CN110783542A - Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery - Google Patents

Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery Download PDF

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CN110783542A
CN110783542A CN201911004237.6A CN201911004237A CN110783542A CN 110783542 A CN110783542 A CN 110783542A CN 201911004237 A CN201911004237 A CN 201911004237A CN 110783542 A CN110783542 A CN 110783542A
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mos
composite material
micro
paper towel
water
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张昭良
刘馨蔓
张景皓
辛颖
李倩
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University of Jinan
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The invention belongs to the technical field of new energy materials, and particularly relates to a paper towel derived carbon fiber loaded MoS 2A preparation method of the micro-flower composite material and application of the micro-flower composite material in a lithium-sulfur battery material. The method comprises the following steps: soaking commercial paper towels in hydrochloric acid for 24 hours, washing with water and drying; dissolving ammonium molybdate tetrahydrate and thiourea in water to obtain a mixed solution; immersing the treated paper towel into the mixed solution, carrying out hydrothermal treatment, and then washing and drying to obtain a sample; calcining the sample in inert atmosphere to obtain the paper towel derived carbon fiber negativeMoS-carrying 2A composite material of micro-flower rice. The invention prepares the carbon fiber loaded MoS derived from commercial paper towel 2The method of the micron flower composite material is mild, raw materials are easy to obtain, the cost is low, and the micron flower composite material has a plurality of effective anchoring sites and is beneficial to the adsorption and catalytic conversion of LiPSs. The content of active substances is up to 72 percent.

Description

Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a paper towel derived carbon fiber loaded MoS 2A preparation method of the micro-flower composite material and application of the micro-flower composite material in a lithium-sulfur battery material.
Background
With the rapid development of social economy and the rapid increase of energy demand, people pay attention to the development and utilization of clean renewable energy sources in order to reduce the dependence on fossil fuels, but the renewable energy sources are intermittent, so that the renewable energy sources need to be matched with advanced energy storage technology to meet the requirements of life and production, and with the large-scale application of the renewable energy sources, the demands of people on batteries with high energy/power density, strong stability, long service life, high reliability and low cost are increasingly strong. Lithium-sulfur batteries are expected to be the most promising electrochemical storage system due to their advantages of high theoretical energy density, low cost, etc., but their practical application is still bound by some inherent and troublesome challenges, such as low conductivity of sulfur electrodes, shuttle effect, and LiPSs-retarded redox kinetics.
Carbon nanotubes, graphene and the like are used as carbon substrates, have good conductivity and unique micro-nano structures, but the cost of the carbon nanotubes and graphene is high. However, the cost of lithium sulfur batteries can be greatly reduced by using low cost commercial paper towel derived carbon as the conductive carbon matrix. The molybdenum disulfide not only has stronger adsorption capacity to the LiPSs, but also can improve the catalytic conversion rate of the LiPSs, so that the lithium-sulfur battery has longer cycle life and higher sulfur utilization rate. The molybdenum disulfide micro-flowers with the three-dimensional structure can be used as effective anchoring sites for adsorbing LiPSs and catalyzing conversion, and the molybdenum disulfide micro-flowers are loaded on carbon fibers, so that excessive interfaces between carbon and electrolyte can be reduced to the maximum extent, the interaction between an electrode and the electrolyte is sufficient, the electron transmission is rapid, the Li ion transfer is promoted, and the redox kinetics is enhanced. Journal of Material chemistry A (Materials Ch)emistry a, 2019, 7) reported a method of doping carbon nanotubes/two-dimensional MoS by nitrogen 2The nano-thin sheet core-shell structure material is used as a positive electrode material applied to a lithium-sulfur battery, the sulfur capacity of an active substance is 70%, and the first-circle specific discharge capacity of the nano-thin sheet core-shell structure material is 1305 mAhg at 0.5 DEG C -1The capacity fade per cycle after 100 cycles was 0.2%, which is inferior in electrochemical performance, by comparison.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a paper towel derived carbon fiber loaded MoS 2
The preparation method of the micro-flower composite material has the advantages of easily obtained raw materials, simple process, easy realization and good electrochemical performance.
The invention also provides a paper towel derived carbon fiber loaded MoS 2The application of the micro-flower composite material in a lithium-sulfur battery material.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention provides a paper towel derived carbon fiber loaded MoS 2The preparation method of the micro-flower rice composite material comprises the following steps:
(1) soaking commercial paper towels in hydrochloric acid for 24 hours, washing with water and drying;
(2) dissolving ammonium molybdate tetrahydrate and thiourea in water to obtain a mixed solution;
(3) soaking the paper towel processed in the step (1) into the mixed solution prepared in the step (2), performing hydrothermal treatment, and then washing and drying to obtain a sample;
(4) the sample obtained in the step (3) is heated to 800 ℃ in an inert atmosphere oC, calcining to obtain paper towel derived carbon fiber loaded MoS 2A micro-flower rice composite;
the paper towel derived carbon fiber loaded MoS 2The composite material of the micro-flower rice consists of two-dimensional nano-sheet petals, wherein the petals are densely arranged and vertically arranged and are provided with a plurality of nano holes.
Further, in the step (1), the concentration of the hydrochloric acid is 1-2mol/L, and the addition amount of the hydrochloric acid is 10-30 mL.
Further, the specific process of the step (2) is as follows: 60-90mg of ammonium molybdate tetrahydrate and 1-5 mg of thiourea are dissolved in 10-30 mL of water to obtain a mixed solution.
Further, in the step (3), the mass of the paper towel is 60-90 mg; the temperature of the hydrothermal treatment is 100-250 ℃, and the treatment time is 24 h; the drying temperature is 50-100 deg.C oC。
Further, in the step (4), the inert atmosphere is argon, and the calcination temperature is 700- oC, the heating rate is 5-10 ℃/min, and the calcination time is 1-5 h.
The invention also provides the paper towel derived carbon fiber loaded MoS prepared by the preparation method 2The application of the micro-flower composite material in the positive electrode material of the lithium-sulfur battery.
The lithium-sulfur battery positive electrode material provided by the invention is prepared by the following method:
（1）S-MoS 2preparation of/C: mixing sulfur powder and MoS 2Mixing the raw materials at a certain ratio, grinding, and sealing
In a glass vial, and then the mixture was placed under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
(2) Preparation of slurry: drying the S-MoS 2Mixing conductive agent and binder, adding solvent I, stirring and mixing to obtain slurry, uniformly coating the slurry on a current collector by adopting a blade coating method, and heating to 80 DEG oAnd C, drying to obtain the cathode material.
Further, in the step (1), the sulfur powder and MoS 2The ratio of/C is 7: 3 or 8: 2.
further, in the step (2), the S-MoS 2and/C, the mass ratio of the conductive carbon to the binder is 8:1:1 or 7:2: 1.
Further, the conductive agent in the step (2) is acetylene black or super.P; the binder is water-based binder or oil-soluble binder, and the water-based binder is styrene butadiene rubber or sodium carboxymethylcellulose; the oil-soluble binder is polyvinylidene fluoride; when the binder is an oil-soluble binder, the solvent I is N-methyl pyrrolidone; when the binder is a water-based binder, the solvent I is water; the current collector is aluminum foil, carbon-coated aluminum foil, conductive carbon paper, conductive carbon felt or conductive carbon cloth.
Commercial paper towels used in the present invention are commercially available.
The invention uses paper towel derived carbon fiber to load MoS 2The specific assembling method of the lithium-sulfur battery prepared from the micro-flower composite material comprises the following steps: uniformly coating the slurry on a current collector at 50-90 deg.C oAnd C, drying for 6-48 h, finally cutting into a circular pole piece with the diameter of 8 mm, taking the prepared pole piece as a positive pole, Celgard 2300 as a diaphragm, a commercial metal Li piece as a negative pole, and adding ether electrolyte or carbonate electrolyte into a glove box filled with argon to finish the assembly of the battery.
The invention has the beneficial effects that:
1. the invention prepares the carbon fiber loaded MoS derived from commercial paper towel 2The method of the micron flower composite material is mild, raw materials are easy to obtain, the cost is low, and the micron flower composite material has a plurality of effective anchoring sites and is beneficial to the adsorption and catalytic conversion of LiPSs. The content of active substances is up to 72 percent.
2. Unique 3D MoS of the invention 2The flower has many nano-sheets and voids, and is connected with the carbon fiber through electrons, and compared with the conventional sulfur-carrying matrix, the effective electron transfer provides the advantages of high conductivity and effective adsorption to polysulfide.
3. MoS prepared by the invention 2Commercial paper towel derived carbon fiber composite material tool with micro-popcorn in-situ growth
Has good mechanical stability and reduces excessive interface between carbon and electrolyte. The electrodes and the electrolyte are fully interacted, which is beneficial to the rapid transmission of electrons.
4. The invention uses S-MoS 2the/C promotes Li as the positive electrode material of the lithium-sulfur battery +The transfer of the compound further promotes the redox conversion of the lithium polysulfide, accelerates the kinetic reaction process and effectively inhibits the shuttle effect.
Drawings
FIG. 1 is a MoS prepared in example 1 2XRD spectrum of/C.
FIG. 2 is a MoS prepared in example 1 2FESEM and SEM images for/C.
FIG. 3 is the S-MoS prepared in example 1 2C and S-C prepared in comparative example 1, S loading was 4.2 mg cm -2Cycle performance plot of 100 cycles at 0.5C.
FIG. 4 is the S-MoS prepared in example 1 2and/C is a multiplying power performance graph under different multiplying powers.
Detailed Description
The principles and features of the present invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
MoS 2Preparation of/C: commercial paper towels (fresh air) were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed with water to neutrality, 80% oC oven drying overnight, dissolving 76.7mg ammonium molybdate tetrahydrate and 1 g thiourea in 20 mL water, immersing 76.7mg of the treated paper towel in the above solution, 180% oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oDrying overnight under C, putting the obtained sample into a vacuum tube furnace, and placing the sample in an Ar atmosphere for 800 hours oAnd C, calcining for 2 h.
S-MoS 2Preparation of/C: mixing sulfur powder and MoS 2Mixing with/C, grinding thoroughly, sealing in a small bottle, and placing the small bottle in a vacuum tube furnace under Ar atmosphere for 300 times oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
Preparation of slurry: 80 mg S-MoS is weighed 2And C, 10 mg Super P and 10 mg PVDF are ball-milled for 3 hours by 200 mu L NMP and are uniformly mixed to prepare slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) the prepared pole piece is used as a positive electrode, Celgard 2300 is used as a diaphragm, a commercial metal Li piece is used as a negative electrode, and 30 mu L of ether electrolyte is added to complete the assembly of the battery in a glove box filled with argon.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
FIG. 1 shows the MoS prepared in this example 2XRD spectrum of/C and MoS 2From this figure we can see that MoS was successfully prepared 2And C, sampling.
FIG. 2 shows the MoS prepared in this example 2FESEM and SEM images of/C, from which it can be seen that MoS is present on commercial tissue-derived carbon fibers 2The flowers showed a uniform, compact arrangement, and MoS is seen from the high power SEM image 2The flower is composed of petals (two-dimensional nanosheets), the petals are densely arranged and vertically arranged, and a plurality of nano holes are formed.
FIG. 3 shows the S-MoS prepared in this example 2Cycle performance plot of 100 cycles at 0.5C for C and S/C prepared in comparative example 1. As can be seen in the figure, the S-MoS2/C electrode maintained 1032 mAh g after 100 cycles -1The capacity retention rate was 88% and the coulombic efficiency was 100%. In contrast, S/C had only a low discharge capacity and low capacity retention after 100 cycles. Can see the S-MoS 2The electrochemical performance of the/C is excellent.
FIG. 4 shows S-MoS 2The specific volume of the positive electrode/C is 1149, 1027, 856, 723 and 608 mA h g respectively when the current density is 0.2C, 0.5C, 1C, 2C and 4C -1. When the current density returned to 0.5C, the specific capacity was 913mA hr g -1And has good capacity reversibility.
Example 2
MoS 2Preparation of C-12: commercial paper towels were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed to neutrality with water, 80% oC oven drying overnight, dissolving 76 mg ammonium molybdate tetrahydrate and 1 g thiourea in 20 mL water, immersing 76 mg of the treated paper towel in the above solution, 180% oC, carrying out hydrothermal treatment for 12h, then carrying out suction filtration, and washing with water untilNeutral at 80 oDrying overnight under C, putting the obtained sample into a vacuum tube furnace, and placing the sample in an Ar atmosphere for 800 hours oAnd C, calcining for 2 h.
S-MoS 2Preparation of C-12: mixing sulfur powder and MoS 2Mixing with/C-12, grinding thoroughly, sealing in a vial, and placing the vial containing the mixture in a vacuum tube furnace under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C-12。
Preparation of slurry: 80 mg S-MoS is weighed 2and/C-12, 10 mg Super P and 10 mg PVDF, and 200 mu of LNMP are ball-milled for 3h and are uniformly mixed to prepare slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) the prepared pole piece is used as a positive electrode, Celgard 2300 is used as a diaphragm, a commercial metal Li piece is used as a negative electrode, and 30 mu L of ether electrolyte is added to complete the assembly of the battery in a glove box filled with argon.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
S-MoS prepared in example 2 2C-12 after 100 cycles, the S-MoS2/C-12 electrode maintained 604 mAh g -1The discharge capacity and coulombic efficiency of (1) were 97%.
Example 3
MoS 2Preparation of/C: commercial paper towels were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed to neutrality with water, 80% oC oven dried overnight, 76 mg ammonium molybdate tetrahydrate and 1 g thiourea were dissolved in 20 mL water and 140 mg of the treated paper towel was dipped in the above solution, 180 oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oDrying overnight under C, putting the obtained sample into a vacuum tube furnace, and placing the sample in an Ar atmosphere for 800 hours oAnd C, calcining for 2 h.
S-MoS 2Preparation of/C: mixing sulfur powder and MoS 2Mixing the raw materials with the water, and mixing the raw materials,grinding thoroughly, sealing in a vial, and placing the vial containing the mixture in a vacuum tube furnace under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
Preparation of slurry: 80 mg S-MoS is weighed 2And C, 10 mg Super P and 10 mg PVDF are ball-milled for 3 hours by 200 mu L NMP and are uniformly mixed to prepare slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) the prepared pole piece is used as a positive electrode, Celgard 2300 is used as a diaphragm, a commercial metal Li piece is used as a negative electrode, and 30 mu L of ether electrolyte is added into a glove box filled with argon to complete the assembly of the battery.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
The material prepared in example 3 maintained 809mAh g of electrode after 50 cycles -1The discharge capacity and the coulombic efficiency of (1) were 96%.
Example 4
MoS 2Preparation of/C: commercial paper towels were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed to neutrality with water, 80% oAnd C, drying overnight. 76 mg of ammonium molybdate tetrahydrate and 1 g of thiourea were dissolved in 20 mL of water and 140 mg of the treated paper towel was dipped in the above solution, 100 oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oAnd C, drying overnight. The obtained sample was placed in a vacuum tube furnace under Ar atmosphere 800 oAnd C, calcining for 2 h.
S-MoS 2Preparation of/C: mixing sulfur powder and MoS 2mix/C, grind well, then seal in a vial. Finally, the vial containing the mixture was placed in a vacuum tube furnace under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
Preparation of slurry: 80 mg S-MoS is weighed 2/C、10And (5) uniformly mixing the P and 10 mg of PVDF in a ball mill of 200 mu L NMP for 3h to prepare slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) taking the prepared pole piece as a positive electrode, Celgard 2300 as a diaphragm, a commercial metal Li piece as a negative electrode, adding 300 ether electrolyte, and completing the assembly of the battery in a glove box filled with argon.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
The material prepared in example 4 has S-MoS2/C electricity of 705mAh g after 50 cycles -1The discharge capacity and the coulombic efficiency of (1) were 100%.
Comparative example 1
Preparing carbon fibers: commercial paper towels were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed to neutrality with water, 80% oAnd C, drying overnight.
Preparation of S-C: the sulfur powder and carbon fibers were mixed, ground thoroughly, mixed and then sealed in a glass vial. Finally, the mixture is placed under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-C.
Preparation of slurry: weighing 80 mg of S-C, 10 mg of Super P and 10 mg of PVDF, and ball-milling 200 mu of LNMP for 3h to prepare slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) the prepared pole piece is used as a positive electrode, Celgard 2300 is used as a diaphragm, a commercial metal Li piece is used as a negative electrode, and 30 mu L of ether electrolyte is added into a glove box filled with argon to complete the assembly of the battery.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
As can be seen from FIG. 3, the S-HCS was maintained at 494 mA h g after 100 cycles -1Has a low capacity retention rate, and is similar to that of S-MoS in example 1 2the/C material is at a disadvantage compared to the electrochemical performance.
Comparative example 2
MoS 2Preparation: 76 mg of ammonium molybdate tetrahydrate and 1 g of thiourea were dissolved in 20 mL of water, 180 oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oAnd C, drying overnight. The obtained sample is placed in a vacuum tube furnace under the argon atmosphere 800 oAnd C, calcining for 2 h.
S-MoS 2The preparation of (1): mixing sulfur powder and MoS 2Mixing, grinding thoroughly, sealing in a small bottle, and placing the small bottle in a vacuum tube furnace under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2。
Preparation of slurry: 80 mg S-MoS is weighed 210 mg Super P and 10 mg PVDF, and 200 mu L NMP were ball milled for 3h and mixed uniformly to make slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) the prepared pole piece is used as a positive electrode, Celgard 2300 is used as a diaphragm, a commercial metal Li piece is used as a negative electrode, and 30 mu 0 ether electrolyte is added into a glove box filled with argon to complete the assembly of the battery.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
After 100 cycles, the electrode can only keep 400mAh g -1The discharge capacity and the coulomb efficiency of (1) are 90 percent, and the electrochemical performance is poorer
Comparative example 3
MoS 2Preparation of/C: commercial paper towels were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed to neutrality with water, 80% oC drying overnight. 76.7mg of ammonium molybdate tetrahydrate and 1 g of thiourea were dissolved in 20 mL of water and 76.7mg of the treated paper towel was immersed in the above solution at 180 deg.C oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oAnd C, drying overnight. The obtained sample was placed in a vacuum tube furnace under Ar atmosphere 800 oAnd C, calcining for 2 h.
S-MoS 2Preparation of/C: carrying sulfur by a melting diffusion method, and mixing sulfur powder and MoS 2Mixing with/C, grinding thoroughly, placing in a glass vial, sealing in a hydrothermal kettle, 155 oC, preserving the heat for 12 hours, and cooling to room temperature to obtain S-MoS 2/C。
Preparation of slurry: weighing 80 mg S-MoS2/C, 10 mg Super P and 10 mg PVDF, and ball-milling 200 mu L NMP for 3h to prepare slurry.
Manufacturing an electrode slice: the slurry was uniformly coated on a carbon-coated aluminum foil by knife coating at 80 deg.C oAnd C, drying for 12h, and cutting into circular pole pieces with the diameter of 8 mm.
Assembling the battery: and (3) the prepared pole piece is used as a positive electrode, Celgard 2300 is used as a diaphragm, a commercial metal Li piece is used as a negative electrode, and 30 mu L of ether electrolyte is added into a glove box filled with argon to complete the assembly of the battery.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
The sulfur loading of the method is only 60 percent, which is lower than that of the gas-phase sulfur loading method of the invention, and the electrochemical performance is poorer.
Comparative example 4
MoS 2Preparation of/C: commercial paper towels (fresh air) were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed with water to neutrality, 80% oC oven dried overnight, 100 mg ammonium molybdate tetrahydrate and 1 g thiourea were dissolved in 20 mL water and 76.7mg of the treated paper towel was immersed in the above solution 180 oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oDrying overnight under C, putting the obtained sample into a vacuum tube furnace, and placing the sample in an Ar atmosphere for 800 hours oC calcination 2 h。
S-MoS 2Preparation of/C: mixing sulfur powder and MoS 2Mixing with/C, grinding thoroughly, sealing in a small bottle, and placing the small bottle in a vacuum tube furnace under Ar atmosphere for 300 times oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
The other steps are the same as in example 1.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
No micro-flower-like balls were formed, and after 100 cycles, the S-MoS2/C electrode only maintained 550mAh g -1The discharge capacity of (2) was 88% in coulombic efficiency, and the electrochemical properties were poor. And when the addition amount of ammonium molybdate tetrahydrate is less than 60mg, micrometer flower-shaped products cannot be prepared, the particles are not uniform, and the electrochemical performance of the finally prepared electrode is poor.
Comparative example 5
MoS 2Preparation of/C: commercial paper towels (fresh air) were soaked in 20 mL of 1 mol/L HCl for 24 h and then washed with water to neutrality, 80% oC oven dried overnight, 76.7mg ammonium molybdate tetrahydrate and 1 g thiourea were dissolved in 20 mL water and 76.7mg of the treated paper towel was dipped in the above solution 300 oC, performing hydrothermal treatment for 24 hours, then performing suction filtration, washing with water to neutrality, and performing hydrothermal treatment at 80 DEG C oDrying overnight under C, putting the obtained sample into a vacuum tube furnace, and placing the sample in an Ar atmosphere for 800 hours oAnd C, calcining for 2 h.
S-MoS 2Preparation of/C: mixing sulfur powder and MoS 2Mixing with/C, grinding thoroughly, sealing in a small bottle, and placing the small bottle in a vacuum tube furnace under Ar atmosphere for 300 times oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
The other steps are the same as in example 1.
And (3) electrochemical performance testing: the invention adopts a blue-current LANCHET 2001A 1 mA and 2 mA charging and discharging instrument of Wuhanlanbo electronic Limited company to carry out constant-current charging and discharging and cycle performance test.
The micro-popcorn structure was not formed, and the discharge capacity of the S-MoS2/C electrode was 460mAh g after 100 cycles -1The coulomb efficiency is 85%, and the electrochemical performance is poor.
The above-described examples are illustrative of the present invention, and it should be understood that they are merely exemplary of the present invention and are not to be construed as limiting the present invention, and any modifications, additions, equivalents and the like which fall within the spirit of the present invention are intended to be included therein.

Claims (10)

1. Paper towel derived carbon fiber loaded MoS 2The preparation method of the micro-flower rice composite material is characterized by comprising the following steps:
(1) soaking commercial paper towels in hydrochloric acid for 24 hours, washing with water and drying;
(2) dissolving ammonium molybdate tetrahydrate and thiourea in water to obtain a mixed solution;
(3) soaking the paper towel processed in the step (1) into the mixed solution prepared in the step (2), performing hydrothermal treatment, and then washing and drying to obtain a sample;
(4) the sample obtained in the step (3) is heated to 800 ℃ in an inert atmosphere oC, calcining to obtain paper towel derived carbon fiber loaded MoS 2A micro-flower rice composite;
the paper towel derived carbon fiber loaded MoS 2The composite material of the micro-flower rice consists of two-dimensional nano-sheet petals, wherein the petals are densely arranged and vertically arranged and are provided with a plurality of nano holes.
2. The method according to claim 1, wherein the hydrochloric acid is added in an amount of 10 to 30 mL in step (1) at a concentration of 1 to 2 mol/L.
3. The preparation method according to claim 1, wherein the specific process of step (2) is as follows: 60-90mg of ammonium molybdate tetrahydrate and 1-5 mg of thiourea are dissolved in 10-30 mL of water to obtain a mixed solution.
4. The method according to claim 1, wherein in the step (3), the mass of the napkin is 60-90 mg; the temperature of the hydrothermal treatment is 100-250 ℃, and the treatment time is 24 h; the drying temperature is 50-100 deg.C oC。
5. The method as claimed in claim 1, wherein in step (4), the inert atmosphere is argon, and the calcination temperature is 700-900- oC, the heating rate is 5-10 ℃/min, and the calcination time is 1-5 h.
6. MoS loaded with paper towel derived carbon fiber prepared by the preparation method according to any one of claims 1 to 5 2The application of the micro-flower composite material in the positive electrode material of the lithium-sulfur battery.
7. The use of claim 6, wherein the lithium-sulfur battery positive electrode material is prepared by the following method:
（1）S-MoS 2preparation of/C: mixing sulfur powder and MoS 2Mixing the above materials at a certain ratio, grinding thoroughly, sealing in a glass vial, and placing the mixture under Ar atmosphere 300 oC is heated for 4 hours and cooled to room temperature to obtain S-MoS 2/C。
(2) Preparation of slurry: drying the S-MoS 2Mixing conductive agent and binder, adding solvent I, stirring and mixing to obtain slurry, uniformly coating the slurry on a current collector by adopting a blade coating method, and heating to 80 DEG oAnd C, drying to obtain the cathode material.
8. Use according to claim 7, wherein in step (1), the sulphur powder and MoS are present 2The ratio of/C is 7: 3 or 8: 2.
9. use according to claim 7, wherein in step (2) the S-MoS is used 2and/C, the mass ratio of the conductive carbon to the binder is 8:1:1 or 7:2: 1.
10. Use according to claim 7, wherein the conductive agent in step (2) is acetylene black or super. P; the binder is water-based binder or oil-soluble binder, and the water-based binder is styrene butadiene rubber or sodium carboxymethylcellulose; the oil-soluble binder is polyvinylidene fluoride; when the binder is an oil-soluble binder, the solvent I is N-methyl pyrrolidone; when the binder is a water-based binder, the solvent I is water; the current collector is aluminum foil, carbon-coated aluminum foil, conductive carbon paper, conductive carbon felt or conductive carbon cloth.
CN201911004237.6A 2019-10-22 2019-10-22 Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery Pending CN110783542A (en)

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