CN115504450A - Nitrogen-sulfur co-doped porous carbon and preparation method and application thereof - Google Patents
Nitrogen-sulfur co-doped porous carbon and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode materials, and particularly relates to nitrogen and sulfur co-doped porous carbon and a preparation method and application thereof. The invention provides a preparation method, which comprises the following steps: mixing asphalt, sodium chloride, a nitrogen-sulfur source and a polar organic solvent to obtain mixed slurry; drying the mixed slurry, and then sequentially carrying out first carbonization and second carbonization to obtain the nitrogen-sulfur co-doped porous carbon; the nitrogen sulfur source comprises one or more of thiourea, rhodamine and thiazole. The data of the embodiment show that when the nitrogen and sulfur co-doped porous carbon is used as the negative electrode material of the potassium ion battery, the nitrogen and sulfur co-doped porous carbon is 0.1 A.g ‑1 The reversible specific capacity under the current density can reach 240-300 mAh.g ‑1 And is andat 2 A.g ‑1 Can still retain 150-200 mAh.g under the heavy current density ‑1 The reversible specific capacity has excellent reversible capacity and rate capability.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to nitrogen and sulfur co-doped porous carbon and a preparation method and application thereof.
Background
The development demand of the new era promotes the development of new energy technology. Among them, the lithium ion battery, as the most mature energy storage product for commercialization, has high energy density and long cycle life, and thus is widely used in our daily life. However, limited lithium resources, increased manufacturing costs, and non-uniform distribution have become key to the containment of large-scale applications of lithium ion batteries. Therefore, development of battery technology with low cost and abundant reserves has attracted attention.
As an energy storage device with great prospect which can replace a lithium ion battery, a potassium ion battery is receiving more and more attention due to the advantages of abundant reserves, high energy density and the like. A common negative electrode material, graphite, has a value of 279mA g -1 But due to the larger ionic radius of potassium ions
The electrode material is easy to generate volume expansion, and the cycle performance is poor. Therefore, the design and development of a novel potassium ion battery anode material are very significant and necessary.
Currently, various types of potassium ion battery anode materials have been reported, such as carbon materials, alloy materials, metal oxides/sulfides, and organic materials, wherein carbon materials are considered as the most promising anode materials due to their low cost, abundant resources, and environmental friendliness. However, carbon-based materials can generate high voltage polarization during charging and discharging, and even potassium metal deposition occurs under high rate, resulting in poor electrochemical performance.
Disclosure of Invention
In view of the above, the invention aims to provide nitrogen and sulfur co-doped porous carbon and a preparation method and application thereof.
In order to solve the problems, the invention provides a preparation method of nitrogen and sulfur co-doped porous carbon, which comprises the following steps:
mixing asphalt, sodium chloride, a nitrogen-sulfur source and a polar organic solvent to obtain mixed slurry;
drying the mixed slurry, and then sequentially carrying out first carbonization and second carbonization to obtain the nitrogen-sulfur co-doped porous carbon;
the nitrogen sulfur source comprises one or more of thiourea, rhodamine and thiazole;
the temperature of the first carbonization is 250-450 ℃, and the heat preservation time is 1-3 h;
the temperature of the second carbonization is 600-1000 ℃, and the heat preservation time is 2-10 h.
Preferably, the bitumen comprises coal tar pitch and/or petroleum pitch.
Preferably, the mass ratio of the asphalt to the sodium chloride is 1:4-10.
Preferably, the evaporation is water bath evaporation, the temperature of the water bath evaporation is 60-100 ℃, and the heat preservation time is 3-12 h.
Preferably, the mixing is preferably a first mixing of the asphalt, sodium chloride and the polar organic solvent, and a second mixing of the obtained dispersion and the nitrogen sulfur source to obtain a mixed slurry.
The invention also provides the nitrogen-sulfur co-doped porous carbon prepared by the preparation method, wherein the aperture is 100-300 nm, the doping content of nitrogen is 3-10 at.%, and the doping content of sulfur is 2-8 at.%.
The invention also provides application of the nitrogen and sulfur co-doped porous carbon as a potassium ion battery negative electrode material.
The invention also provides a potassium ion battery cathode which comprises a copper sheet copper foil and a cathode material coated on the surface of the copper foil, wherein the cathode material comprises nitrogen and sulfur co-doped porous carbon, a conductive agent and a binder, and the nitrogen and sulfur co-doped porous carbon is the nitrogen and sulfur co-doped porous carbon.
Preferably, the conductive agent includes acetylene black, and the binder includes sodium carboxymethyl cellulose.
Preferably, the mass ratio of the nitrogen-sulfur co-doped porous carbon to the conductive agent to the binder is 70.
The invention provides a preparation method of nitrogen and sulfur co-doped porous carbon, which comprises the following steps: mixing asphalt, sodium chloride, a nitrogen-sulfur source and a polar organic solvent to obtain mixed slurry; drying the mixed slurry, and then sequentially carrying out first carbonization and second carbonization to obtain the nitrogen-sulfur co-doped porous carbon; the nitrogen and sulfur source comprises one or more of thiourea, rhodamine and thiazole; the temperature of the first carbonization is 250-450 ℃, and the heat preservation time is 1-3 h; the temperature of the second carbonization is 600-1000 ℃, and the heat preservation time is 2-10 h. According to the invention, nitrogen and sulfur atoms are introduced into the carbon frame, so that the carbon layer spacing is enlarged, and the structural defects and potassium storage active sites are increased, therefore, the nitrogen and sulfur co-doped porous carbon provided by the invention has higher reversible specific capacity when being used as a potassium ion battery cathode material.
In addition, due to a reasonable uniform mixing mode and proper reaction conditions, the nitrogen and sulfur co-doped porous carbon provided by the invention has a large doping amount of nitrogen and sulfur elements and is uniformly doped, and the nitrogen and sulfur co-doped porous carbon provided by the invention has a large and uniform doping amount of nitrogen and sulfur, so that a carbon matrix has rich defects, potassium storage active sites, large carbon layer intervals and a stable network structure, and is beneficial to rapid and stable transmission of potassium ions so as to improve the electrochemical performance. The data of the embodiment show that when the nitrogen and sulfur co-doped porous carbon is used as the negative electrode material of the potassium ion battery, the nitrogen and sulfur co-doped porous carbon is 0.1 A.g -1 Current densityThe reversible specific capacity under the temperature can reach 240-300 mAh.g -1 And is in the range of 2 A.g -1 Can still retain 150-200 mAh.g under the heavy current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
Drawings
FIG. 1 is an SEM test chart of nitrogen and sulfur co-doped porous carbon prepared in example 1;
FIG. 2 is an XRD test pattern of nitrogen and sulfur co-doped porous carbon prepared in example 1;
fig. 3 is a graph of rate performance of the nitrogen and sulfur co-doped porous carbon prepared in example 1 under different current densities.
Detailed Description
The invention provides a preparation method of a nitrogen and sulfur co-doped porous carbon material, which comprises the following steps:
mixing asphalt, sodium chloride, a nitrogen-sulfur source and a polar organic solvent to obtain mixed slurry;
drying the mixed slurry, and then sequentially carrying out first carbonization and second carbonization to obtain the nitrogen and sulfur co-doped porous carbon;
the temperature of the first carbonization is 250-450 ℃, and the heat preservation time is 1-3 h;
the temperature of the second carbonization is 600-1000 ℃, and the heat preservation time is 2-10 h.
In the invention, the nitrogen sulfur source comprises one or more of thiourea, rhodamine and thiazole, and preferably rhodanine. In the present invention, the pitch is preferably coal pitch and/or petroleum pitch, and is preferably coal pitch. In the invention, the softening point of the coal tar pitch is preferably 120 ℃, the coking value is preferably more than or equal to 45%, the moisture is preferably less than or equal to 3%, the ash content is preferably less than or equal to 0.4%, and the sulfur content is preferably less than or equal to 0.3% by mass. In the present invention, the polar organic solvent is preferably methanol.
In the present invention, the mass ratio of the asphalt to the sodium chloride is 1:4 to 10, more preferably 1:5 to 8. In the present invention, the mass ratio of the nitrogen sulfur source to the asphalt is preferably 1:1 to 3, more preferably 1:2. in the present invention, the ratio of the mass of the asphalt to the volume of the polar organic solvent is preferably 1g:5 to 15mL, more preferably 1g:10mL.
In the present invention, the mixing is preferably performed by first mixing the asphalt, the sodium chloride and the polar organic solvent, and second mixing the obtained dispersion and the nitrogen sulfur source to obtain a mixed slurry.
In the invention, the drying is preferably carried out by water bath evaporation, the temperature of the water bath evaporation is preferably 60-100 ℃, more preferably 80-90 ℃, and the time is preferably 3-12 h, more preferably 5-10 h.
In the present invention, the first carbonization and the second carbonization are preferably performed in a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon. In the present invention, the flow rate of the protective atmosphere in the first carbonization or the second carbonization is preferably 200 to 400sccm, and more preferably 250 to 350sccm. In the invention, the temperature of the first carbonization is 250-450 ℃, preferably 300 ℃, and the heat preservation time of the first carbonization is 1-3 h, more preferably 2h; in the present invention, the rate of temperature rise to the first carbonization temperature is preferably 2 to 10 ℃/min, and more preferably 3 ℃/min.
In the invention, the temperature of the second carbonization is 600-1000 ℃, preferably 800 ℃, and the heat preservation time of the second carbonization is preferably 2-10 h, more preferably 3h. In the present invention, the rate of temperature rise to the second carbonization temperature is preferably 2 to 10 ℃/min, and more preferably 5 ℃/min.
In the invention, the sectional carbonization is adopted to fully contact and mix with nitrogen and sulfur sources before the asphalt is pyrolyzed.
In the present invention, after the second carbonization reaction, it is preferable to further comprise washing, filtering and drying the product obtained by the second carbonization in sequence.
In the present invention, the washing reagent is preferably hydrochloric acid and distilled water, and the concentration of the hydrochloric acid is preferably 1mol/L.
The filtration is not particularly limited in the present invention, and the filtration may be performed by an operation known to those skilled in the art. In the present invention, the reagent for filtration is preferably water. In the present invention, the drying temperature is preferably 60 to 90 ℃, the drying time is not particularly limited in the present invention, and the product may be dried.
The invention also provides the nitrogen and sulfur co-doped porous carbon prepared by the preparation method. In the invention, the aperture of the nitrogen-sulfur co-doped porous carbon is 100-300 nm, preferably 150-250 nm.
In the invention, the doping content of nitrogen in the nitrogen and sulfur co-doped porous carbon is 3-10 at.%, preferably 5-8 at.%; the doping content of sulfur is 2-8 at.%, preferably 4-6 at.%.
The invention also provides application of the nitrogen and sulfur co-doped porous carbon in a potassium ion battery cathode.
The invention also provides a potassium ion battery cathode, which preferably comprises a copper sheet copper foil and a cathode material coated on the surface of the copper foil; the negative electrode material preferably comprises nitrogen and sulfur co-doped porous carbon, a conductive agent and a binder.
In the present invention, the conductive agent preferably includes acetylene black, and the binder preferably includes sodium carboxymethyl cellulose. In the present invention, the mass ratio of the nitrogen-sulfur co-doped porous carbon, the conductive agent and the binder is preferably 70.
In the present invention, the coating density is preferably 0.6 to 1.5mg/cm 2 More preferably 1 to 1.2mg/cm 2 。
In order to further illustrate the present invention, the following embodiments are provided to describe the technical solutions of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 1g of coal tar pitch, 10g of sodium chloride and 80mL of tetrahydrofuran, adding 1g of rhodanine after the coal tar pitch is uniformly dissolved, evaporating the obtained mixed solution in a water bath to dryness (the temperature is 80 ℃ and the time is 4 hours), and sequentially performing first carbonization and second carbonization on the evaporated product, wherein the protective atmosphere of the first carbonization is argon, the flow rate of the argon is 200sccm, the temperature of the first carbonization is 350 ℃, and the heat preservation time is 2 hours; and the second protective atmosphere is argon, the flow rate of the argon is 200sccm, the temperature of the second carbonization is 800 ℃, the heat preservation time is 2 hours, products obtained by the second carbonization are sequentially subjected to pickling with 1M hydrochloric acid, distilled water is filtered for multiple times, and the products are dried (at the temperature of 60 ℃) to obtain the nitrogen-sulfur co-doped porous carbon.
According to the invention, SEM test is carried out on the nitrogen and sulfur co-doped porous carbon prepared in the embodiment 1, the test result is shown in figure 1, and as can be seen from figure 1, the nitrogen and sulfur co-doped porous carbon has a mutually connected 3D porous structure, and the pore diameter structure is 100-300 nm.
According to the invention, XRD test is carried out on the nitrogen and sulfur co-doped porous carbon prepared in the example 1, the test result is shown in figure 2, and as can be seen from figure 2, the amorphous peak (002) of the nitrogen and sulfur co-doped porous carbon shifts from 25.4 degrees to 25.1 degrees leftwards, and the interlayer spacing becomes larger.
According to the invention, the nitrogen and sulfur co-doped porous carbon prepared in the embodiment 1, acetylene black and sodium carboxymethyl cellulose are uniformly ground according to the mass ratio of 70; and coating the slurry on the surface of the copper foil; vacuum drying at 80 deg.C for 12h, and cutting into negative plate with proper size; taking metal potassium as a reference electrode and a counter electrode, taking an electrode material as a working electrode, adopting glass fiber as a diaphragm and taking 0.8M KPF 6 The EC/DEC (volume ratio of 1:1) of (A) is taken as an electrolyte, a button cell is assembled in a glove box filled with argon, and then an electrochemical performance test is carried out on a Land cell test system.
Fig. 3 is a multiplying power performance diagram of the nitrogen and sulfur co-doped porous carbon prepared in example 1 under different current densities; as can be seen from FIG. 3, the amount of the nitrogen and sulfur co-doped porous carbon in the potassium ion battery using the negative electrode material is 0.1 A.g -1 The reversible specific capacity under the current density can reach 249 mAh.g -1 And at 2A · g -1 Can still retain 185 mAh.g under the high current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
Example 2
Mixing 1g of coal tar pitch, 8g of sodium chloride and 70mL of tetrahydrofuran, adding 1g of rhodanine after the coal tar pitch is uniformly dissolved, evaporating the obtained mixed solution in a water bath to dryness (the temperature is 80 ℃ and the time is 4 hours), and sequentially performing first carbonization and second carbonization on the evaporated product, wherein the protective atmosphere of the first carbonization is argon, the flow rate of the argon is 200sccm, the temperature of the first carbonization is 350 ℃, and the heat preservation time is 2 hours; and the second protective atmosphere is argon, the flow rate of the argon is 200sccm, the temperature of the second carbonization is 800 ℃, the heat preservation time is 2 hours, products obtained by the second carbonization are sequentially subjected to pickling with 1M hydrochloric acid, distilled water is filtered for multiple times, and the products are dried (the temperature is 70 ℃) to obtain the nitrogen-sulfur co-doped porous carbon.
And (3) electrochemical performance testing: the electrochemical performance test of example 1 was different only in that the nitrogen and sulfur co-doped porous carbon prepared in example 1 was replaced with the nitrogen and sulfur co-doped porous carbon prepared in example 2. The test results are as follows: at 0.1 A.g -1 The reversible specific capacity under the current density can reach 260 mA.h.g -1， And is in the range of 5 A.g -1 Can still retain 150 mA.h.g under the large current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
Example 3
Mixing 1g of coal tar pitch, 10g of sodium chloride and 80mL of toluene, adding 1g of rhodanine after the coal tar pitch is uniformly dissolved, evaporating the obtained mixed solution in a water bath to dryness (the temperature is 70 ℃ and the time is 5 hours), and sequentially performing first carbonization and second carbonization on the evaporated product, wherein the protective atmosphere of the first carbonization is argon, the flow rate of the argon is 200sccm, the temperature of the first carbonization is 400 ℃, and the heat preservation time is 1 hour; and the second protective atmosphere is argon, the flow rate of the argon is 200sccm, the temperature of the second carbonization is 800 ℃, the heat preservation time is 2 hours, products obtained by the second carbonization are sequentially subjected to pickling with 1M hydrochloric acid, distilled water is filtered for multiple times, and the products are dried (the temperature is 80 ℃) to obtain the nitrogen-sulfur co-doped porous carbon.
And (3) electrochemical performance testing: the electrochemical performance test of example 1 was different only in that the nitrogen and sulfur co-doped porous carbon prepared in example 1 was replaced with the nitrogen and sulfur co-doped porous carbon prepared in example 3. The test results are: at 0.1 A.g -1 The reversible specific capacity can reach 270 mA.h.g under the current density -1 And is in the range of 5 A.g -1 Can still retain 160 mA.h.g under the large current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
Example 4
Mixing 1g of coal tar pitch, 8g of sodium chloride and 70mL of toluene, adding 1g of rhodanine after the coal tar pitch is uniformly dissolved, evaporating the obtained mixed solution in a water bath to dryness (the temperature is 70 ℃ and the time is 5 hours), and sequentially performing first carbonization and second carbonization on the evaporated product, wherein the protective atmosphere of the first carbonization is argon, the flow rate of the argon is 200sccm, the temperature of the first carbonization is 400 ℃, and the heat preservation time is 1 hour; and the second protective atmosphere is argon, the flow rate of the argon is 200sccm, the temperature of the second carbonization is 900 ℃, the heat preservation time is 2 hours, products obtained by the second carbonization are sequentially subjected to 1M hydrochloric acid pickling, distilled water is filtered for multiple times, and the products are dried (the temperature is 90 ℃) to obtain the nitrogen-sulfur co-doped porous carbon.
And (3) electrochemical performance testing: the electrochemical performance test of example 1 was different only in that the nitrogen and sulfur co-doped porous carbon prepared in example 1 was replaced with the nitrogen and sulfur co-doped porous carbon prepared in example 4. The test results are: at 0.1A · g -1 The reversible specific capacity can reach 250 mA.h.g under the current density -1 And is in the range of 5 A.g -1 Can still retain 140 mA.h.g under the large current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
Example 5
Mixing 1g of coal tar pitch, 10g of sodium chloride and 80mL of dimethylbenzene, adding 0.5g of rhodanine after the coal tar pitch is uniformly dissolved, evaporating the obtained mixed solution in a water bath to dryness (the temperature is 60 ℃ and the time is 4 hours), and sequentially performing first carbonization and second carbonization on the evaporated product, wherein the protective atmosphere of the first carbonization is argon, the flow rate of the argon is 400sccm, the temperature of the first carbonization is 300 ℃, and the heat preservation time is 2 hours; and the second protective atmosphere is argon, the flow rate of the argon is 400sccm, the temperature of the second carbonization is 900 ℃, the heat preservation time is 2 hours, products obtained by the second carbonization are sequentially subjected to pickling by 1M hydrochloric acid, distilled water is filtered for multiple times, and the products are dried (the temperature is 70 ℃) to obtain the nitrogen-sulfur co-doped porous carbon.
And (3) electrochemical performance testing: the electrochemical performance test of example 1 was different only in that the nitrogen and sulfur co-doped porous carbon prepared in example 1 was replaced with the nitrogen and sulfur co-doped porous carbon prepared in example 5. The test results are: at 0.1 A.g -1 The reversible specific capacity under the current density can reach 265 mA.h.g -1 And is in the range of 5 A.g -1 Can still retain 160 mA.h.g under the large current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
Example 6
Mixing 1g of coal tar pitch, 6g of sodium chloride and 60mL of dimethylbenzene, adding 0.5g of rhodanine after the coal tar pitch is uniformly dissolved, evaporating the obtained mixed solution in a water bath to dryness (the temperature is 60 ℃ and the time is 4 hours), and sequentially performing first carbonization and second carbonization on the evaporated product, wherein the protective atmosphere of the first carbonization is argon, the flow rate of the argon is 200sccm, the temperature of the first carbonization is 300 ℃, and the heat preservation time is 1 hour; and the second protective atmosphere is argon, the flow rate of the argon is 200sccm, the temperature of the second carbonization is 900 ℃, the heat preservation time is 3h, products obtained by the second carbonization are sequentially subjected to 1M hydrochloric acid pickling, distilled water is filtered for multiple times, and the products are dried (the temperature is 80 ℃) to obtain the nitrogen-sulfur co-doped porous carbon.
And (3) electrochemical performance testing: the electrochemical performance test of example 1 was different only in that the nitrogen and sulfur co-doped porous carbon prepared in example 1 was replaced with the nitrogen and sulfur co-doped porous carbon prepared in example 6. The test results are as follows: at 0.1 A.g -1 The reversible specific capacity can reach 270 mA.h.g under the current density -1 And is in the range of 5 A.g -1 Can still retain 170 mA.h.g under the large current density -1 The reversible specific capacity has excellent reversible capacity and rate capability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (10)
1. The preparation method of the nitrogen and sulfur co-doped porous carbon material is characterized by comprising the following steps of:
mixing asphalt, sodium chloride, a nitrogen-sulfur source and a polar organic solvent to obtain mixed slurry;
drying the mixed slurry, and then sequentially carrying out first carbonization and second carbonization to obtain the nitrogen-sulfur co-doped porous carbon; the nitrogen and sulfur source comprises one or more of thiourea, rhodamine and thiazole;
the temperature of the first carbonization is 250-450 ℃, and the heat preservation time is 1-3 h;
the temperature of the second carbonization is 600-1000 ℃, and the heat preservation time is 2-10 h.
2. The method according to claim 1, wherein the asphalt comprises coal asphalt and/or petroleum asphalt.
3. The method according to claim 1, wherein the mass ratio of the asphalt to the sodium chloride is 1:4 to 10.
4. The preparation method according to claim 1, wherein the drying mode comprises water bath evaporation, the temperature of the water bath evaporation is 60-100 ℃, and the holding time is 3-12 h.
5. The production method according to claim 1, characterized in that the mixing is preferably a first mixing of the asphalt, sodium chloride and the polar organic solvent, and a second mixing of the resulting dispersion and the nitrogen sulfur source to obtain a mixed slurry.
6. The nitrogen and sulfur co-doped porous carbon prepared by the preparation method of any one of claims 1 to 6, wherein the pore diameter is 100 to 300nm, the doping content of nitrogen is 3 to 10at.%, and the doping content of sulfur is 2 to 8at.%.
7. The application of the nitrogen and sulfur co-doped porous carbon as the negative electrode material of the potassium ion battery in claim 6.
8. The potassium ion battery negative electrode comprises a copper sheet copper foil and a negative electrode material coated on the surface of the copper foil, and is characterized in that the negative electrode material comprises nitrogen and sulfur co-doped porous carbon, a conductive agent and a binder, and the nitrogen and sulfur co-doped porous carbon is the nitrogen and sulfur co-doped porous carbon in claim 6.
9. The potassium-ion battery anode of claim 8, wherein the conductive agent comprises acetylene black and the binder comprises sodium carboxymethyl cellulose.
10. The potassium ion battery negative electrode as claimed in claim 8, wherein the mass ratio of the nitrogen-sulfur co-doped porous carbon to the conductive agent to the binder is 70.
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