yellow powder.
(4) Pre-carbonizing the hydrotalcite intercalated with the precursor polymer in an inert gas protective atmosphere to pre-carbonize the precursor polymer in an interlayer structure of the hydrotalcite, and then removing the hydrotalcite template by an acid washing method to obtain a pre-carbonized product; the pre-carbonization temperature is 600 ℃ to 800 ℃, the heating rate is 1 ℃/min to 10 ℃/min, and the heat preservation time is 1h to 6 h. The acid cleaning is performed by adopting hydrochloric acid aqueous solution and hydrofluoric acid aqueous solution.
(5) And carrying out secondary carbonization on the pre-carbonized product in the inert gas protective atmosphere to obtain the sulfur-doped two-dimensional carbon material. The second carbonization temperature is 600 ℃ to 800 ℃, the heating rate is 1 ℃/min to 10 ℃/min, and the heat preservation time is 1h to 6 h.
In the preparation process of the in-situ sulfur-doped two-dimensional carbon material, precursor organic matters containing a sulfur source and a carbon source enter an interlayer structure of a hydrotalcite template in an anion form, and then are required to be pre-carbonized firstly, namely the organic matters are subjected to primary carbonization under the fixing action of the template between the layers, then the template is removed, and secondary carbonization is required after the template is removed. In the experiment, the sulfur-doped carbon material which is pre-carbonized and template-removed is used as the cathode material of the sodium ion battery, and the found poor performance is probably because the existence of the template influences the crystallization performance of the material in the carbonization process, and finally the performance is influenced when the material is used as the battery material. After the material is carbonized for the second time, the crystallization performance and the battery performance of the prepared sulfur-doped two-dimensional carbon material are obviously improved. In addition, in the second carbonization, it is experimentally found that the doping amount of sulfur is influenced by the carbonization annealing temperature, and the higher the temperature is, the less the two-dimensional carbon material lattice defects are, and accordingly, the less the sulfur is doped in the carbon material, so that it is necessary to control the carbonization annealing temperature appropriately.
The precursor of the sulfur-doped two-dimensional carbon material is used as a sulfur source and a carbon source at the same time, and no additional reagent is needed to be added. The in-situ sulfur-doped carbon material with the two-dimensional structure is designed from the structure and the components, the steps are simple, the obtained carbon and sulfur doping content is high, the sulfur doping amount is 4.77-6.90%, and the specific surface area is 679m2g-1～930.6m2g-1The carbon material has a hierarchical pore structure, and provides a certain idea for preparing the in-situ highly-doped carbon material at present. The material has the advantages of two-dimensional structure, hierarchical pore structure and the like, so that sodium ions can be rapidly transmitted and diffused, the rate capability of the material is improved, and the in-situ sulfur-doped two-dimensional carbon material can be used as a sodium ion battery cathode material and shows excellent performance.
The following are examples:
example 1
(1) Adding water into the basic magnesium carbonate and the sodium metaaluminate to mix (the molar ratio of Mg to Al is 2:1), stirring for 12 hours, washing with deionized water, and drying in an oven at 60 ℃ to obtain the hydrotalcite template.
(2) Preparing 50mg/mL sodium p-styrenesulfonate solution, placing the solution in a three-necked bottle, and continuously introducing N2And stirring for 12 hours for later use.
(3) And (3) heating the hydrotalcite template to 475 ℃ in Ar atmosphere, preserving the temperature for 3h, and quickly introducing the hydrotalcite template into the three-necked bottle in the step (2) after cooling to room temperature along with the furnace. Stirring at 80 deg.C for 12 hr, washing with deionized water, vacuum filtering, and drying the solid in oven.
(4) Dispersing the product obtained in (3) in a solvent containing 200mL of 0.1mol/L K2S2O8Aqueous solutionHeating in 80 deg.C water bath, stirring for 1 hr, washing with deionized water, and oven drying.
(5) And (3) placing the product in the step (4) in an alumina crucible, heating to 600 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 3h, cooling to room temperature, taking out the product, placing the product in a beaker filled with 1mol/L hydrochloric acid, stirring for 48h, then carrying out suction filtration, then placing the product in a diluted HF aqueous solution, and stirring for 24h to remove residual oxides. Then washing with deionized water, and drying in a 60 ℃ oven.
And (3) placing the product obtained in the step (5) in an alumina crucible, placing the alumina crucible in a tube furnace, carrying out second carbonization annealing treatment, heating the product to 700 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 2h, cooling the product to room temperature, taking out the product, coating the product according to a certain proportion, and sealing the battery.
FIG. 1 is a flow chart of the preparation of example 1 of the present invention. FIG. 2 is a scanning electron microscope image of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention. The product is a sheet structure and has folds similar to graphene, and the carbon material prepared by the method is preliminarily judged to be a two-dimensional nano carbon material.
FIG. 3 is a transmission electron microscope image of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention. The product can be seen as a large-area nano-sheet, further verifying that the invention is feasible.
FIG. 4 is an XRD spectrum of the products obtained in steps (1), (3), (4) and (5) of example 1 of the present invention. Indicating that the precursors passed between the layers into the hydrotalcite template, resulting in a two-dimensional structure after annealing.
FIG. 5 is an XPS spectrum of a sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention. The in-situ sulfur doping of the invention is feasible, and the sulfur doping content is 5.7 atom%.
Fig. 6 is an adsorption and desorption curve and a pore diameter curve of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention. It can be seen that the material has distinct micropores and mesopores, and is a hierarchical pore structure.
FIG. 7 is a diagram showing electrochemical cycle performance of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention. Indicating the final productArticle 1A g-1The reversible specific capacity after 600 cycles is up to 252.0mAh g under the current density of-1Coulombic efficiency approaches 100%.
FIG. 8 shows the rate capability of the sulfur-doped two-dimensional carbon material prepared in example 1 of the present invention. At 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10A g-1The reversible specific capacities are 361.8, 333.6, 298.7, 268.0, 235.7, 184.8, 153.4 and 125.0mAh g respectively under the current density of (1)-1And when the current returns to 0.2 and 0.1A g-1The reversible specific capacity can be respectively recovered to 331.3 mAh g and 349.6mAh g-1The rate capability of the material is excellent.
The material prepared in the example is a two-dimensional material, wherein the doped sulfur content is 5.7 atom%, and the specific surface area is 804.6m2g-1Pore structure micropore volume: 0.303m3g-1Mesoporous volume of 0.302m3g-1。
Example 2
(1) Adding water into the basic magnesium carbonate and the sodium metaaluminate to mix (the molar ratio of Mg to Al is 2:1), stirring for 12 hours, then repeatedly washing with deionized water, and drying in an oven at 60 ℃ to obtain the hydrotalcite template.
(2) Preparing 50mg/mL sodium p-styrenesulfonate solution, placing the solution in a three-necked bottle, and continuously introducing N2And stirring for 12 hours for later use.
(3) And (3) heating the hydrotalcite template to 475 ℃ in Ar atmosphere, preserving the temperature for 3h, and quickly introducing the hydrotalcite template into the three-necked bottle in the step (2) after cooling to room temperature. After stirring for 12h at 80 ℃, washing with deionized water, and drying in an oven.
(4) Dispersing the product obtained in (3) in a solvent containing 200mL of 0.1mol/L K2S2O8Heating in water bath at 80 deg.C, stirring for 1 hr, washing with deionized water, and oven drying.
(5) And (3) placing the product in the step (4) in an alumina crucible, heating to 600 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 3h, cooling to room temperature, taking out the product, placing the product in a beaker filled with 1mol/L hydrochloric acid, stirring for 48h, then carrying out suction filtration, then placing the product in a diluted HF aqueous solution, and stirring for 24h to remove residual oxides. Then washing with deionized water, and drying in a 60 ℃ oven.
And (3) placing the product obtained in the step (5) in an alumina crucible, placing the alumina crucible in a tube furnace, carrying out second carbonization annealing treatment, heating the product to 600 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving the heat for 2h, cooling the product to room temperature, taking out the product, coating the product according to a certain proportion, and sealing the battery.
The material prepared in the embodiment is a two-dimensional material, wherein the doping amount of sulfur is 6.90atom percent, and the specific surface area is 930.6m2g-1The pore structure: micropore volume: 0.351m3g-1The mesoporous volume: 0.321m3g-1。
Example 3
(1) Adding water into the basic magnesium carbonate and the sodium metaaluminate to mix (the molar ratio of Mg to Al is 2:1), stirring for 12 hours, washing with deionized water, and drying in an oven at 60 ℃ to obtain the hydrotalcite template.
(2) Preparing 50mg/mL sodium p-styrenesulfonate solution, placing the solution in a three-necked bottle, and continuously introducing N2And stirring for 12 hours for later use.
(3) And (3) heating the hydrotalcite template to 475 ℃ in Ar atmosphere, preserving the temperature for 3h, and quickly introducing the hydrotalcite template into the three-necked bottle in the step (2) after cooling to room temperature. After stirring for 12h at 80 ℃, washing with deionized water, and drying in an oven.
(4) Dispersing the product obtained in (3) in a solvent containing 200mL of 0.1mol/L K2S2O8Heating in water bath at 80 deg.C, stirring for 1 hr, washing with deionized water, and oven drying.
(5) And (3) placing the product in the step (4) in an alumina crucible, heating to 600 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 3h, cooling to room temperature, taking out the product, placing the product in a beaker filled with 1mol/L hydrochloric acid, stirring for 48h, then carrying out suction filtration, then placing the product in a diluted HF aqueous solution, and stirring for 24h to remove residual oxides. Then washing with deionized water, and drying in a 60 ℃ oven.
And (3) placing the product obtained in the step (5) in an alumina crucible, placing the alumina crucible in a tube furnace, carrying out second carbonization annealing treatment, heating to 800 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 2h, cooling to room temperature, taking out, coating according to a certain proportion, and sealing the battery.
The material prepared in the example is a two-dimensional material, wherein the doping amount of sulfur is 4.77atom percent, and the specific surface area is 679.0m2g-1Pore structure micropore volume: 0.238m3g-1Mesoporous volume of 0.310m3g-1。
Example 4
(1) Adding water into the basic magnesium carbonate and the sodium metaaluminate to mix (the molar ratio of Mg to Al is 2:1), stirring for 12 hours, then repeatedly washing with deionized water, and drying in an oven at 60 ℃ to obtain the hydrotalcite template.
(2) Preparing 50mg/mL sodium p-styrenesulfonate solution, placing the solution in a three-necked bottle, and continuously introducing N2And stirring for 12 hours for later use.
(3) And (3) heating the hydrotalcite template to 475 ℃ in Ar atmosphere, preserving the temperature for 3h, and quickly introducing the hydrotalcite template into the three-necked bottle in the step (2) after cooling to room temperature. After stirring for 12h at 80 ℃, washing with deionized water, and drying in an oven.
(4) Dispersing the product obtained in (3) in a solvent containing 200mL of 0.5mol/L K2S2O8Heating in water bath at 80 deg.C, stirring for 1 hr, washing with deionized water, and oven drying.
(5) And (3) placing the product in the step (4) in an alumina crucible, heating to 600 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 3h, cooling to room temperature, taking out the product, placing the product in a beaker filled with 1mol/L hydrochloric acid, stirring for 48h, then carrying out suction filtration, then placing the product in a diluted HF aqueous solution, and stirring for 24h to remove residual oxides. Then washing with deionized water, and drying in a 60 ℃ oven.
And (3) placing the product obtained in the step (5) in an alumina crucible, placing the alumina crucible in a tube furnace, carrying out second carbonization annealing treatment, heating the product to 700 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 2h, cooling the product to room temperature, taking out the product, coating the product according to a certain proportion, and sealing the battery.
Comparative example 1
(1) Adding water into the basic magnesium carbonate and the sodium metaaluminate to mix (the molar ratio of Mg to Al is 2:1), stirring for 12 hours, washing with deionized water, and drying in an oven at 60 ℃ to obtain the hydrotalcite template.
(2) Preparing 50mg/mL sodium p-styrenesulfonate solution, placing the solution in a three-necked bottle, and continuously introducing N2And stirring for 12 hours for later use.
(3) And (3) heating the hydrotalcite template to 475 ℃ in Ar atmosphere, preserving the temperature for 3h, and quickly introducing the hydrotalcite template into the three-necked bottle in the step (2) after cooling to room temperature along with the furnace. Stirring at 80 deg.C for 12 hr, washing with deionized water, vacuum filtering, and drying the solid in oven.
(4) Dispersing the product obtained in (3) in a solvent containing 200mL of 0.1mol/L K2S2O8Heating in water bath at 80 deg.C, stirring for 1 hr, washing with deionized water, and oven drying.
(5) And (3) placing the product in the step (4) in an alumina crucible, heating to 600 ℃ at the heating rate of 5 ℃/min in Ar atmosphere, preserving heat for 3h, cooling to room temperature, taking out the product, placing the product in a beaker filled with 1mol/L hydrochloric acid, stirring for 48h, then carrying out suction filtration, then placing the product in a diluted HF aqueous solution, and stirring for 24h to remove residual oxides. Then washing with deionized water, and drying in a 60 ℃ oven. Coating a film according to a certain proportion and sealing the battery.
In the preparation process of the material of the example, only one annealing is carried out, after the template is removed and dried, the battery is coated and sealed according to a certain proportion, the rate performance of the obtained product is shown in FIG. 9, FIG. 9 shows that if the annealing is carried out only one time, the obtained product has extremely low capacity under different current densities, and the capacity is more close to zero along with the increase of the current density.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a sodium ion battery negative electrode material sulfur-doped two-dimensional carbon material is characterized by comprising the following steps:
(1) carrying out heat treatment on hydrotalcite by taking the hydrotalcite as a template to remove hydroxyl and carbonate among hydrotalcite layers to obtain the heat-treated hydrotalcite; the hydrotalcite is hydrotalcite with a memory effect;
(2) cooling the hydrotalcites subjected to heat treatment, mixing the cooled hydrotalcites with the precursor solution, and fully stirring to enable the precursor to be inserted into the hydrotalcite layers in an anion form; filtering, washing filter residue with water, and drying to obtain hydrotalcite with precursor intercalation; the precursor solution is an unsaturated organic sulfonate solution, and the unsaturated organic sulfonate is sodium styrene sulfonate;
(3) under the action of an oxidant, the precursor intercalated hydrotalcite is subjected to oxidative polymerization reaction to obtain precursor polymer intercalated hydrotalcite;
(4) pre-carbonizing the hydrotalcite intercalated with the precursor polymer in an inert gas protective atmosphere to pre-carbonize the precursor polymer in an interlayer structure of the hydrotalcite, and then removing the hydrotalcite template by an acid washing method to obtain a pre-carbonized product; the pre-carbonization temperature is 600 DEG CoC~800oC；
(5) Carrying out secondary carbonization on the pre-carbonized product in the inert gas protective atmosphere to obtain a sulfur-doped two-dimensional carbon material; the second carbonization temperature is 600 DEG CoC-800 ℃, and the heat preservation time is 1-6 h.
2. The method according to claim 1, wherein the hydrotalcite of step (1) is a Mg-Al based hydrotalcite or a Zn-Al based hydrotalcite.
3. The method according to claim 1, wherein the heat treatment in step (1) is specifically: the heat treatment temperature was 400 deg.CoC~600oAnd C, preserving the heat for 1-4 hours.
4. The method according to claim 1, wherein the oxidizing agent in the step (3) is a potassium persulfate solution having a concentration of 0.1 to 0.5mol/L, and the oxidative polymerization reaction time is 0.5 to 4 hours.
5. The method according to claim 1, wherein the pre-carbonization in the step (4) is performed at a temperature increase rate of 1oC/min~10oC/min, and the heat preservation time is 1-6 h.
6. The production method according to claim 1, wherein the temperature increase rate of the second carbonization in the step (5) is 1oC/min~10oC/min。
7. The sulfur-doped two-dimensional carbon material for the negative electrode material of the sodium-ion battery is prepared according to the preparation method of any one of claims 1 to 6.
8. The sodium-ion battery negative electrode material sulfur-doped two-dimensional carbon material as claimed in claim 7, wherein the sulfur doping amount is 4.77 atom% to 6.90 atom%, and the specific surface area is 679m2g-1~930.6 m2g-1And has a hierarchical pore structure.
9. The use of the sulfur-doped two-dimensional carbon material as claimed in claim 7 or 8 for preparing a negative electrode material for sodium-ion batteries.
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