CN111573742B - Ferrous disulfide taking MOF as precursor and preparation method thereof - Google Patents
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Abstract
The invention belongs to the field of material preparation, and particularly relates to ferrous disulfide taking MOF as a precursor and a preparation method thereof. The structure of the ferrous disulfide is MOF type, and a carbon coating layer is arranged on the surface of the material; the preparation method comprises the following specific steps: step (1): dissolving iron salt, a carbon source, a precipitator, a dispersing agent and the like into a solvent, and preserving the solution in an oven for a certain time to obtain a Fe-based precursor; step (2): dissolving the Fe-based precursor obtained in the step (1) and carboxylic acid in a solvent according to a ratio, and preserving heat in an oven to obtain a Fe-MOF precursor; and (3): and (3) calcining the Fe-MOF precursor and the sulfur powder obtained in the step (2) in an inert atmosphere according to a ratio to obtain the MOF ferrous disulfide with carbon-coated surface. The method of the invention can regulate and control the particle size and the pore structure of the precursor. The FeS2 prepared by the method is applied to the cathode material of the sodium-ion battery, so that the cycle life of the battery is effectively prolonged, and the battery has good electrochemical performance.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to ferrous disulfide taking MOF as a precursor and a preparation method thereof.
Background
Metal organic framework Materials (MOFs) generally refer to highly structured crystalline materials that are built up as a framework from organic groups, inorganic metal nodes or metal cluster secondary building units are used as connection points, and are coordinated and self-assembled under hydrothermal or solvothermal conditions. Other types of interactions, such as hydrogen bonding and van der waals forces, may also play a role in forming the three-dimensional structures of MOFs. Currently, many 20000 MOFs materials have been discovered by scientists. Because its structure is similar to that of zeolites, and the framework is relatively soft, it is also known as "soft zeolites".
The MOF material has an ultra-large specific surface area, is rich in pore channels and exposed active sites inside, is beneficial to charge accumulation, electrolyte infiltration and rapid ion movement, and can effectively improve the electrochemical performance of the material through the design of the MOF structure, so that the MOF material becomes a large direction for the application of the MOF material when being used in the electrochemical field. Since the Yaghi task group first defined the metal organic framework material in 1995, MOF materials have been rapidly developed and widely used in many fields such as lithium sulfur batteries, lithium ion batteries, adsorption, catalysis, and sensing, etc., for example, as a positive electrode material of lithium sulfur batteries, a positive electrode of lithium ion batteries, a negative electrode material, and an electrocatalyst for hydrogen evolution reaction and oxygen evolution reaction, etc. The applications of MOF materials and their derivatives to electrochemistry have been increasingly reported in recent years. The preparation approaches of the MOF material are many, and currently, hydrothermal/solvothermal synthesis, microwave synthesis, electrochemical synthesis, ultrasonic synthesis and the like are common.
Ferrous disulfide has an ultra-high theoretical specific capacity, but the poor conductivity of the material itself limits its development for electrode materials.
Disclosure of Invention
The invention aims to provide ferrous disulfide taking MOF as a precursor and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows: the ferrous disulfide takes MOF as a precursor, the structure of the ferrous disulfide is MOF type, and a carbon coating layer is arranged on the surface of the material.
A method for preparing the ferrous disulfide comprises the steps of preparing a Fe-MOF precursor and sintering and vulcanizing at high temperature; and adding a carbon source in the preparation of the MOF precursor, and separating out carbon in the carbon source in the subsequent high-temperature sintering and vulcanizing step to obtain the ferrous disulfide coated with carbon on the surface.
The method comprises the following specific steps:
step (1): dissolving iron salt, a carbon source, a precipitator, a dispersing agent and the like into a solvent, and preserving the solution in an oven for a certain time to obtain a Fe-based precursor;
step (2): dissolving the Fe-based precursor obtained in the step (1) and carboxylic acid in a solvent according to a ratio, and preserving heat in an oven to obtain a Fe-MOF precursor;
and (3): and (3) calcining the Fe-MOF precursor and the sulfur powder obtained in the step (2) in an inert atmosphere according to a ratio to obtain the MOF ferrous disulfide with carbon-coated surface.
Further, the step (1) is specifically as follows: dissolving Fe, a carbon source and a precipitating agent in ferric salt in deionized water according to a molar ratio of 1: 1.5-2: 1.6-2, uniformly stirring, then adding a dispersing agent into the uniformly stirred solution, uniformly stirring and mixing, transferring the solution to a reaction kettle, preserving heat for 8-12h at 160-180 ℃ to obtain a black suspension, then centrifugally washing the obtained black suspension with deionized water and ethanol to obtain black powder, and drying for 8-12h at 60 ℃ in a vacuum oven to obtain an Fe-based precursor.
Further, the ferric salt is one of ferric chloride hexahydrate and ferric nitrate nonahydrate.
Further, the carbon source is sodium citrate, the precipitator is urea, and the dispersant is PVP.
Further, the step (2) is specifically as follows: dissolving the Fe-based precursor and carboxylic acid obtained in the step (1) into DMF (dimethyl formamide) according to the mol ratio of Fe to carboxylic acid in iron salt of 2:1, transferring the prepared solution into a reaction kettle, preserving the heat for 16-20 h at 110-120 ℃, fully cleaning with deionized water and absolute ethyl alcohol, and drying in a vacuum oven at 150 ℃ for 8h to obtain orange MIL-101-Fe, namely the Fe-MOF precursor.
Further, the molar weight ratio of the dispersant PVP (K60) to the iron in the iron salt is 1: 0.000005.
further, the carboxylic acid is terephthalic acid.
Further, the step (3) is specifically as follows: mixing a Fe-MOF precursor and sulfur powder according to a mass ratio of 1: 3-5, putting the mixture into a tubular furnace, placing the uniformly mixed sample into a 500-doped container for heat preservation reaction at a temperature of 600 ℃ for 8-12h under the protection of argon at a heating rate of 3-5 ℃/min, and cooling to room temperature after the reaction is finished to obtain the Fe-MOF precursorTo FeS coated with carbon on the surface2@C。
Compared with the prior art, the invention has the remarkable advantages that:
(1) according to the invention, through a simple-process low-cost water/solvothermal method, an iron-based MOF precursor is obtained firstly, and then sintering and vulcanizing at high temperature are carried out to obtain the FeS with the carbon-coated surface2(ii) a The ion transmission distance can be shortened by taking the MOF as a template, and the problem that the original short plate with lower conductivity can be solved after the surface is coated with carbon is solved, so that the prepared ferrous disulfide is very suitable for being used as a negative electrode material of a sodium ion battery; can effectively prolong the cycle life of the battery, has good electrochemical performance, and is expected to be applied to the fields of electrochemical catalysis, energy conversion, energy storage and the like.
(2) FeS prepared by the water/solvothermal and solid-phase reaction method2By adjusting the types and the quantity of the raw materials and the sintering temperature, the particle size of the material can be effectively regulated, and the sulfur content, the pore structure and the electrical conductivity can be regulated.
Drawings
FIG. 1 shows FeS in example 12Scanning Electron microscopy of @ C.
FIG. 2 shows FeS in example 12@ C and standard FeS2X-ray diffraction contrast chart of (1).
FIG. 3 shows FeS in example 22Scanning Electron microscopy of @ C.
FIG. 4 shows FeS in example 32Scanning Electron microscopy of @ C.
FIG. 5 shows FeS in example 42Scanning Electron microscopy of @ C.
FIG. 6 shows FeS in example 52Scanning Electron microscopy of @ C.
FIG. 7 shows FeS in example 62Scanning Electron microscopy of @ C.
FIG. 8 shows FeS in example 12@ C is used as the specific capacity-cycle diagram of the negative electrode material of the sodium ion half-cell.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The invention aims to provide a preparation method of ferrous disulfide taking MOF as a template, which adopts low-cost raw materials, obtains an iron-based MOF precursor through a hydrothermal method, and obtains ferrous disulfide with uniform and controllable size after high-temperature heat treatment and vulcanization.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of ferrous disulfide taking MOF as a template comprises the following specific steps:
step 1: dissolving ferric salt, a carbon source and a precipitator into deionized water according to the molar ratio of Fe to the carbon source to the precipitator of 1: 1.5-2: 1.6-2, uniformly stirring, then adding a certain molar amount of a dispersing agent into the uniformly stirred solution, uniformly stirring and mixing, transferring the solution to a reaction kettle, and preserving heat at 160-180 ℃ for 12 hours. And then, centrifugally washing the obtained black suspension by using deionized water and ethanol to obtain black powder, and drying the black powder in a vacuum oven at 60 ℃ for 8-12h to obtain the iron-based precursor.
Step 2: and (2) dissolving the iron-based precursor and carboxylic acid obtained in the step (1) in DMF (dimethyl formamide) according to the molar ratio of iron to carboxylic acid of 2:1, transferring the prepared solution to a reaction kettle, preserving the temperature for 16-20 h at 110-120 ℃, fully cleaning with deionized water and absolute ethyl alcohol, and drying in a vacuum oven at 150 ℃ for 8h to obtain orange MIL-101-Fe.
And step 3: mixing the precursor and sulfur powder according to a mass ratio of 1: 3-5, putting the mixture into a tube furnace, placing the uniformly mixed sample at 500-600 ℃ for heat preservation reaction for 8-12h under the protection of argon at a heating rate of 3-5 ℃/min, and cooling to room temperature after the reaction is finished to obtain FeS with the surface coated with carbon2@C。
The ferric salt is selected from ferric chloride hexahydrate and ferric nitrate nonahydrate, the carbon source is sodium citrate, the precipitator is urea, and the dispersing agent is PVP.
The molar weight ratio of the dispersant PVP (K60) to the iron salt is 1: 0.000005.
the carboxylic acid is terephthalic acid.
Example 1
Step 1: dissolving 0.0082mol of ferric trichloride hexahydrate, 0.0131mol of urea and 0.0123mol of sodium citrate in 100mL of deionized water, placing the mixture on a magnetic stirrer, stirring for 30min until the mixture is fully dissolved, adding 0.6g of PVP, stirring for 1h, transferring the solution into a reaction kettle after the mixture is fully dissolved, and preserving the heat for 12h in an oven at 180 ℃. And then, centrifugally washing the obtained black suspension by using deionized water and ethanol to obtain black powder, and drying the black powder in a vacuum oven at 60 ℃ for 12 hours to obtain the iron-based precursor.
Step 2: dissolving 0.004mol of iron-based precursor and 0.002mol of terephthalic acid in 120mL of N, N-Dimethylformamide (DMF), stirring until the iron-based precursor and the terephthalic acid are uniformly dissolved, transferring the mixture into a reaction kettle, taking out the material, fully cleaning the material with deionized water and absolute ethyl alcohol, and drying the material in a vacuum oven at 150 ℃ for 8 hours to obtain orange MIL-101-Fe.
And step 3: weighing the obtained precursor and sulfur powder according to the mass ratio of 1:3, uniformly mixing, putting into a tubular furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 8 h. Naturally cooling after the heat preservation is finished to obtain the FeS with the carbon-coated surface2@C。
The scanning electron microscope characterization is shown in FIG. 1, and the diameter of the particle is about 160-180 nm. FeS2@ C and pure FeS2The XRD spectrum pair of (A) is as shown in figure 2. FeS2The capacity cycle of the material used as the positive electrode material of the sodium-ion half-cell is shown in figure 6, the specific capacity can reach 1000mAh/g under the current density of 50mA/mg, after the material is cycled for 40 circles under different current densities, the specific capacity can still reach 600mAh/g by using the current density of 50mA/mg again, and good electrochemical cycling stability is reflected.
Example 2
Similar to example 1, except that the sulfidation temperature in step 3 was changed to 500 ℃, the scanning electron microscopy characterization is as shown in fig. 3, and the diameter of the particles is about 5 μm.
Example 3
Similar to example 1, except that the sulfidation temperature in step 3 was changed to 550 ℃, the scanning electron microscopy characterization is shown in fig. 4, and the particles had a diameter of about 5-6 μm.
Example 4
Similar to example 1, except that in step 1, the molar amount of ferric trichloride hexahydrate was changed to 0.0068mol, urea was changed to 0.0108mol, sodium citrate was changed to 0.0102mol, deionized water was changed to 120ml, and PVP was changed to 0.9 g. And 3, changing the mass ratio of the precursor to the sulfur powder in the step 3 into 1: 5. The scanning electron microscope is characterized in that as shown in figure 5, the particle diameter is about 5-6 μm, and the particle contains more impurities.
Example 5
Similar to example 1, except that the ferric trichloride hexahydrate in step 1 was changed to ferric nitrate nonahydrate. The scanning electron micrograph is shown in FIG. 6. It can be seen that the particles have uneven appearance and more impurities, so ferric chloride hexahydrate is more suitable for the ferric salt.
Example 6
Similar to example 1, except that the molar ratio of ferric trichloride hexahydrate, sodium citrate and urea in step 1 was changed to 1:2: 2. The scanning electron micrograph is shown in FIG. 7, which shows that the particles have large size, serious agglomeration and uneven morphology.
By the above examples: the product obtained by adopting the molar ratio of ferric trichloride hexahydrate, sodium citrate and urea of 1:1.5:1.6 has more uniform appearance, the mass ratio of the precursor to the sulfur powder is 1:3, the particle diameter can reach the nanometer level when the vulcanization temperature is 600 ℃, and the electrochemical performance is optimal.
Claims (6)
1. A method for preparing ferrous disulfide taking MOF as precursor is characterized in that the structure of the ferrous disulfide is MOF type, and a carbon coating layer is arranged on the surface of the material, and the method comprises the steps of preparing Fe-MOF precursor and sintering and vulcanizing at high temperature; adding a carbon source in the preparation of the MOF precursor, and separating out carbon in the carbon source in the subsequent high-temperature sintering and vulcanizing step to obtain ferrous disulfide coated with carbon on the surface;
the method comprises the following specific steps:
step (1): dissolving ferric salt, a carbon source, a precipitator and a dispersing agent in a solvent, and preserving the solution in an oven for a certain time to obtain a Fe-based precursor; dissolving Fe, a carbon source and a precipitating agent in ferric salt in deionized water according to a molar ratio of 1: 1.5-2: 1.6-2, uniformly stirring, then adding a dispersing agent into the uniformly stirred solution, uniformly stirring and mixing, transferring the solution to a reaction kettle, preserving heat for 8-12h at 160-180 ℃ to obtain a black suspension, then centrifugally washing the obtained black suspension with deionized water and ethanol to obtain black powder, and drying for 8-12h at 60 ℃ in a vacuum oven to obtain an Fe-based precursor; the carbon source is sodium citrate, the precipitator is urea, and the dispersant is PVP;
step (2): dissolving the Fe-based precursor obtained in the step (1) and carboxylic acid in a solvent according to a ratio, and preserving heat in an oven to obtain a Fe-MOF precursor;
and (3): and (3) calcining the Fe-MOF precursor and the sulfur powder obtained in the step (2) in an inert atmosphere according to a ratio to obtain the MOF ferrous disulfide with carbon-coated surface.
2. The method of claim 1, wherein the iron salt is one of ferric chloride hexahydrate and ferric nitrate nonahydrate.
3. The method according to claim 2, characterized in that the step (2) is in particular: dissolving the Fe-based precursor and carboxylic acid obtained in the step (1) into DMF (dimethyl formamide) according to the mol ratio of Fe to carboxylic acid in iron salt of 2:1, transferring the prepared solution into a reaction kettle, preserving the heat for 16-20 h at 110-120 ℃, fully cleaning with deionized water and absolute ethyl alcohol, and drying in a vacuum oven at 150 ℃ for 8h to obtain orange MIL-101-Fe, namely the Fe-MOF precursor.
4. The method according to claim 3, wherein the molar weight ratio of the dispersant PVP-K60 to iron in the iron salt is 1: 0.000005.
5. the process of claim 4, wherein the carboxylic acid is terephthalic acid.
6. The method according to claim 5, characterized in that the step (3) is in particular: mixing a Fe-MOF precursor and sulfur powder according to a mass ratio of 1: 3-5, putting the mixture into a tubular furnace, and heating at a high speed under the protection of argonThe rate is 3-5 ℃ per min, the uniformly mixed sample is placed at 500 ℃ and 600 ℃ for heat preservation reaction for 8-12h, and after the reaction is finished, the reaction is cooled to room temperature to obtain FeS with the surface coated with carbon2@C。
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