CN110504426B - MOFs-based layered porous copper sulfide/sulfur nanocomposite material, preparation method thereof, lithium-sulfur battery anode and battery - Google Patents
MOFs-based layered porous copper sulfide/sulfur nanocomposite material, preparation method thereof, lithium-sulfur battery anode and battery Download PDFInfo
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Abstract
The invention discloses a layered porous copper sulfide/sulfur nano composite material based on MOFs (metal organic frameworks), a preparation method thereof, a lithium-sulfur battery anode and a battery, wherein three-dimensional layered porous copper-based MOFs are prepared by a solvothermal method, a tube furnace is used for vulcanizing sulfur powder at high temperature to generate copper sulfide, and a layer of elemental sulfur is attached to the surface of the prepared porous layered copper sulfide by using a vapor deposition method to perform sulfur fumigation to form the three-dimensional copper sulfide/sulfur composite material with a unique appearance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a layered porous copper sulfide/sulfur nanocomposite based on MOFs (metal-organic frameworks), a preparation method thereof, a lithium sulfur battery anode and a battery.
Background
Since fossil fuels are limited and combustion causes a series of environmental problems, clean energy sources such as solar energy, hydraulic energy, nuclear energy and the like have not been developed as alternative energy sources.
Lithium sulfur battery asFor the promising next generation energy storage battery, sulfur is used as an active anode material, and polysulfide is formed between the active anode material and a lithium cathode material to generate current, and the theoretical capacity of the current is about 1675 mAh g-1And will further reduce battery cost thanks to the abundance of sulfur in the earth's crust. However, sulfur is poor in conductivity as an insulator and varies greatly in volume during charge and discharge, and the generated polysulfide dissolves in an electrolyte to cause loss of an active material, thereby drastically decreasing battery performance due to it.
Disclosure of Invention
In order to solve the technical problems, the invention provides a layered porous copper sulfide/sulfur nano composite material based on MOFs (metal-organic frameworks), a preparation method thereof, a lithium-sulfur battery anode and a battery. The invention provides a novel preparation method of a composite material with high yield and low cost, aiming at the technical problems of poor circulation stability and the like of copper sulfide as an electrode material.
The technical scheme adopted by the invention is as follows:
a preparation method of a layered porous copper sulfide/sulfur nanocomposite material based on MOFs comprises the following steps:
(1) dissolving copper salt and terephthalic acid in an organic solvent, carrying out solvothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain three-dimensional layered copper-based MOFs;
(2) respectively placing the three-dimensional layered copper-based MOFs and sulfur powder at two ends of a magnetic boat, covering the magnetic boat, placing the magnetic boat in a tubular furnace for calcining, and naturally cooling to obtain layered porous copper sulfide based on the MOFs;
(3) and (3) carrying out sulfur fumigation on the MOFs-based layered porous copper sulfide obtained in the step (2), so as to obtain the MOFs-based layered porous copper sulfide/sulfur nano composite material.
Further, in the step (1), the copper salt is copper nitrate trihydrate; the organic solvent is N, N-dimethylformamide.
In the step (1), the copper salt and the p-phenylene bisThe mass ratio of formic acid is 2: 1; the concentration of the copper salt in the organic solvent is 0.03-0.27 mol L-1Preferably 0.09mol L-1。
In the step (1), the solvothermal reaction is carried out for 0.5-20 hours at 90-130 ℃.
In the step (2), the mass ratio of the layered copper-based MOFs to the sulfur powder is 2: 1; the calcining condition is calcining for 1-4 hours at 400-600 ℃, preferably for 1 hour; and (2) decomposing MOFs in the three-dimensional layered copper-based MOFs obtained in the step (1) at the calcining temperature to remove a terephthalate ligand bonded with copper, and further reacting with sulfur powder to form porous layered copper sulfide.
And (3) sealing the layered porous copper sulfide and the sublimed sulfur powder based on the MOFs obtained in the step (2) in a polytetrafluoroethylene bottle filled with argon, and keeping the temperature at 150-160 ℃ for 20-26 hours to finish sulfur smoking.
Or in the step (3), sublimed sulfur powder is ultrasonically dissolved in carbon disulfide, the MOFs-based layered porous copper sulfide obtained in the step (2) is added into the carbon disulfide for ultrasonic dispersion, then the mixture is dried into powder, the powder is sealed in a polytetrafluoroethylene bottle filled with argon, and the powder is kept at the temperature of 150-160 ℃ for 20-26 hours, so that the sulfuration is completed. Thus ensuring the uniformity of the elemental sulfur attached on the surface of the copper sulfide. The drying is carried out in an oven at the temperature of 35-50 ℃ for 6-8 h; the mass volume ratio of the sublimed sulfur powder to the carbon disulfide is 0.05-0.2 g/10 mL, and preferably 0.1 g/10 mL.
In the step (3), the mass ratio of the layered porous copper sulfide based on the MOFs to the sublimed sulfur powder is 1: 1-3, preferably 1: 2.
The MOFs-based layered porous copper sulfide/sulfur nano composite material prepared by the preparation method is formed by loading sulfur particles on the surface of layered porous copper sulfide.
The invention also provides a lithium-sulfur battery anode which is prepared by taking the MOFs-based layered porous copper sulfide/sulfur nano composite material as an active substance.
The invention also provides a lithium-sulfur battery which is prepared by taking the lithium-sulfur battery positive electrode as a positive electrode.
In the preparation method of the MOFs-based layered porous copper sulfide/sulfur nano composite material, copper salt is used as a raw material, terephthalic acid is used as an organic ligand, and a solvothermal reaction is carried out in a DMF solvent to synthesize a three-dimensional layered copper-based MOFs precursor; and sulfurizing the copper powder at high temperature by using a tube furnace to generate copper sulfide, wherein in the step, as the combination mode between the terephthalic acid and the copper is the combination of coordination bonds, the MOFs starts to decompose at about 350 ℃, and the decomposition is complete at 400 ℃, the terephthalic acid radical of the organic ligand can be removed, the appearance of the organic ligand is still laminar, and the porous copper sulfide is generated; the method for fumigating sulfur is utilized to attach a layer of elemental sulfur on the surface of the prepared porous layered copper sulfide to form a three-dimensional copper sulfide/sulfur composite material with a unique appearance, so that the problem of poor conductivity of the elemental sulfur is solved, the three-dimensional porous structure can contain more elemental sulfur, the problem of volume expansion of the sulfur in the charging and discharging processes is solved, the battery has better stability, and the material has the advantages of good cycle performance, high specific energy density and the like when being applied to a lithium sulfur battery.
Compared with the prior art, the invention has the following advantages:
(1) the prepared copper sulfide can well keep the porous layered structure of MOFs and can provide a large specific surface area;
(2) the prepared copper sulfide/sulfur composite material has stable performance, is not easy to denature in air and is easy to store;
(3) the prepared copper sulfide/sulfur composite material is used as a lithium-sulfur battery positive electrode material and has larger specific capacity and better cycle performance;
(4) the raw materials are low in price, the synthesis process is simple, and batch production can be carried out.
Drawings
FIG. 1 is an SEM image of a copper-based MOFs composite material prepared in comparative example 1;
FIG. 2 is an SEM photograph of copper sulfide prepared in comparative example 1;
FIG. 3 is an XRD pattern of copper sulfide prepared in comparative example 1, and example 2;
FIG. 4 is an SEM image of a copper sulfide/sulfur composite prepared in comparative example 1;
FIG. 5 is an SEM image of copper sulfide prepared in example 1;
FIG. 6 is an SEM image of a copper sulfide/sulfur composite prepared in example 1;
FIG. 7 is an XRD pattern of the copper sulfide/sulfur composite prepared in example 1;
FIG. 8 is an SEM image of copper sulfide prepared in example 2;
FIG. 9 is an SEM image of a copper sulfide/sulfur composite prepared in example 2;
FIG. 10 is an SEM image of a copper sulfide/sulfur composite prepared in example 3;
FIG. 11 is a graph showing the cycling stability test of the copper sulfide/sulfur composite prepared in example 1 as a positive electrode material for a lithium-sulfur battery at a current density of 0.1C;
fig. 12 is a charge-discharge curve diagram of the copper sulfide/sulfur composite material prepared in example 1 as a positive electrode material of a lithium-sulfur battery at a current density of 0.1C.
Detailed Description
The invention will be described in detail below with reference to the following examples and the accompanying drawings.
Comparative example 1
A preparation method of a layered porous copper sulfide/sulfur nanocomposite based on MOFs comprises the following steps:
(1) preparing copper-based MOFs: weighing 2.7 mmol Cu (NO)3)2·3H2Adding 30 mL of N, N-dimethylformamide into a beaker together with O and 1.35 mmol of terephthalic acid, completely dissolving the N, N-dimethylformamide under ultrasound, pouring the obtained solution into a 50 mL inner container of a polytetrafluoroethylene reaction kettle, reacting for 8 hours at 110 ℃, centrifuging at 8000 revolutions per minute after the reaction is finished, respectively cleaning the solution with N, N-dimethylformamide and absolute ethyl alcohol for three times, and drying the solution in vacuum at 60 ℃ for 12 hours to obtain copper-based MOFs with adjustable and layered sizes, wherein the SEM picture of the copper-based MOFs is shown in figure 1, and the copper-based MOFs with smooth surfaces can be seen from the SEM picture;
(2) and (3) a vulcanization procedure: weighing 0.24 g of the copper-based MOFs prepared in the step (1), placing the copper-based MOFs at one end of a magnetic boat, weighing 0.12 g of sublimed sulfur, placing the sublimed sulfur at the other end of the magnetic boat, keeping a certain distance between the two ends, placing one end of sulfur powder in the direction of an air outlet of a tube furnace, and reacting for 1h at 300 ℃ to prepare a dark green powdery sample, wherein an SEM (scanning electron microscope) diagram of the sample is shown in figure 2, and the sample can be seen to keep the layered morphology of the copper-based MOFs, form porous substances on the surface of the copper-based MOFs, but the MOFs are not completely decomposed and only partially converted into CuS; the XRD pattern is shown in (a) of FIG. 3, from which it can be seen that the product obtained in this step is CuS, but the terephthalic acid ligand in the MOFs remains;
(3) a sulfuration procedure: weighing 0.1 g of product in the step (2) after vacuum drying in a sulfurated polytetrafluoroethylene bottle, weighing 0.2g of sublimed sulfur powder, placing the sublimed sulfur powder in the polytetrafluoroethylene bottle, uniformly mixing, placing the polytetrafluoroethylene bottle in a glove box with water less than or equal to 0.01ppm and oxygen value less than or equal to 0.01ppm for more than 1h to fill argon gas, sealing, placing the sealed polytetrafluoroethylene bottle in an oven, and keeping the temperature at 155 ℃ for 24 h to obtain dark green powder, namely the MOFs-based layered porous copper sulfide/sulfur nano composite material, wherein an SEM image is shown in figure 4, and sulfur particles are further deposited on the surface of the CuS layered porous structure after the reaction in the step.
Example 1
A preparation method of a layered porous copper sulfide/sulfur nanocomposite based on MOFs comprises the following steps:
(1) the preparation method of copper-based MOFs was the same as that of comparative example 1;
(2) and (3) a vulcanization procedure: weighing 0.24 g of the copper-based MOFs prepared in the step (1), placing the copper-based MOFs at one end of a magnetic boat, weighing 0.12 g of sublimed sulfur, placing the sublimed sulfur at the other end of the magnetic boat, keeping a certain distance between the two ends, placing one end of sulfur powder in the direction of an air outlet in a tube furnace, and reacting for 1h at 400 ℃ to prepare a dark green powdery sample, wherein an SEM picture of the sample is shown in FIG. 5, and the sample can keep the layered morphology of the copper-based MOFs, but the MOFs are completely decomposed and converted into porous substances; the XRD pattern is shown in (b) of FIG. 3, from which it can be seen that the product obtained in this step is allPart is Cu1.81S, no terephthalic acid ligand exists;
(3) a sulfuration procedure: weighing 0.1 g of product in the step (2) after vacuum drying in a sulfurated polytetrafluoroethylene bottle, weighing 0.2g of sublimed sulfur powder, placing the sublimed sulfur powder in the polytetrafluoroethylene bottle, uniformly mixing, placing the bottle in a glove box with water less than or equal to 0.01ppm and oxygen value less than or equal to 0.01ppm for more than 1h to fill argon, placing the bottle in an oven after sealing, and keeping the bottle at 155 ℃ for 24 h to obtain dark green powder, namely the MOFs-based layered porous copper sulfide/sulfur nanocomposite. The SEM image is shown in FIG. 6, from which it can be seen that after this step of reaction, Cu is present1.81The XRD pattern of the S-layered porous structure with sulfur particles deposited on the surface is shown in fig. 7, and it can be seen that the product obtained in this step is a copper sulfide/sulfur composite material.
Example 2
A preparation method of a layered porous copper sulfide/sulfur nanocomposite based on MOFs comprises the following steps:
(1) the preparation method of copper-based MOFs was the same as in example 1.
(2) And (3) a vulcanization procedure: weighing 0.24 g of the copper-based MOFs prepared in the step (1), placing the copper-based MOFs at one end of a magnetic boat, weighing 0.12 g of sublimed sulfur at the other end of the magnetic boat, keeping a certain distance between the two ends, placing one end of sulfur powder in the direction of an air outlet in a tube furnace, and reacting for 1h at 500 ℃ to prepare a brown powdery sample, wherein an SEM (scanning electron microscope) diagram of the sample is shown in FIG. 8, and the copper-based MOFs can be seen to keep the layered morphology, but are completely decomposed and converted into porous substances; the XRD pattern is shown in FIG. 3 (c), from which it can be seen that the product obtained in this step is Cu in its entirety1.96S, no terephthalic acid ligand exists;
(3) a sulfuration procedure: weighing 0.1 g of product in the step (2) after vacuum drying in a sulfurated polytetrafluoroethylene bottle, weighing 0.2g of sublimed sulfur powder, placing the sublimed sulfur powder in the polytetrafluoroethylene bottle, mixing uniformly, placing the bottle in a glove box with the water value less than or equal to 0.01ppm and the oxygen value less than or equal to 0.01ppm for more than 1h to fill the bottle with argon, sealing, and placing the bottle in the glove boxKeeping the temperature in an oven at 155 ℃ for 24 hours to obtain dark green powder, namely the MOFs-based layered porous copper sulfide/sulfur nano composite material, wherein an SEM picture is shown in figure 9, and as can be seen from the SEM picture, after the reaction, Cu is added1.96Sulfur particles are deposited on the surface of the S-shaped layered porous structure.
Example 3
A preparation method of a layered porous copper sulfide/sulfur nanocomposite based on MOFs comprises the following steps:
(1) the preparation method of copper-based MOFs was the same as in example 1.
(2) And (3) a vulcanization procedure: the vulcanization procedure was the same as in example 2.
(3) A sulfuration procedure: weighing 0.2g of sublimed sulfur powder, dissolving in 10 mL of carbon disulfide under ultrasonic waves, adding 0.1 g of copper sulfide in the step (2), performing ultrasonic waves to uniformly disperse the copper sulfide, placing the obtained liquid in an oven at 40 ℃ for 6 h to completely dry the liquid, placing the obtained powder in a polytetrafluoroethylene bottle, placing the bottle in a glove box with the water value of less than or equal to 0.01ppm and the oxygen value of less than or equal to 0.01ppm for more than 1h to fill the bottle with argon, placing the bottle in the oven after sealing, and keeping the bottle at 155 ℃ for 24 h to obtain a copper sulfide and sulfur compound, wherein an SEM (scanning electron microscope) diagram of the compound is shown in figure 10, and sulfur is loaded between each layer of porous layered copper sulfide.
Example 4
Application of layered porous copper sulfide/sulfur nanocomposite material based on MOFs as positive active material of lithium battery
The MOFs-based layered porous copper sulfide/sulfur nanocomposite material prepared in example 1 is used as an active material, and is uniformly mixed with conductive carbon black and PVDF according to the proportion of 7:2:1 or 6:3:1, then the mixture is magnetically stirred for 8-12 hours to be uniformly dispersed in N-methyl pyrrolidone, the prepared slurry is coated on an aluminum foil by using a coater, the aluminum foil is placed in a vacuum drying box at the temperature of 60-80 ℃, and after drying for 8-12 hours, the aluminum foil is taken out and cut into a small round electrode plate by using a cutting machine.
And assembling the prepared electrode slice into a button cell in a glove box which is filled with high-purity argon and has the water oxygen value of less than or equal to 0.01 ppm. 1.0M of LiTFSI was dissolved in a solution of 1, 3 dioxolane and ethylene glycol dimethyl ether mixed at a volume ratio of 1:1, and 1% LiNO was added3And preparing the electrolyte. The specific method for assembling the battery comprises the following steps: the method comprises the steps of dropping a drop of electrolyte on a motor shell, placing an electrode plate, then dropping two drops of electrolyte, placing a diaphragm, dropping a drop of electrolyte on the diaphragm, placing a lithium sheet as a counter electrode, then respectively placing a gasket and an elastic sheet, tightly pressing and sealing a battery by using a hydraulic machine, and placing for 6-8 hours.
Then, the cycling performance and the charging and discharging performance of the button cell are carried out under the current of 0.1C, and as shown in fig. 11 and 12, the capacity of the button cell can still be maintained at about 300mAh/g after 1000 cycles, as can be seen from fig. 11, the first discharging platform is about 2.15V and the second discharging platform is about 1.95V in the discharging process, and the button cell has a stable charging and discharging platform in the charging and discharging process.
The above detailed description of a MOFs-based layered porous copper sulfide/sulfur nanocomposite, a method for preparing the same, a lithium sulfur battery positive electrode and a battery, with reference to examples, is illustrative and not restrictive, and several examples can be cited within the scope of the present invention, so that variations and modifications thereof without departing from the general concept of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A preparation method of a layered porous copper sulfide/sulfur nanocomposite material based on MOFs is characterized by comprising the following steps:
(1) dissolving copper salt and terephthalic acid in an organic solvent, carrying out solvothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain three-dimensional layered copper-based MOFs;
(2) respectively placing the three-dimensional layered copper-based MOFs and sulfur powder at two ends of a magnetic boat, covering the magnetic boat, placing the magnetic boat in a tubular furnace for calcining, and naturally cooling to obtain layered porous copper sulfide based on the MOFs;
(3) carrying out sulfur fumigation on the MOFs-based layered porous copper sulfide obtained in the step (2), so as to obtain the MOFs-based layered porous copper sulfide/sulfur nano composite material;
in the step (1), the solvothermal reaction is carried out for 0.5-20 hours at the temperature of 90-130 ℃;
in the step (2), the calcining condition is 400-600 ℃ for 1-4 hours.
2. The method according to claim 1, wherein in the step (1), the copper salt is copper nitrate trihydrate; the organic solvent is N, N-dimethylformamide; the mass ratio of the copper salt to the terephthalic acid is 2: 1; the concentration of the copper salt in the organic solvent is 0.03-0.27 mol L-1。
3. The production method according to claim 1, wherein in the step (2), the mass ratio of the layered copper-based MOFs to the sulfur powder is 2: 1.
4. The preparation method according to claim 1, wherein in the step (3), the MOFs-based layered porous copper sulfide and sublimed sulfur powder obtained in the step (2) are sealed in a polytetrafluoroethylene bottle filled with argon gas, and the temperature is kept at 150-160 ℃ for 20-26 hours, so that the sulfuring is completed.
5. The preparation method according to claim 1, wherein in the step (3), sublimed sulfur powder is ultrasonically dissolved in carbon disulfide, the MOFs-based layered porous copper sulfide obtained in the step (2) is added to the carbon disulfide for ultrasonic dispersion, then the mixture is dried into powder, the powder is sealed in a polytetrafluoroethylene bottle filled with argon, and the temperature is kept at 150-160 ℃ for 20-26 hours, so that the sulfur smoking is completed.
6. The method according to claim 1, 4 or 5, wherein in the step (3), the mass ratio of the layered porous copper sulfide based on MOFs to the sublimed sulfur powder is 1:1 to 3.
7. The layered porous copper sulfide/sulfur nanocomposite based on MOFs prepared by the preparation method according to any one of claims 1 to 6.
8. A lithium-sulfur battery positive electrode, characterized by being prepared from the MOFs-based layered porous copper sulfide/sulfur nanocomposite as claimed in claim 7 as an active material.
9. A lithium-sulfur battery, characterized by being produced from the positive electrode for a lithium-sulfur battery according to claim 8 as a positive electrode.
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