CN114162874A - Preparation method of composite metal sulfide loaded mixed carbon material serving as sulfur main body material of lithium-sulfur battery - Google Patents

Preparation method of composite metal sulfide loaded mixed carbon material serving as sulfur main body material of lithium-sulfur battery Download PDF

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CN114162874A
CN114162874A CN202111499654.XA CN202111499654A CN114162874A CN 114162874 A CN114162874 A CN 114162874A CN 202111499654 A CN202111499654 A CN 202111499654A CN 114162874 A CN114162874 A CN 114162874A
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sulfur
lithium
carbon material
metal sulfide
composite metal
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CN114162874B (en
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曹瑞国
杨善
焦淑红
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University of Science and Technology of China USTC
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • H—ELECTRICITY
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a mixed carbon material loaded with a composite metal sulfide as a sulfur main body material of a lithium-sulfur battery. The microstructure of the sulfur main body material of the lithium-sulfur battery contains a stable continuous conductive network, transition metal sulfides with good adsorption and catalytic performances grow in situ on the surface of the sulfur main body material, and the transition metal sulfides are distributed uniformly, so that the sulfur main body material has good conductivity, the utilization rate of sulfur is improved, the loss of sulfur-containing substances in the charge-discharge cycle process of the battery can be effectively reduced, and the long cycle stability of the lithium-sulfur battery is finally improved; meanwhile, the preparation process of the sulfur main body material of the lithium-sulfur battery is simple, and the lithium-sulfur battery has good universality.

Description

Preparation method of composite metal sulfide loaded mixed carbon material serving as sulfur main body material of lithium-sulfur battery
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of a sulfur main body material of a lithium-sulfur battery.
Background
In order to improve the comprehensive performance of the secondary battery to meet the requirement of the secondary battery in actual productionIn addition to further upgrading the conventional lithium ion battery, the development of a new secondary battery system is urgent. The lithium-sulfur battery takes lithium metal as a negative electrode, elemental sulfur as a positive electrode and reaction Li + S ═ Li2The secondary battery system which can be charged and discharged circularly based on S has the advantages of high theoretical energy density, rich sulfur storage in the earth crust, no pollution to the environment and the like, so the secondary battery system becomes the key point of research of researchers. Since sulfur itself has poor conductivity and a large volume change during charge and discharge, it is necessary to use a positive electrode material having good physicochemical properties as a main body for supporting sulfur to effectively improve the long cycle performance of the lithium-sulfur battery.
The carbon material is suitable for being used as a sulfur main body material of a lithium-sulfur battery due to the advantages of rich pore structure, large specific surface area, good conductivity and the like. Various carbon materials have been used as sulfur host materials for lithium-sulfur batteries, such as carbon fibers, carbon nanotubes, graphene, MXene, and hollow carbon spheres, and all of them have achieved certain effects. However, the performance improvement of a single kind of carbon material used as a sulfur main body material of a lithium sulfur battery is still relatively limited, so researchers currently try to uniformly mix carbon materials with multiple dimensions according to a certain mass ratio to construct a multi-dimensional mixed carbon material system, which has a more stable conductive network, a richer pore structure and a larger specific surface area, so that more active substances can be supported and the utilization rate of sulfur in a long-cycle process can be improved, and the combination of a one-dimensional carbon material and a two-dimensional carbon material has good development potential.
Since the carbon material itself has no polarity and the carbon material itself has no catalytic activity, it is necessary to introduce certain metal compounds (e.g., metal oxides, metal sulfides, metal nitrides, etc.) into the sulfur host material of the lithium sulfur battery in order to effectively promote the kinetics of polysulfide conversion in the lithium sulfur battery reaction, and they are used as an adsorbent and a catalyst for polysulfide. The transition metal sulfide can be used as lithium sulfide because the transition metal element has good catalytic activity due to its unique electronic structureA catalyst for polysulfides in the cell sulfur host material. VS4Is a linear transition metal sulfide with better conductivity, wherein adjacent V is4+(S2 2-)2The chains are bonded by weak van der Waals forces, thereby promoting the rapid charge transfer kinetics of the chains, and having good catalytic activity and a VS of the multilayer type2Stronger adsorption capacity to polysulfide. At the same time, iron sulfide (e.g. FeS, FeS)2Etc.) has an excellent adsorption function for polysulfides. Thus, turn VS4And iron sulfide (FeS)x) Both are feasible to incorporate into the sulfur host material of a lithium sulfur battery as an adsorbent and catalyst for polysulfides.
At present, a single carbon material is used as a sulfur main body material of a lithium sulfur battery, but a mixed multi-dimensional carbon material structure formed by combining carbon materials with different dimensions is less applied to the sulfur main body material of the lithium sulfur battery, and a composite sulfide composed of two transition metal sulfides is not grown in situ on the mixed multi-dimensional carbon material structure to be used as the sulfur main body material of the lithium sulfur battery.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon fiber and graphene mixed carbon material loaded with iron sulfide and vanadium tetrasulfide composite metal sulfide, which is used as a sulfur main body material of a lithium-sulfur battery, so that the problems of poor conductivity of sulfur in the lithium-sulfur battery and serious polysulfide loss in a long circulation process are solved, the long circulation performance of the lithium-sulfur battery is effectively improved, and the practical application of the lithium-sulfur battery is promoted.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a composite metal sulfide-loaded mixed carbon material serving as a sulfur main body material of a lithium-sulfur battery comprises the following steps:
1) slowly adding concentrated sulfuric acid into concentrated nitric acid to obtain a strong acid mixed solution; adding carbon fibers into the strong acid mixed solution, and performing reflux reaction under the condition of an oil bath to obtain carbon fiber CNFO subjected to acidification treatment;
2) uniformly mixing the CNFO obtained in the step 1) with graphene oxide powder to obtain a mixed carbon material;
3) mixing Na3VO4Sequentially dissolving TAA (thioacetamide) and CTAB (cetyl trimethyl ammonium bromide) in deionized water, and fully stirring to obtain a clear solution A; adding the mixed carbon material prepared in the step 2) into the solution A, and uniformly stirring after ultrasonic dispersion to obtain a suspension B;
4) carrying out hydrothermal reaction on the suspension B, and obtaining an intermediate after the reaction is finished;
5) weighing a certain amount of FeSO4·7H2Adding O into deionized water, and fully stirring and dissolving to obtain a uniform solution C;
6) adding the intermediate prepared in the step 4) into a mixed solution of deionized water and absolute ethyl alcohol, and uniformly stirring after ultrasonic dispersion to form a suspension D;
7) slowly adding the solution C into the suspension D under the condition of continuous stirring, and then fully stirring to obtain a suspension E; carrying out suction filtration on the suspension E to obtain a wet precursor on filter paper, and then drying to obtain a dry precursor;
8) flatly paving the precursor obtained in the step 7) in a corundum square boat, placing the square boat in a tubular furnace, heating in argon atmosphere for reaction, cooling to room temperature in argon atmosphere after the reaction is finished, and obtaining the carbon fiber and graphene mixed carbon material loaded with iron sulfide and vanadium tetrasulfide composite metal sulfide as the sulfur main material of the lithium-sulfur battery, wherein the carbon fiber and graphene mixed carbon material is recorded as FeSx-VS4@(rGO+CNF)。
Preferably, in the step 1), 25mL to 37.5mL of concentrated nitric acid is added into every 12.5mL to 75mL of concentrated sulfuric acid, 250mg to 1000mg of carbon fiber is added into every 37.5mL to 112.5mL of strong acid mixed solution, the temperature of the reflux reaction is controlled to be 75 ℃ to 85 ℃, and the reaction time is controlled to be 2h to 4 h.
Preferably, in the step 2), the mass ratio of the graphene oxide powder to the CNFO is 90mg to 100 mg: 100mg to 110 mg.
Preferably, 165mg to 185mg of deionized water are added into every 20mL to 25mL of deionized water in the step 3)Na of (2)3VO4650-750 mg of TAA and 100-120 mg of CTAB, and 190-210 mg of the mixed carbon material is added into every 20-25 mL of the solution A.
Preferably, step 4), the hydrothermal reaction is specifically: adding the suspension B into a hydrothermal reaction kettle, sealing, controlling the filling ratio to be 50-60%, placing into an electric constant-temperature air-blast drying oven, controlling the reaction temperature to be 155-165 ℃ and controlling the reaction time to be 22-26 h.
Preferably, in the step 5), 680mg to 720mg of FeSO is added into every 45mL to 55mL of deionized water4·7H2O。
Preferably, in the step 6), 20mL to 30mL of anhydrous ethanol is added into every 20mL to 30mL of deionized water, and 100mg to 120mg of intermediate is added into every 40mL to 60mL of mixed solution.
Preferably, in step 7), the solution C is slowly added to the suspension D, and then stirred for 2 to 4 hours, and the temperature for drying the wet precursor is 80 ℃.
Preferably, in the step 8), the temperature rise reaction is carried out at a temperature rise rate of 3-5 ℃/min to 250-350 ℃ and heat preservation treatment is carried out for 1-3 h.
The mixed carbon material loaded with the composite metal sulfide prepared by the invention can be used as a sulfur main body material of a lithium-sulfur battery.
Compared with the prior art, the invention has the beneficial effects that:
1) the sulfur main body material of the lithium-sulfur battery prepared by the invention utilizes a mixed carbon material structure which is formed by one-dimensional carbon fibers and two-dimensional graphene, and has a continuous conductive network with a more stable microstructure, so that the impedance of the battery is favorably reduced; and the pore structure is richer, the specific surface area is larger, and the sulfur carrying capacity is stronger.
2) The sulfur main body material of the lithium-sulfur battery prepared by the invention comprises FeSxAnd VS4Complexes of two transition metal sulfides, FeSxAnd VS4Each can be used as an adsorbent and a catalyst to effectively adsorb polysulfides and promote the kinetics of polysulfide conversion reactions, thereby minimizing active species during long cyclesLoss of the solution; at the same time, FeSxAnd VS4The composite sulfide has better synergistic effect, can more efficiently complete the adsorption and catalysis of polysulfide, and further improves the utilization rate of sulfur in the long-cycle process.
3) The FeS-based carbon material grows on the surface of a mixed carbon material structure composed of one-dimensional carbon fibers and two-dimensional graphene in situxAnd VS4The composite metal sulfide successfully combines the advantages of the mixed carbon material structure with the advantages of the composite metal sulfide, thereby comprehensively solving the defects of the sulfur main body material of the lithium sulfur battery only containing a single carbon material or a single metal compound adsorption-catalyst and effectively improving the long cycle performance of the lithium sulfur battery.
4) FeS prepared by the inventionx-VS4After the sulfur main body material of the @ lithium sulfur battery (rGO + CNF) bears sulfur by a melting diffusion method, a corresponding positive pole piece is prepared and the lithium sulfur full battery is assembled for testing, the charging and discharging performance is excellent, and the first discharging specific capacity under the multiplying power of 0.2C can reach 1164.6 mAh/g; after 50 charge-discharge cycles, the discharge specific capacity is still kept at 898.7mAh/g, and the long-cycle stability is excellent.
5) The preparation process is simple and has good universality.
Drawings
FIG. 1 is a FeS prepared according to example 1 of the present inventionx-VS4The X-ray diffraction pattern of the @ material (rGO + CNF);
FIG. 2 is a FeS prepared according to example 1 of the present inventionx-VS4Raman spectra of @ material (rGO + CNF);
FIGS. 3A and 3B show FeS prepared in example 1 of the present inventionx-VS4Scanning electron microscopy images of the @ material (rGO + CNF) at different magnifications;
FIG. 4 is FeS prepared according to example 1 of the present inventionx-VS4A graph of the change of specific discharge capacity along with cycle times is obtained by testing after the @ material bears sulfur;
FIG. 5 is a graph of a film made according to example 2 of the present inventionPrepared FeSx-VS4The X-ray diffraction pattern of the @ material (rGO + CNF);
FIG. 6 is FeS prepared according to example 2 of the present inventionx-VS4Raman spectra of @ material (rGO + CNF);
FIG. 7 is FeS prepared according to example 2 of the present inventionx-VS4Scanning electron microscopy of the @ material (rGO + CNF);
FIG. 8 is FeS prepared according to example 3 of the present inventionx-VS4The X-ray diffraction pattern of the @ material (rGO + CNF);
FIG. 9 is FeS prepared according to example 3 of the present inventionx-VS4Raman spectra of @ material (rGO + CNF);
FIG. 10 is a FeS prepared according to example 3 of the present inventionx-VS4Scanning electron microscopy of the @ material (rGO + CNF).
Detailed Description
Embodiments of the invention are described in further detail below:
the invention discloses a preparation method of a mixed carbon material loaded with composite metal sulfide as a sulfur main body material of a lithium-sulfur battery, which comprises the following steps:
1) slowly adding 12.5-75 mL of concentrated sulfuric acid into 25-37.5 mL of concentrated nitric acid, adding carbon fiber into the strong acid mixed solution, adding 250-1000 mg of carbon fiber into each 37.5-112.5 mL of strong acid mixed solution, and performing reflux reaction for 2-4 h under the condition of an oil bath at 75-85 ℃ to obtain acidified carbon fiber (CNFO).
2) Uniformly mixing 100-110 mg of CNFO obtained in the step 1) with 90-100 mg of graphene oxide powder to obtain the mixed carbon material.
3) 165-185 mgNa3VO4650 mg-750 mg TAA and 100 mg-120 mg CTAB are dissolved in 20 mL-25 mL deionized water in sequence, and a clear solution A is obtained after full stirring; and then adding 190-210 mg of the mixed carbon material prepared in the step 2) into 20-25 mL of the solution A, and stirring uniformly after ultrasonic dispersion to obtain a suspension B.
4) And adding the suspension B into a hydrothermal reaction kettle, sealing, controlling the filling ratio to be 50-60%, then putting the suspension B into an electric constant-temperature air-blast drying oven, carrying out hydrothermal reaction for 22-26 h at the reaction temperature of 155-165 ℃, and obtaining an intermediate after the reaction is finished.
5) Weighing 680-720 mg of FeSO4·7H2Adding O into 45-55 mL of deionized water, and fully stirring and dissolving to obtain a uniform solution C.
6) Adding the intermediate prepared in the step 4) into a mixed solution of 20-30 mL of deionized water and 20-30 mL of absolute ethyl alcohol, adding 100-120 mg of the intermediate into every 40-60 mL of the mixed solution, performing ultrasonic dispersion, and uniformly stirring to form a suspension D.
7) Slowly adding the solution C into the suspension D under the condition of continuous stirring, and then fully stirring for 2-4 h to obtain fully mixed suspension E; and carrying out suction filtration on the suspension E to obtain a wet precursor on filter paper, and then drying the wet precursor at the temperature of 80 ℃ to obtain a dried precursor.
8) Flatly paving the precursor obtained in the step 7) in a corundum square boat, putting the square boat in a tube furnace, heating to 250-350 ℃ at the speed of 3-5 ℃/min in the argon atmosphere, then preserving heat for 1-3 h, cooling to room temperature in the argon atmosphere after the reaction is finished, and finally obtaining FeSx-VS4The host material of the @ lithium sulfur battery sulfur is rGO + CNF.
The present invention is described in further detail below with reference to specific examples:
example 1
1) 75mL of concentrated sulfuric acid was slowly added to 25mL of concentrated nitric acid, 1000mg of carbon fiber was added to the strong acid mixed solution, and then a reflux reaction was performed for 3 hours under an oil bath condition at 80 ℃ to obtain an acidified carbon fiber (CNFO).
2) Uniformly mixing 100mg of the CNFO obtained in step 1) with 100mg of graphene oxide powder to obtain a mixed carbon material.
3) Adding 175mgNa3VO4700mgTAA and 110mgCTAB are dissolved in 22.5mL deionized water in sequence, and a clear solution A is obtained after full stirring; adding 200mg of the mixed carbon material prepared in the step 2) into 22.5mL of the solutionAnd in the step A, uniformly stirring after ultrasonic dispersion to obtain a suspension B.
4) And adding the suspension B into a hydrothermal reaction kettle, sealing, controlling the filling ratio to be 55%, then placing the hydrothermal reaction kettle into an electric constant-temperature air-blast drying oven, carrying out hydrothermal reaction for 24 hours at the reaction temperature of 160 ℃, and obtaining an intermediate after the reaction is finished.
5) 700mg of FeSO are weighed4·7H2And adding O into 50mL of deionized water, and fully stirring and dissolving to obtain a uniform solution C.
6) Adding 110mg of the intermediate prepared in the step 4) into a mixed solution of 25mL of deionized water and 25mL of absolute ethyl alcohol, and uniformly stirring after ultrasonic dispersion to form a suspension D.
7) Slowly adding the solution C to the suspension D under continuous stirring, followed by stirring thoroughly for 3h to obtain a well-mixed suspension E; and carrying out suction filtration on the suspension E to obtain a wet precursor on filter paper, and then drying the wet precursor at the temperature of 80 ℃ to obtain a dried precursor.
8) Flatly paving the precursor obtained in the step 7) in a corundum square boat, putting the square boat in a tube furnace, heating to 300 ℃ at a speed of 4 ℃/min in an argon atmosphere, then preserving heat for 2h, cooling to room temperature in the argon atmosphere after the reaction is finished, and finally obtaining FeSx-VS4The host material of the @ lithium sulfur battery sulfur is rGO + CNF.
To test the electrochemical performance of the sulfur host material of the lithium sulfur battery obtained in this example, a battery was assembled and subjected to electrochemical testing as follows: uniformly mixing the sulfur main material of the lithium-sulfur battery synthesized in the embodiment with sulfur powder according to the mass ratio of 3:7, spreading the obtained mixture powder in a corundum ark, placing the ark in a blast drying oven, heating to 155 ℃ in air atmosphere, then preserving heat for 12 hours, and cooling to room temperature after heat preservation is finished, thereby obtaining FeS loaded with sulfur prepared by a melting diffusion methodx-VS4@ S (rGO + CNF) Sulfur host Material (i.e., S/FeS)x-VS4@ (rGO + CNF) cathode material); then the S/FeS is addedx-VS4The effective mass ratio of the @ (rGO + CNF) anode material to the carbon nano tube, the sodium carboxymethyl cellulose (CMC) and the Styrene Butadiene Rubber (SBR) is 8: 1.5: 0.25:0.25 of the slurry is prepared and coated on the carbon-coated aluminum foil to prepare a positive pole piece; 1.0mol/LLITFSI and 0.1mol/L LiNO dissolved in 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio is 1: 1)3Is an electrolyte; a polypropylene (PP) single-layer film is used as a diaphragm, and the diaphragm is assembled into a CR2032 type button battery in an argon glove box. And performing a multiplying power charge and discharge test at 25 ℃ and within a voltage range of 1.7-2.8V and a multiplying power of 0.2C by using a LAND-CT-2001A test system.
FIG. 1 shows FeS prepared in this examplex-VS4X-ray diffraction pattern of the @ material rGO + CNF. As can be seen from fig. 1, the diffraction peak at 26.2 ° except 2 θ corresponds to the carbon material in the sulfur host material, and all the other diffraction peaks correspond to VS4Corresponding to the PDF standard card (87-0603), it shows that VS exists in the sulfur main body material of the lithium-sulfur battery prepared in the embodiment4。
FIG. 2 shows FeS prepared in this examplex-VS4Raman spectrum of @ material rGO + CNF. As can be seen from FIG. 2, the sulfur host material of the lithium-sulfur battery prepared in this example not only has VS4Also the presence of FeSx。
FIGS. 3A and 3B show FeS prepared in this examplex-VS4Scanning electron microscope images of the sulfur main material of the @ lithium sulfur battery (rGO + CNF) at different magnifications. As can be seen from fig. 3A and 3B, the mixed carbon structure material composed of carbon fibers and graphene has a continuous conductive network which is interwoven with each other, transition metal sulfides are grown in situ on the surface of the mixed carbon structure material, and the distribution is relatively uniform. From the above results, the sulfur host material of the lithium sulfur battery prepared in this example was FeSx-VS4@(rGO+CNF)。
FIG. 4 shows FeS prepared in this examplex-VS4The graph of the specific discharge capacity of the @ material (rGO + CNF) along with the change of the cycle number is obtained through testing after the material carries sulfur by a melting diffusion method. As can be seen from FIG. 4, the FeS prepared in this examplex-VS4After the @ material bears sulfur, the corresponding full battery has excellent charge and discharge performance, the first discharge specific capacity of the material under the multiplying power of 0.2C can reach 1164.6mAh/g, and 50 charge and discharge cycles are carried outAfter the ring is closed, the specific discharge capacity is still maintained at 898.7 mAh/g. Thus, FeS was foundx-VS4The electrochemical performance of the sulfur main body material of the @ lithium sulfur battery (rGO + CNF) is good, and the sulfur main body material has excellent long-cycle stability.
Example 2
1) 12.5mL of concentrated sulfuric acid was slowly added to 37.5mL of concentrated nitric acid, and 250mg of carbon fiber was added to the strong acid mixed solution, followed by reflux reaction at 75 ℃ for 2 hours in an oil bath to obtain acidified carbon fiber (CNFO).
2) Uniformly mixing 110mg of the CNFO obtained in step 1) with 90mg of graphene oxide powder to obtain a mixed carbon material.
3) Adding 165mgNa3VO4650mgTAA and 100mgCTAB are dissolved in 20mL deionized water in sequence, and a clear solution A is obtained after full stirring; then 190mg of the mixed carbon material prepared in step 2) was added to 20mL of the solution a, and the mixture was ultrasonically dispersed and stirred to obtain a suspension B.
4) And adding the suspension B into a hydrothermal reaction kettle, sealing, controlling the filling ratio to be 50%, then placing the suspension B into an electric constant-temperature air-blast drying oven, carrying out hydrothermal reaction for 22h at the reaction temperature of 155 ℃, and obtaining an intermediate after the reaction is finished.
5) 680mg of FeSO are weighed4·7H2And adding O into 45mL of deionized water, and fully stirring and dissolving to obtain a uniform solution C.
6) Adding 100mg of the intermediate prepared in the step 4) into a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring after ultrasonic dispersion to form a suspension D.
7) Slowly adding the solution C to the suspension D under continuous stirring, followed by stirring thoroughly for 2h to obtain a well-mixed suspension E; and carrying out suction filtration on the suspension E to obtain a wet precursor on filter paper, and then drying the wet precursor at the temperature of 80 ℃ to obtain a dried precursor.
8) Spreading the precursor obtained in the step 7) in a corundum square boat, placing the square boat in a tube furnace, heating to 250 ℃ at the speed of 3 ℃/min in an argon atmosphere, then preserving heat for 1h, and after the reaction is finished, keeping the temperature in the argon atmosphereCooling to room temperature to finally obtain FeSx-VS4The host material of the @ lithium sulfur battery sulfur is rGO + CNF.
FIG. 5 shows FeS prepared in this examplex-VS4X-ray diffraction pattern of the @ material rGO + CNF. As can be seen from fig. 5, the diffraction peak at 26.2 ° except 2 θ corresponds to the carbon material in the sulfur host material, and all the other diffraction peaks correspond to VS4The corresponding PDF standard card (87-0603) shows that the sulfur main body material of the lithium-sulfur battery prepared in the embodiment contains VS4。
FIG. 6 shows FeS prepared in this examplex-VS4Raman spectrum of @ material rGO + CNF. As can be seen from fig. 6, iron sulfide (FeS) is also present in the sulfur host material of the lithium sulfur battery prepared in this examplex)。
FIG. 7 shows FeS prepared in this examplex-VS4Scanning electron microscopy of the @ material (rGO + CNF). As can be seen from fig. 7, the mixed carbon structure material composed of carbon fiber and graphene has a stable continuous conductive network, on the surface of which transition metal sulfide is grown in situ and distributed uniformly. From the above results, the sulfur host material of the lithium sulfur battery prepared in this example is FeSx-VS4@(rGO+CNF)。
Example 3
1) 50mL of concentrated sulfuric acid was slowly added to 25mL of concentrated nitric acid, and 750mg of carbon fiber was added to the strong acid mixed solution, followed by a reflux reaction at 85 ℃ for 4 hours in an oil bath to obtain an acidified carbon fiber (CNFO).
2)105mg of the CNFO obtained in step 1) was uniformly mixed with 95mg of graphene oxide powder to obtain a mixed carbon material.
3) 185mgNa3VO4750mgTAA and 120mgCTAB are dissolved in 25mL deionized water in sequence, and a clear solution A is obtained after full stirring; and then adding 210mg of the mixed carbon material prepared in the step 2) into 25mL of the solution A, performing ultrasonic dispersion, and uniformly stirring to obtain a suspension B.
4) And adding the suspension B into a hydrothermal reaction kettle, sealing, controlling the filling ratio to be 60%, then placing the suspension B into an electric constant-temperature air-blast drying oven, carrying out hydrothermal reaction for 26 hours at the reaction temperature of 165 ℃, and obtaining an intermediate after the reaction is finished.
5) 720mg of FeSO are weighed out4·7H2And adding O into 55mL of deionized water, and fully stirring and dissolving to obtain a uniform solution C.
6) 120mg of the intermediate prepared in step 4) was added to a mixed solution of 30mL of deionized water and 30mL of anhydrous ethanol, and stirred for a certain period of time after ultrasonic dispersion to form a suspension D.
7) Slowly adding solution C to suspension D with constant stirring, followed by stirring well for 4h to obtain well-mixed suspension E; carrying out suction filtration on the suspension E to obtain a wet precursor on filter paper, and then drying the wet precursor at the temperature of 80 ℃ to obtain a dried precursor;
8) flatly paving the precursor obtained in the step 7) in a corundum square boat, putting the square boat in a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min in an argon atmosphere, then preserving heat for 3h, cooling to room temperature in the argon atmosphere after the reaction is finished, and finally obtaining FeSx-VS4The host material of the @ lithium sulfur battery sulfur is rGO + CNF.
FIG. 8 shows FeS prepared in this examplex-VS4X-ray diffraction pattern of the @ material rGO + CNF. As can be seen from fig. 8, the diffraction peak at 26.2 ° except 2 θ corresponds to the carbon material in the sulfur host material, and all the other diffraction peaks correspond to VS4The corresponding PDF standard card (87-0603) shows that the sulfur main body material of the lithium-sulfur battery prepared in the embodiment also contains VS4。
FIG. 9 shows FeS prepared in this examplex-VS4Raman spectrum of @ material rGO + CNF. As can be seen from FIG. 9, the sulfur host material for the lithium-sulfur battery prepared in this example contains VS4While also containing FeSx。
FIG. 10 shows FeS prepared in this examplex-VS4Scanning electron microscopy of the @ material (rGO + CNF). As can be seen from FIG. 10, the mixed carbon structure material composed of carbon fiber and graphene has a stable continuous conductive network, on the surface of which a more uniformly distributed in-situ growth is also performedA transition metal sulfide. From the above results, it can be seen that the sulfur host material for the lithium-sulfur battery prepared in this example is also FeSx-VS4@(rGO+CNF)。
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a composite metal sulfide-loaded mixed carbon material serving as a sulfur main body material of a lithium-sulfur battery is characterized by comprising the following steps of:
1) slowly adding concentrated sulfuric acid into concentrated nitric acid to obtain a strong acid mixed solution; adding carbon fibers into the strong acid mixed solution, and performing reflux reaction under the condition of an oil bath to obtain carbon fiber CNFO subjected to acidification treatment;
2) uniformly mixing the CNFO obtained in the step 1) with graphene oxide powder to obtain a mixed carbon material;
3) mixing Na3VO4Sequentially dissolving TAA and CTAB in deionized water, and fully stirring to obtain a clear solution A; adding the mixed carbon material prepared in the step 2) into the solution A, and uniformly stirring after ultrasonic dispersion to obtain a suspension B;
4) carrying out hydrothermal reaction on the suspension B, and obtaining an intermediate after the reaction is finished;
5) weighing a certain amount of FeSO4·7H2Adding O into deionized water, and fully stirring and dissolving to obtain a uniform solution C;
6) adding the intermediate prepared in the step 4) into a mixed solution of deionized water and absolute ethyl alcohol, and uniformly stirring after ultrasonic dispersion to form a suspension D;
7) slowly adding the solution C into the suspension D under the condition of continuous stirring, and then fully stirring to obtain a suspension E; carrying out suction filtration on the suspension E to obtain a wet precursor on filter paper, and then drying to obtain a dry precursor;
8) spreading the precursor obtained in the step 7) in a corundum ark,placing the ark in a tubular furnace, heating up and reacting in argon atmosphere, cooling to room temperature in argon atmosphere after reaction is finished, and obtaining the carbon fiber and graphene mixed carbon material loaded with the iron sulfide and vanadium tetrasulfide composite metal sulfide as the main sulfur material of the lithium-sulfur battery, and recording the carbon fiber and graphene mixed carbon material as FeSx-VS4@(rGO+CNF)。
2. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 1), 25mL to 37.5mL of concentrated nitric acid is added into every 12.5mL to 75mL of concentrated sulfuric acid, 250mg to 1000mg of carbon fiber is added into every 37.5mL to 112.5mL of strong acid mixed solution, the temperature of reflux reaction is controlled to be 75 ℃ to 85 ℃, and the reaction time is controlled to be 2h to 4 h.
3. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 2), the mass ratio of the graphene oxide powder to the CNFO is 90 mg-100 mg: 100mg to 110 mg.
4. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 3), 165-185 mg of Na is added into each 20-25 mL of deionized water3VO4650-750 mg of TAA and 100-120 mg of CTAB, and 190-210 mg of the mixed carbon material is added into every 20-25 mL of the solution A.
5. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: step 4), the hydrothermal reaction is specifically as follows: adding the suspension B into a hydrothermal reaction kettle, sealing, controlling the filling ratio to be 50-60%, placing into an electric constant-temperature air-blast drying oven, controlling the reaction temperature to be 155-165 ℃ and controlling the reaction time to be 22-26 h.
6. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 5), 680 mg-720 mg of FeSO is added into every 45 mL-55 mL of deionized water4·7H2O。
7. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 6), 20mL to 30mL of absolute ethyl alcohol is added into every 20mL to 30mL of deionized water, and 100mg to 120mg of intermediate is added into every 40mL to 60mL of mixed solution.
8. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 7), the solution C is slowly added into the suspension D, the stirring time is 2-4 h, and the temperature for drying the wet precursor is 80 ℃.
9. The method for producing a composite metal sulfide-loaded mixed carbon material as a sulfur host material for a lithium sulfur battery according to claim 1, wherein: in the step 8), the temperature rise reaction is carried out at the temperature rise rate of 3-5 ℃/min to 250-350 ℃, and the heat preservation treatment is carried out for 1-3 h.
10. A mixed carbon material carrying a composite metal sulfide, which is obtained by the production method according to any one of claims 1 to 9.
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