CN115724426A - Preparation method of in-situ nitrogen-doped coal-based porous carbon lithium-sulfur battery positive electrode material - Google Patents
Preparation method of in-situ nitrogen-doped coal-based porous carbon lithium-sulfur battery positive electrode material Download PDFInfo
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- 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
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Abstract
The invention discloses a preparation method of an in-situ nitrogen-doped coal-based porous carbon lithium-sulfur battery positive electrode material, which comprises the following steps: (1) Coal powder is used as an activation raw material, coal powder and an alkali activator are uniformly mixed, and high-temperature activation is carried out to prepare coal-based activated carbon; (2) Performing alkali washing, acid washing and deashing on the coal-based activated carbon obtained in the step (1), and drying to obtain purified coal-based activated carbon; (3) Uniformly dispersing a nitrogen-containing precursor into a solvent, then adding the coal-based activated carbon obtained in the step (2), uniformly stirring, fully stirring and drying; (4) And (4) putting the dried product obtained in the step (3) into a porcelain boat, putting the porcelain boat into a tubular furnace, heating and carbonizing the porcelain boat under the protection of nitrogen atmosphere, cooling the porcelain boat along with the furnace, and sieving the porcelain boat with a 300-mesh sieve to obtain a compound of graphite-phase carbon nitride and coal-based activated carbon, namely the lithium-sulfur battery anode sulfur-carrying material. The invention can greatly improve the problems of low battery capacity and poor cycle performance after the coal-based porous carbon is directly loaded with sulfur.
Description
Technical Field
The invention relates to the field of lithium-sulfur batteries, in particular to a preparation method of an in-situ nitrogen-doped coal-based porous carbon lithium-sulfur battery cathode material.
Background
With the development of social science and technology, the demand of human beings on efficient electrochemical energy storage devices is continuously increased. Lithium sulfur batteries are of great interest because of their ultra-high theoretical specific capacity of 1675mAh/g, however, shuttling effects caused by dissolution of polysulfides in lithium sulfur batteries result in lower coulombic efficiencies. To address these issues, framework materials that can be loaded with sulfur are often added. At present, sulfur-carrying materials are widely applied to various conductive carbon materials, such as carbon nanofibers, carbon nanotubes, lamellar graphene, three-dimensional porous carbon and the like. However, the preparation cost of the materials is high, and the coal-based carbon prepared by activating coal has the advantages of developed pore structure, rich active sites and the like, can store a large amount of sulfur, but has low cycle efficiency.
Chinese patent document 202210327307.7 provides a lithium-sulfur battery positive electrode material and a preparation method thereof, the lithium-sulfur battery uses two nitrogen-containing compounds as precursors, and a conductive carbon material as a coating material, and the lithium-sulfur battery positive electrode material is obtained by mixing, coating, drying and calcining; the scheme has the following disadvantages: the nitrogen-doped raw material requires that two graphite-like phase carbon nitride materials which can realize different heterojunctions can be used, so that the effect of inhibiting lithium polysulfide shuttling is realized, and in the provided optimal embodiment, the maximum specific capacitance of the obtained lithium-sulfur battery electrode is only 790mAh/g, and the capacity is reduced to 410mAh/g after 150 cycles.
Chinese patent document 201910556440.8 provides a nitrogen-doped graphene-like activated carbon material and a preparation method and application thereof, wherein melamine and L-cysteine are used as raw materials, mixed and ball-milled according to different proportions, and carbonized under the protection of inert gas to obtain the nitrogen-doped graphene-like activated carbon material; the scheme has the following disadvantages: the raw materials are melamine and L cysteine containing nitrogen, the carbon content is low, the nitrogen-doped graphene activated carbon material prepared after carbonization has low carbon content, and in order to ensure the carbon content, the carbonization temperature can be increased, so that the yield is further reduced. Meanwhile, melamine and L-cysteine are relatively high in price, which greatly increases the cost of the electrode material of the lithium-sulfur battery.
Chinese patent document 201910130099.x provides a preparation method of a anthracite-based lithium-sulfur battery positive electrode material, which comprises the steps of subjecting anthracite to pyrolysis at 1000-1400 ℃ to obtain carbonized anthracite, grinding a proper amount of the carbonized anthracite and sulfur, uniformly mixing, and placing the mixture in a hydrothermal reaction kettle to carry sulfur to obtain a anthracite/sulfur composite material as a lithium-sulfur battery positive electrode; the scheme has the following disadvantages: the carbonized coal is used as a raw material and is not subjected to deashing treatment, so that the ash content in the material is high, the capacitance is extremely low, and the capacitance is only less than 200mAh/g after 2 cycles of circulation.
Disclosure of Invention
The invention aims to provide a preparation method of an in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery anode material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of an in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery positive electrode material comprises the following steps:
(1) Coal powder is taken as an activation raw material, coal powder and an alkali activator are uniformly mixed, and the coal-based activated carbon is prepared by high-temperature activation;
(2) Performing alkaline washing, acid washing and ash removal on the coal-based activated carbon obtained in the step (1), and drying to obtain purified coal-based activated carbon;
(3) Uniformly dispersing a nitrogen-containing precursor into a solvent, then adding a proper amount of the coal-based activated carbon obtained in the step (2), uniformly stirring, fully stirring and drying;
(4) And (4) putting the dried product obtained in the step (3) into a porcelain boat, putting into a tubular furnace, heating and carbonizing under the protection of nitrogen atmosphere, cooling along with the furnace, and sieving by a 300-mesh sieve to obtain a compound of graphite-phase carbon nitride and coal-based activated carbon, namely the lithium-sulfur battery anode sulfur-carrying material.
Optionally, raw materials of the coal powder in the step (1) include, but are not limited to, long flame coal, coking coal, 1/3 coking coal and the like; the alkali activating agent comprises potassium hydroxide, sodium hydroxide and a mixture thereof, wherein the mass ratio of alkali to carbon is 1; the activation temperature is 700-1200 ℃;
preferably, the long flame coal is used as a carbon source, the potassium hydroxide is used as an activating agent, the mass ratio of alkali to carbon is 1.
Optionally, the coal-based activated carbon in the step (2) is subjected to alkaline washing, acid washing purification and deashing, and alkaline washing liquid comprises but is not limited to aqueous solution of potassium hydroxide, sodium hydroxide, a mixture thereof and the like; the acid washing solution includes but is not limited to aqueous solution of hydrofluoric acid, hydrochloric acid, ammonium fluoride and their mixture, etc., to make the coal-based activated carbon purity reach above 95%, and the grain size D50 is 2-5 μm.
Preferably, the alkaline solution is 1 mol/L potassium hydroxide solution, and the pH value of the alkaline solution is 14.
Optionally, the dispersing solvent in step (3) includes water, ethanol, acetone, etc. Preferably, a mixed solution of water and ethanol in a mass ratio of 1.
Optionally, the nitrogen-containing precursor in step (3) includes, but is not limited to, melamine, dicyandiamide, urea, thiourea, and the like.
Preferably, the nitrogen-containing precursor in step (3) is dicyandiamide.
Optionally, the carbonization temperature in the step (4) is 600-900 ℃, the activation time is 2-4h, the heating rate is 2-5 ℃/min, and the specific temperature is adjusted according to the nitrogen content of the precursor.
The electrical property test method of the lithium-sulfur battery anode sulfur-carrying material comprises the following steps: and (2) taking sublimed sulfur as a sulfur source, and loading sulfur into the lithium-sulfur battery anode sulfur-loaded material by a secondary sulfur melting method according to the mass ratio of 1:1 of sulfur to the lithium-sulfur battery anode sulfur-loaded material to obtain the lithium-sulfur battery anode material. The in-situ nitrogen-doped coal-based porous carbon after sulfur loading is taken as the anode of the lithium-sulfur battery, elemental lithium is taken as the cathode, a CR2025 button cell is formed in a glove box, and the electrical properties of the button cell are measured under different current densities.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention can greatly improve the problems of low battery capacity and poor cycle performance after the coal-based porous carbon is directly loaded with sulfur;
(2) The raw material of the invention is coal which is easy to obtain, the additional value of the coal can be effectively increased, meanwhile, the raw material is coal-based porous carbon after deashing treatment, the coal-based porous carbon has a developed pore structure, when the coal-based porous carbon is mixed with a nitrogen-containing precursor solution, the nitrogen-containing precursor can be adsorbed, and the carbon-containing precursor is heated and converted into graphite-phase carbon nitride in the carbonization process, thereby being beneficial to the anchoring effect on lithium polysulfide in a lithium sulfur battery.
(3) In the carbonization process, pores of the coal-based porous carbon can collapse to a certain degree, so that the pores are reduced, and sulfur loading is facilitated; in the carbonization process, the nitrogen-containing precursor is decomposed, the higher the carbonization temperature is, the lower the nitrogen content of the final product is, and the nitrogen content and the pore size in the prepared anode sulfur-carrying material can be controlled by adjusting the carbonization temperature
(4) The nitrogen precursor is easy to obtain, the preparation process is simple, the carbonized product is carbon dioxide and ammonia gas, the ammonium carbonate can be prepared after mixing treatment, the environmental pollution is small, and the byproducts also have certain additional values.
Drawings
Fig. 1 is an SEM image of a sulfur-bearing material of a positive electrode of a lithium sulfur battery prepared in example 1;
fig. 2 is an SEM image of the sulfur-carrying material of the positive electrode of the lithium sulfur battery prepared in example 2;
fig. 3 is an SEM image of the sulfur-carrying material of the positive electrode of the lithium sulfur battery prepared in comparative example 1;
fig. 4 is an SEM image of the sulfur-carrying material of the positive electrode of the lithium sulfur battery prepared in comparative example 2;
FIG. 5 is a graph of specific capacities of examples and comparative examples.
Detailed Description
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given with reference to the preferred embodiments.
Example 1:
a preparation method of an in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery positive electrode material comprises the following steps:
(1) Mixing long flame coal powder serving as an activation raw material with KOH according to a mass ratio of 1;
(2) Performing potassium hydroxide alkaline washing on the coal-based activated carbon obtained in the step (1), performing hydrochloric acid washing to remove ash, and drying to obtain purified coal-based activated carbon;
(3) Uniformly dispersing thiourea in deionized water, then adding the coal-based activated carbon obtained in the step (2), uniformly stirring the thiourea and the coal-based activated carbon according to a mass ratio of 1;
(4) And (4) putting the dried product obtained in the step (3) into a porcelain boat, and then putting into a tube furnace, and heating and carbonizing at 550 ℃ under the protection of nitrogen atmosphere. And (3) cooling along with the furnace, and then sieving with a 300-mesh sieve to obtain a compound of graphite-phase carbon nitride and coal-based activated carbon, so as to obtain the sulfur-carrying material of the positive electrode of the lithium-sulfur battery, wherein the shape of the material is shown in figure 1.
The electrical properties of the resulting lithium sulfur battery tested at 0.2C are shown in fig. 5, with a first capacity of 775.40mAh/g and 70.3% after 100 cycles.
Example 2:
a preparation method of an in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery positive electrode material comprises the following steps:
(1) The method comprises the following steps of (1) mixing KOH and NaOH according to a mass ratio of 1;
(2) Performing potassium hydroxide alkaline washing on the coal-based activated carbon obtained in the step (1), performing hydrochloric acid washing, deashing and drying to obtain purified coal-based activated carbon;
(3) Uniformly dispersing urea in deionized water, then adding the coal-based activated carbon obtained in the step (2), uniformly stirring the urea and the coal-based activated carbon according to a mass ratio of 1;
(3) And (4) putting the dried product obtained in the step (3) into a porcelain boat, and then putting into a tube furnace, and heating and carbonizing at 550 ℃ under the protection of nitrogen atmosphere. And (3) cooling along with the furnace, and then sieving with a 300-mesh sieve to obtain a compound of graphite-phase carbon nitride and coal-based activated carbon, so as to obtain the sulfur-carrying material for the positive electrode of the lithium-sulfur battery, wherein the shape of the material is shown in figure 2.
The resulting lithium sulfur cell tested electrical properties at 0.2C as shown in fig. 5, with a first capacity of 842.95mAh/g, 63.8% after 100 cycles.
Comparative example 1:
(1) Taking lean coal as a raw material, mixing potassium hydroxide and sodium hydroxide in a mass ratio of 1;
(2) Putting the mixture obtained in the step (1) into a porcelain boat, then putting the porcelain boat into a tube furnace, and heating and activating the porcelain boat at 1000 ℃ under the protection of nitrogen atmosphere to obtain coal-based activated carbon;
(3) And (3) performing potassium hydroxide alkaline washing on the coal-based activated carbon prepared in the step (2), washing with hydrochloric acid to remove ash, drying to obtain purified coal-based activated carbon, and sieving with a 300-mesh sieve to obtain the lithium-sulfur battery anode sulfur-carrying material, wherein the material morphology is shown in figure 3.
The electrical properties of the resulting lithium sulfur cell tested at 0.2C are shown in fig. 5, with a first capacity of 549.83mAh/g, 63.2% after 100 cycles.
Comparative example 2:
and (3) putting thiourea into a porcelain boat, putting the porcelain boat into a tubular furnace, heating and carbonizing at 550 ℃ under the protection of nitrogen atmosphere, cooling along with the furnace, and sieving by using a 300-mesh sieve to obtain graphite-phase carbon nitride, namely the sulfur-carrying material for the positive electrode of the lithium-sulfur battery, wherein the appearance of the material is shown in figure 4.
Compositional lithium sulfur batteries tested electrical performance at 0.2C as shown in figure 5, with a first capacity of 499.13mAh/g, 78.2% after 100 cycles.
FIG. 5 is a battery cycle performance curve of the sulfur-carrying material at 0.2C for the positive electrode of the lithium-sulfur battery prepared in the example and the comparative example, and it can be seen that the specific capacity of the example is higher than that of the comparative example, wherein the battery assembled in the example 2 has the primary capacity of 842.95mAh/g at the most, and the material has good cycle stability after carrying sulfur.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. The preparation method of the in-situ nitrogen-doped coal-based porous carbon lithium-sulfur battery positive electrode material is characterized by comprising the following steps of:
(1) Coal powder is used as an activation raw material, coal powder and an alkali activator are uniformly mixed, and high-temperature activation is carried out to prepare coal-based activated carbon;
(2) Performing alkali washing, acid washing and deashing on the coal-based activated carbon obtained in the step (1), and drying to obtain purified coal-based activated carbon;
(3) Uniformly dispersing a nitrogen-containing precursor into a solvent, then adding the coal-based activated carbon obtained in the step (2), uniformly stirring, fully stirring and drying;
(4) And (4) putting the dried product obtained in the step (3) into a porcelain boat, putting the porcelain boat into a tubular furnace, heating and carbonizing the porcelain boat under the protection of nitrogen atmosphere, cooling the porcelain boat along with the furnace, and sieving the porcelain boat with a 300-mesh sieve to obtain a compound of graphite-phase carbon nitride and coal-based activated carbon, namely the lithium-sulfur battery anode sulfur-carrying material.
2. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 1, wherein the raw materials of the coal powder in the step (1) include but are not limited to long flame coal, coking coal, 1/3 coking coal; the alkali activating agent comprises potassium hydroxide, sodium hydroxide and a mixture thereof, wherein the mass ratio of alkali to carbon is 1; the activation temperature is 700-1200 ℃.
3. The preparation method of the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material according to claim 2, wherein the coal powder in the step (1) is prepared from long flame coal, the alkali activator is potassium hydroxide, the mass ratio of alkali to carbon is 1.
4. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 1, wherein the coal-based activated carbon in the step (2) is subjected to alkali washing, acid washing, purification and deliming, and alkali washing liquid comprises but is not limited to aqueous solution of potassium hydroxide, sodium hydroxide and mixture thereof; acid wash solutions include, but are not limited to, aqueous solutions of hydrofluoric acid, hydrochloric acid, ammonium fluoride, and mixtures thereof.
5. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 4, wherein the pH value of the alkaline solution is 14.
6. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 1, wherein the dispersion solvent in the step (3) comprises water, ethanol and acetone.
7. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material according to claim 6, wherein the dispersion solvent in the step (3) is a mixed solution of water and ethanol in a mass ratio of 1.
8. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 1, wherein the nitrogen-containing precursor in step (3) includes, but is not limited to, melamine, dicyandiamide, urea, thiourea.
9. The method for preparing the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 8, wherein the nitrogen-containing precursor in the step (3) is dicyandiamide.
10. The preparation method of the in-situ nitrogen-doped coal-based porous carbon lithium sulfur battery cathode material as claimed in claim 1, wherein the carbonization temperature in the step (4) is 600-900 ℃, the activation time is 2-4h, and the heating rate is 2-5 ℃/min.
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| CN116282014A (en) * | 2023-03-13 | 2023-06-23 | 中国矿业大学 | Preparation method and application of coal-based porous carbon material |
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